to. t r.

q,3

SYNTHESIS AND CHARACTERIZATION OF

TRTORGANOPHOSPHTNEGOLD (I)

THIOLATES

by

PETER D. COOKSON B.Sc. (Hons)

Thesis submitted for the degree of

Master of Science
in
The Deparrnent of Chemistry
of the
University of Adelaide

June, 1993

Áworded tqq+
Additional References for Chapter 1.

B.M. Sutton, Gold Bull.,19, 15 (1986).

R.V. Parish and S.M. Cottrill, GoId 8u11.,20,3 (1987).
'Walz, | (1982).
A.J. Lewis and D.T. Prog. Med. Chem.,19,

R. Koch, Deut. Med. Wochenschr.,16,756 (1890).

C. Bruck and A. Glück, Muenchen. Med. Wochenschr.,60,57 (1913).

F. Junker, Muenchen. Med. Wochenschr.,60, 1376 (1913).

K. Landé, Muenchen. Med. Wochenschr.,74,ll32 (1927).

I. Haiduc and C. Silvestnr, Coord. Chem. Rev.,99,253 (1990).

B.M. Sutton, E. McGusty, D.T. Walz and M.J. DiMartino, J. Med. Chem.,15, 1095 (1972).

G.G. Graham, J.R. Bales, M.C. Grooweld and P.J. Sadler, J. Inorg. Biochem.,25, 163 (1985).

G.G. Graham, T.M. Haavisto, H.M. Jones and G.D. Champion, Biochem. Pharmacol.,33, 1257

(1e84).

T. Stelmaszynska and J.M. Zgliczynski,inCyanide inBiology, Academic Press, pg37I (1981).

D.R. Haynes and M.W. rWhitehouse, in New Developments in Antirheumatic Therapy, K.D.
Rainsford and G.P. Velo @ds.),Inflammation and Drug Therapy Series, Vol. [II, pg2o7 (1989).

Amended version of Table 4.4.2.

Complex ¡12 g9 ¡18 Phenyl Protons Ha H6

6-MPH 8.a5(s) 13.62(br,s) 8.26(s)

[dppm(Au(6-MP))z] 8.36(s) 13.12(br,s) 8.17(s) 7.95 - 7.37(br,m) 4.64(m)

[dppe(AuClXAu(6-MP)] 8.36(s) 13.25(br,s) 8.09(s) 7.87 - 7.47(br,m) 3.02(m)

[dppe(Au(6-MP))z] 8.37(s) 13.13(br,s) 8.2a(s) 7.89 - 7.49(br,m) 3.0a(m)

[dppp (AuClXAu(6-MP))] 8.40(s) 13.22(br,s) 8.20(s) 7.74 - 7.50(br,m) 3.07(m) 1.73(m)

[dppp(Au(6-MP))z] 8.38(s) 13.18(br,s) 8.19(s) 7.83 - 7.42(br,m) 3.16(m) 1.89(m)

Note: Coupling constants, in parentheses, are in units of Hertz: a: 3J¡1-¡¡, b: 3Jp-g and c: Zlp-¡g'.
 ll

DECLARATION

This work contains no material which has been accepted for the awa¡d of any other degree or

diploma in any university or other institution and, to the best of my knowledge and belief,

contains no material previously published or written by another person, except where due

reference has been made in the text.

I give consent to this copy of my thesis, when deposited in the University Library, being

available for photocopying and loan.

SIGNED DATE: T5 ø
 lll

ACKNOWLEDGEMENTS

I would firstly like to thank all the members of Dr. Tiekink's group for their help and
companionship throughout my degree: George Siasios, for his assistance in academic and

practical matters, for his friendship and involvement in so many things; John Faamau, Veronica

Hall, Andrea Collins and Jason Valentine for their friendship and help; and who can forget

Randell Taylor, for adding a certain spice to life to an otherwise conservative working
environment.

In addition to those above, I would also like to extend my special appreciation to all the friends

I have made over the past few years: Ramesh Dhillon, Sarah Rankin, Sonya and Reina

Whitbread, Neil Donoghue, Mark'Chuck'Dallerup, Steven Andrew and Andrew Bevan, for

accepting me into their lives.

Thank you to Peter Schultz, Gary Owens and all those other people who assisted in the

compilation of this thesis, and to Dr. M.W. Whitehouse for the anti-arthritic testing of the

complexes.

My family, be they gone or still with us, deserves to be commended for putting up with me

for all these years, and for giving me full support in this degree through thick and thin and

throughout all my doubts.

Thanks also to other personnel, whose services have been invaluable: Phil Clements for help

with the NMR studies; Tom Blumenthal and George Siasios for FAB mass spectra; and all the
general staff for those little problems that arose.

Finally, to Dr. E.R.T. Tiekink, whose encouragement, advice, companionship and guidance

is just a sample of the many things he has been there for, and without whose help I simply

would not have hnished.

 1V

ABSTRACT

The aim of this work was to synthesize a range of novel triorganophosphinegold(I)

6-mercaptopurinate complexes and to evaluate their potential anti-arthritic activity. The resultant

complexes are based on the P-Au-S moiety, structurally related to the widely available

pharmaceutical Auranofin, where the phosphorus atom is part of a triethylphosphine ligand and

the sulphur atom derived from a tetraacetylated thioglucose anion.

Via alteration of the identity of the triorganophosphine group, a variety of complexes were

synthesized from triorganophosphinegold(I) chloride precursors, falling into three main types:

1) triorganophosphinegold(I) 6-mercaptopurinate complexes with the general formula

[R3PAu(6-MP)], where R3P = Et3P, Cycl3P, PhMe2P, Ph3P, (o-Tol)3P, (lz-Tol)3P or

(p-Tol)¡P; 2) [p-1,n-bis(diphenylphosphino)alkane]gold(I) ctrloride gold(I) 6-mercaptopurinate

complexes with the general formula [(PhzP(CHz)nPPhzXAuClXAu(6-MP))] where n= 2 or 3:

and 3) [¡r-1,n-bis(diphenylphosphino)alkane]bis(gold(I) 6-mercaptopurinate) complexes with

the general formula [(PhzP(CH2)¡PPh2)(Au(6-MP))2] where n = l, 2 or 3. These complexes

and the triorganophosphinegold(I) chloride precursors were characteized using multinuclear

magnetic resonance, infrared and Fast Atom Bombardment mass specftoscopic techniques.

Unambiguous structure determinations of a selection of the complexes were achieved by single

crystal X-ray crystallographic methods. Unit cell dimensions were: [PhMezPAuCl],

orthorhombic space group PZpQt, a = 12.639(4), b= 16.931(6), c= 9.458(3) Å,

V= 2024(1) Å3 and,Z = 4; [PhgPAu(6-MP)].CzHsOH, triclinic space group P1,

a = 11.066(3), b = 13.552(3), c = 8.705(2) Ã, o=9I.51(2), þ = 113.06(2), y = 89-69(2)",

V = 1200.8(5) Å3 and,Z =2; and [(o-Tol)¡PAu(6-MP)].C2H5OH, monoclinic space group

PLln, a = 10.067(2),b = 10.518(2), c =25.416(4) Ã, P =98.42(2)",V =2662.1(9) Å3 and
Z = 4. The structures were refined to final R values of 0.035, 0.034 and 0.040, respectively,

for reflections satisfying the 1> 3.0o(1) critenon: 1608, 3978 anci 4183, respectiveiy. The

results for [PhMe2PAuCll were utilized, in part, for a cone-angle to bond length correlation
 v

study on triorganophosphinegold(I) chloride complexes. The structures of [Ph3PAu(6-MP)]

and [(o-Tol)3PAu(6-MP)] revealed a near linear P-Au-S chromophore, with angles of

173.7I(6) and I77.03(8)", respectively.A crystal structure analysis of a closely related
triorganophosphinegold(I) thiotate complex, [Cycl3PAu(6p2-TU)], revealed a similar P-Au-S

chromophore with an angle of fi7.6(l)'. Unit cell dimensions were: monoclinic space group

P2lc,a=9.539(2),b = 16.452(4), c = 16.880Q) Ã, þ=95.37(2)",V =2637.4(8¡ Ã3 andZ

= 4. The final refinement value was R = 0.043, for 3695 reflections with 1> 3.0o(/). The
results for the three thiolate complexes were utilized in a correlation study of cone-angles to

intramolecular parameters for triorganophosphinegold(I) thiolate complexes in general.

The combined microanalytical, spectroscopic and crystallographic studies verified the

formation of all the thionucleobase complexes mentioned above and demonsrated that the gold

centre is linearly bound to both the phosphorus and sulphur atoms.

A number of the triorganophosphinegold(I) 6-mercaptopurinate complexes were tested for

thei¡ anti-arthritic activity in Dark Agouti rats with promising results.
 vl

ABBREVIATIONS

,A Angström

br broad
.C degree Celsius

13C N/MK carbon-l3 nuclear magnetic resonance

Cycl cyclohexyl

d doublet

dd, dm, dt doublet of doublets, multiplets, triplets

dec. decomposition point

dppe p- 1,2-bis(diphenylphosphino)ethane

dpp- ¡r -bi s (diphenylphosphino)methane

dppp ¡r - 1,3-bis(diphenylphosphino)propane

Et ethyl

FAB-MS Fast Atom Bombardment - mass spectroscopy

(r
Þ $am
ts NM?. proton nuclear magnetic resonance

Hz her:ø

IR, ir infrared spectroscopy

*JAg coupling constant benveen nuclei A and B over x bonds

m multiplet (nmr)

m medium (ir)

M molar (mol dm-3¡

[M]+ molecular ion

2mbaH 2-mercp atobenzoic acid

6m2-TUH 6-methyl-2-thiouracil

Me methyl

MFIz mega-hertz
 vll
rnl millilitre

mmol millimole

m.p. melting point

6-MPH 6-mercaptopurine

lvI\M molecular weight

m/z mass to charge ratio

6p2-TUH 6-n-propyl-2-thiouracil

NMR, nmr nuclear magnetic resonance (Fourier Transform)

N.O. not observed

Obs. obscured

¡tp ¡lMR phosphorus-3 1 nuclear magnetic resonance

Ph phenyl

Pho phenoxy

ppm parts per million

q quartet

S singlet (nmr)

s strong (ir)

sh shoulder

t tiplet
TMS tetramethylsilane

m-Tol ' rrcta-to\yl

o-Tol ortho-tolyl

p-Tol para-tolyl

2-TUH 2-thiouracil

VS very strong

w weak

VoY percentage yield

6(A-B) bending frequency of A-B bond

}\ wavelength

v(A-B) sretching frequency of A-B bond

 vlll

TABLE OF CONTENTS

Declaration ll

Acknowledgements iü

Abstract iv

Abbreviations vi

Table of Contents viü

Chapter 1: Introduction 1

1.1 Introduction 1

t.2 History of gold in medicine J

1.3 Modern applications of gold in medicine 4

1.4 Arthritis and treatnent with gold complexes 5

1.5 Recent advances in ttre treaunent of rheumatoid arthritis

by triorganophosphinegold(I) thiolates 1

1.6 The chemisry of gold and triorganophosphinegold(I) thiolates 9

t.7 Discussion of results 10

Chapter 2: Experimental T2

2.r Introduction t2

2.2 Preparation of the complexes T2

2.3 Instrumentation 16

2.4 Chemicals t9

2.5 CÞystallography : Instrumentation and methods t9

 lx

Chapter 3: Characterization of Triorganophosphinegold(I) Chloride and

[p-1,n-bis(diphenylphosphino)alkane]bis(gold(I) chloride)
Complexes 22

3.1 Introduction 22

3.2 Spectral characterization of the triorganophosphinegold(I) chloride

complexes 23

3.2.1 Infrared spectroscopy 23

3.2.2 lH NtVtR specEoscopy 25

3.2.3 l3C {lH) NMRspecrroscopy 28

3.3 Crystal structure determination of the [PhMe2PAuCl] complex 30

3.4 Cone-anglecorrelation for triorganophosphinegold(I) chloride

complexes JJ

Chapter 4: Spectroscopic Characterization of the Triorganophosphine'

gotd(I) d-mercaptopurinate Complexes 38

4.1 Introduction 38

4.2 An overview of the 6-mercaptopurine ligand 38

4.3 Infra¡edspectroscopy 40

4.4 lH NMR spectoscopy 44

4.5 t3ç 1tg¡ NMR spectroscopy 4l

4.6 3tP 1t¡¡¡ NMR specrroscopy 49

4.7 Fast Atom Bombardment mass spectroscopy 50

Chapter 5: Crystallographic Investigations of the Complexes

[PhsPAu (6-MP)].C2H 5OH and [(o'Tot)¡PAu (6 -MP) ]. C zH 50 H 53

5.1 Introduction 53

5.2 Crystal structure of [Ph3PAu(GMP)].CzH5OH 53

5.3 Crystal structureof [(o-Tol)3PAu(6-MP)].CzHsOH 56

5.4 Comparison between the 6-mercaptopurine moiety in the free

ligand and in the complexes 58

 X

Chapter 6: Crystallographic Investigations of Triorganophosphinegold(I)

Thiolates 63

6.1 Introduction 63

6.2 Crystal structure of the [Cycl3PAu(6p2-TU)] complex 63

6.3 Cone-angle correlation for triorganophosphinegold(I) thiolates 67

Chapter 7: Assessment of Anti-Arthritic Activity 70

Chapter 8: Conclusion 74

References

Appendix: Structure Factor Tables

 CHAPTER 1

Introduction

I.l Introduction

Interest in gold(I) compounds has increased in recent years due to the growing importance of

certain gold(I) complexes in the treatment of a variety of common ailments. The most well

known use of gold compounds in medicine is in the treatment of rheumatoid arthritis, where

commercially available drugs are now utilized widely. The compound known as Myochrysine,

shown in Figure 1.1, is the lead compound for the treatment of rheumatoid arthritis. Another

gold(I) thiolate compound, Auranofin, has been found to be effective in the treatment of both

rheumatoid arthritis and cancerous tumoursl,2, while other less well known compounds, such

as Solganal, Allochrysine and Sanocrisin (Figure 1.1), are also in curent use against

rheumatoid arthritis. Whereas Auranofin displays some anti-tumour activityl,2, the compound

Uis[¡(t,Z-Ais(diphenylphosphino)ethane]gotd(I) chloride has shown more promising results in

the treatment of cancer3. However, these are only a few examples of how gold plays a useful

role in medicine. In fact, gold has a long history of medicinal applications. This chapter will

discuss the history of gold compounds in medicine, and the use of modern day gold

compounds, especially the class of compounds known as phosphinegold(I) thiolates, in the

trearmenr of rheumatoid arthritis. The chemistry of gold and the triorganophosphinegold(I)

thiolate complexes will be introduced, and how the spectroscopic and crystallographic
characterizations of a selection of new triorganophosphinegold(I) thiolates is of interest to this

field will be discussed.

 2

2-

Au-S
r-" u

-CH
I
CH"
l"
c00
OH
n n

Myochrysine Solganal

o 3-
lto
_ /s -o
S Au_S
/
\o
Sanocrisin

Au-S CIìz
- t-
-CH -CHz-SO¡-
OH
n

Alloctrrysine

o
S Au
- -P(C2H5)3
OAc
AcO

Auranofin

Figure l.L: Structures Of Some Biologically Active Gold(l) Thiolates

 J

1.2 History of gold in medicine

The use of gold in medicine dates back to ancient times. As early as 2500 8.C., Chinese and

Arabic physicians were reported to have used gold preparations, whilst Pliny in the lst century

recorded that gold could be used successfully in the cures of such ailments as haemorrhoids,

warts and fistulas4,S. These early remedies were based on concoctions using metallic gold, and

usually associated with ceremonial incantations. Gold was considered a substance of the gods,

a holy metal that possessed magical properties: meso-American Indians saw gold as the'sweat

of the sun'; and the Egyptian pharaohs and priests considered it a giver of life, a connection

between this world and the next4,5. The rarity of gold and its consequent availability to only the

rich and the religious only promoted the superstitious aura sulrounding the metal. In reality, the

chemical inertness of metallic gold meant that it was probably quite inactive in the internal

biochemistry of those who used it. Hence any cures that might have resulted could in a large

part have been of a purely psychological nature.

In the Middle Ages, gold began to be utilized in a less superstitious manner. While metallic

gold was still being used to gild medicinal tablets, and royalty drank wine from gold coated

vessels as a tasteful way of consuming the metal, the 'science' of alchemy was coming to the

fore. In the 13th century, Geber reported the preparation of the substance aqua regía from a

combination of mineral acids, now known to be nitric and hydrochloric acids, having the ability

to dissolve golds. This was an important discovery, as actual compounds of gold could at last

be prepared. However, physicians of the Renaissance expressed little interest in doing so, since

the purity of metallic gold was still considered to be the most important factor in the curative

properties of the metals.

The first significant compound to be prepared after this time was the 'muriate of gold and

soda', Na[AuCl¿]5. The French physician Chrestien in 1811 described this compound as being

an effective treatrnent for syphilis and chronic alcoholism: it is still recognized today as having

legitimate effect against at least the former5. The advances in medical and scientihc knowledge
 4
around this period ma¡k the beginning of modern medicine, and serious investigations into the

medicinal applications of gold compounds began.

1.3 Modern applicatíons of gold in medicine

The beginning of the role of gold in modern medicine began with the discovery early this

century of the effectiveness of aurothioglucose in treating rheumatic fevers. Tuberculosis and

rheumatoid arthritis were also found to be combatted to some extent by gotd compoundss.

Despite the promising results that emerged, concerns about the toxicity and side-effects of these

compounds, which were usually manifested as kidney and liver problems, to a large extent

discouraged further investigations in this context5. It was the almost accidental discovery of the

in vitro anti-cancer activity of the platinum based drug cisplatin6 (a square planar PI(II)
complex: cis-diaminodichloroplatinum), shown in Figure 1.3, that renewed interest in the

possible medicinal usefulness of platinum group metals, and hence research into gold based

drugs gained new momentum.

H¡N CI

ft
/\ CI
H¡N

Figure L.3: Cisplatin

Perhaps the most significant gold compound found to date is Auranofin, discovered in 1972,
which is useful in the treatment of rheumatoid arthritis2. Recent unpublished results from

research conducted in the Department of Chemistry at Adelaide, concentrating on the effect of

triorganophosphinegold(I) thionucleobase complexes on rheumatoid a¡thritis, stems from the

success of Auranofin. The project embodied in this thesis is concerned with the characterization

of certain triorganophosphinegold(I) thiolate complexes which may also prove to be active

against this ailment.

 5

L.4 Arthritis and treatment with gold complexes

The debilitating disease of rheumatoid arthritis is characterizd,by the chronic inflammation of

joint tissue about the skeletal connections in the body, and usually leads with time to the
disintegration of bone structure in these regions, crippling the sufferer. The biochemical cause

for the onset of the disease is still unclear, but the effects can be neutralized in part by the
suppression of the inflammatory action. One physical answer is to apply pressure to the region,

especially during periods of rest, when swelling of the synovial fluid due to inflammation is at

its greatest. The biochemical approach is by application of certain drugs, although the precise

biochemical reactions that make such drugs effective are not known.

The field known as chrysotherapy has hence developed, which is generally def,rned as the

treatment of rheumatoid arthritis with gold-based drugs4. Of these drugs, the gold compounds

depicted in Figure 1.1 have dominated the treatment of this disease. Two classes of compounds

are represented: the polymeric type, such as Solganal (gold sodium thiosulphate), Myochrysine

(sodium aurothiomalate), Allochrysine (gold sodium thiopropanol sulphonate) and Sanocrisin

(gold sodium thiosulphate), and the monomeric type, such as Auranofin (S-2,3,4,5-tetraacetyl-

1-p-D-thioglucose(triethylphosphine)gold(I)). The administration of these two classes of

compounds is determined by their solubilities in bodily fluids: the polymeric compounds are

hydrophilic and are thus injected intravenously, while the monomeric species Auranofin is

lipophilic, and can be administered orallyl. In tenns of ease and expense of application, the

orally administered Auranofin has been found to be the popular compound for routine use.

The difference in solubility and application method might suggest different modes of action for

the two classes of compounds. As has been mentioned above, the exact biochemical reactions

involved to combat the symptoms of rheumatoid arthritis are not known. A few hypotheses

exist, however, as to how the compounds are delivered to the site of inflammation. The
polymeric complexes all feature Au-S bonds, and studies on the activity of Myochrysine have

revealed that this bond is cleaved in the blood stream in order to create another Au-S bond

between the gold and the thiol group of cysteine-34 of a plasma protein albuminl'7. The
 6

resultant auroalbumin complex may then undergo ligand exchange to form a dimeric species,

which is then ingested by certain immunological macrophages to be transported to the site of

disease. Reactive leukocytes at the sites of inflammation have the ability to produce cyanide

from glycine, which reacts with gold(I) to form a [Au(CN)2]- species, thus concentrating gold

in this region. The [Au(CN)2]- anion can permeate many types of cell membrane, possibly then

interfering with DNA-based functions which lead to the production of inflammatory fluids.

A dose of Auranofin, however, consists of discrete molecules, and the interaction of

Auranofin with the albumin protein is likely to be different. Auranofin can be classed as a

triorganophosphinegold(I) thiolate: while clinical trials on gold(I) thiolates have proven to be

ineffective via oral administrationT, a phosphine group bound to the gold imparts lipid solubility

to the complexes, allowing this mode of administration. It is possible for either the phosphine

or thiolate group to be cleaved from Auranofin on reaction with albumin. However, the thiolate

group seems to be the more labile, and initial binding to the albumin appears to occur via loss of

thiolatel. The phosphine group can be substituted for another thiol molecule accompanied by

oxidation of the phosphine, and the gold centre then becomes doubly coordinated by sulphur

atoms, and is thus carried to the site of inflammation. The final fate of the gold is hence the

same for both polymeric and monomeric compounds, the main differences in activity being due

to the initial mode of transportation in the body. This is possibly related to the solubilities of the

moleculesS.

In finding other compounds that might be useful in this held, it is necessary to alter the
structure of the present compounds in order to obtain complexes of differing solubilities (if we

wish to work on the same hypothesis concerning their initial metabolism). The polymeric

molecules are restricted in their chemical composition by the ability to form a polymer.
Monomeric compounds, however, are neutral and discrete, and the structures of the phosphine

and thiolate moieties can potentially be altered to achieve a desired measure of solubility for an

orally ingested drug.

 7
1.5 Recent advances in the treatment of rheumatoid arthritis by triorganophosphinegold(I)

thiolates

Previous work, published and unpublished, has been performed on other compounds

analogous to those appearing in this thesis. The utilization of thionucleobases as the thiolate

component is a choice that can be based on toxicity; the biological system contains many

examples of nucleobases, the most well known being those associated with the macromolecules

RNA and DNA. 2-thiouracil (2TUH), the thio analogue of uracil, bound to gold in the complex

2-thiouracilato(triphenylphosphine)gold(I), Figure 1.5.1, has been tested for anti-arthritic

activity in a model rat strain and found to be comparable with Auranofin9. Other pyrimidine-

and purine-based gold(I) phosphines have also been tested in a studylO which yielded an

interesting general result. The best phosphine found in terms of the activity of the resultant

gold(I) complex was triphenylphosphine; the triethylphosphine analogues, e.g. Figure 1.5.2,

were found to be ineffective and even toxic in some cases. This contrasts with Auranofin,

which is active and contains a Et3P group. Such an anomalous result goes against any

structure-activity correlation that might have been forthcoming from the study.

P-Au-S
NH
o
N

Fi gure 1.5. 1 : 2 - thi o ur aci lat o ( t rip he ny Ip ho sp hi ne ) g o Id( I )

The most effective thionucleobase of those tested was found to be 6-mercaptopurine, with the

complex 6-mercaptopurinato(triphenylphosphine)gold(I), [PhgPAu(6-MP)], shown in Figure

'l 5 ? heino evên rrìôre a¿-tir¡c qsqinct thc rliccqca thqn Ärrrqnnfin Thic ¿-nrnnnnnrl hes alre¡rlv
*" ---J

been noted in the literature as having signihcant antineoplastic activity against leukemia in
 8

H¡C-.
CHz
\
.nlf-o"
,/
H¡C c:r,l"t"", o
N

Fi gure 1.5.22 2 - t hio ur ac iI ato ( tr ie t hy Ip ho s p hi n e ) e o I d ( I )

micell. 6-mercaptopurine (6-MPH) itself has been reported as possessing chemotherapeutic

activity, notably in the treatment of leukemiur2, and its complexes have shown anti-tumor

activity e.g. Cu(IX6-MPH)CI2 and Cd(6-MPH)+Clztz. Other uses found have been for the
inhibitory action by ribonucleoside analogues on de novo puine biosynthesisl4, and against

such conditions as urate microcrystal arthritis in poultryl5. The compound

(8-thiotheophyllinato)(triphenylphosphine)gold(I), a structural variant of [Ph3PAu(6-MP)], has

also been effective in the treaünent of arthritis, leukemia and cancerous tumoursl6'17.

P-Au-S
N

N
(_ N
NH

Figure 1.5.3: 6 -mercaptopurinato( triphenylp hos p hine ) gold( I )

The choice of thiolate for all the complexes prepared in this thesis was thus chosen to be

6-mercaptopurine, and the phosphines chosen were: Et3P, Cycl3P, PhMe2P, Ph3P, (o-Tol)3P,

(llr-Tol)3P and (p-Tol)¡P, to give complexes of the type [R3PAu(6-MP)]; and

¡/-UisqAipnenylphosphino)methan
el, y/-t,Z-Ais(diphenylphosphino)ethanel ana yLl.,3-bis(di-
 9

phenylphosphino)propanel, to give mono- and di-substituted compounds of the type shown

schematically in Figure I.5.4.

P _(cHÐ"_
I
Au Au
I
X S

N
N

Figure 1.5.4: Diagram For Mono- And Di-substituted Complexes.

n = 1,2 or 3;X = Cl For Mono-sttbstituted,X = 6-MP For Di-sttbstituted

l.6The chemistry of gold and triorganoplnsphinesold(I) thiolates

Gold can exist in a variety of oxidation states, but it is dominated in its chemistry by the two

most stable srates, I and III18. Gold(IID has the electronic configuration lXel4f145d8, and is

thus isoelecronic with platinum(Il). This would suggest that gold(Itr) complexes analogous to

cisplatin might have comparable anti-tumour activity. Some complexes have proven activel, but

the reducing mammalian environment tends to reduce the gold(Itr) cornplexes, and so they have

not been found to be generally effective. Gold(I), with the stable 'filled shell' electronic

configuration of LXel4¡ll5¿10, is thus better suited to the body's biochemistry, a fact which is

illustrared by the variety of anti-arthritic gold(I) compounds already mentioned.

Both gold(trI) and gold(I) are soft metal ions, with gold(I) more so, and these ions prefer to

bind to soft donor atoms such as sulphur and phosphorus. Vy'hereas a 'naked' gold(I) ion

would be transmuted to gold(0) and gold(III) in the body, a gold(I) atom stabilized by sulphur

will be less susceptible to oxidation and reduction. The phosphorus of the phosphine ligand is a

o-electron donor, and is also thought to be a r-electron acceptor from the 5d10 orbital of the

gold(I) atom. Thus, both sulphur and phosphorus help to stabilize the gold(I) species.
 10

Triorganophosphinegold(I) thiolates possess certain structural characteristics. Thiolate groups

containing one exocyclic sulphur tend to coordinate in a monodentate mode via the sulphur

atom to the gold centre. Other possible coordinating atoms or functional groups of the thiolate

can associate with the gold but only through secondary interactions. One common feature is the

tendency of nitrogen-containing thiolates to orient themselves in the crystal lanice such that the

nitrogen is in close proximity to the gold centre. The intramolecular distance is invariably less

than the sum of the van der Waals radü. The main feature of these complexes is the presence of
a P-Au-S chromophore, found from crystallographic studies to be nea¡ linear in most examples

regardless as to the identity of the phosphine or thiolate. These structural characteristics were

looked for in the crystal structures reported in this thesis, and how they compare to other

gold(I) thiolate complexes.

The compounds studied in this thesis were prepared via an established method, involving first

the synthesis of a triorganophosphinegold(I) chloride precursor. This is detailed in Chapter 2;

briefly, the procedure involved the reduction of an aqueous gold(Ilf chloride solution, by

using thiodiglycol, to give an aqueous gold(I) species, which was then reacted in situ with the

stoichiometric amount of the desired phosphine. The resultant air-stable triorgano-

phosphinegold(I) chloride was then reacted in an equimolar, metathetical reaction with
6-mercaptopurine in the presence of a base.

L.7 Discussion of results

The focus of this thesis is on the preparation, spectroscopic characterization and, where

appropriate, X-ray crystal structure determination, of series of complexes with the general

formulae of [R3PAu(6-MP)] (where R3P = Et3P, Cycl3P, PhMe2P, Ph3P, (o-Tol)3P,

(m-Tol)¡P or (p-Tol)3P), [(PhzP(CHz)nPPhzXAuCl)(Au(6-MP))] (where n = 2 or 3), and

[(PhzP(CHz)nPPhzXAu(6-MP))z] (where n = l, 2 or 3).

The thesis is divided into three main sections. The fust is the experimental section, in which

the preparative methods employed will be detailed, along with the instrumentation used. The
next two sections are devoted to the spectral characterization of the complexes prepared and of
 11

the triorganophosphinegold(I) chloride precursors that were involved. As little information

exists in the literature regarding the characterizations of triorganophosphinegold(I) chlorides,

this data has been collected here. The X-ray crystal structure of [PhMe2PAuCl] is presented,

followed by a study to find a possible correlation between the phosphine cone-angle and the

Au-Cl bond length in triorganophosphinegold(I) chloride complexes. The effects on the

6-mercaptopurine moiety upon complexation to gold are deduced from spectroscopic and

crystallographic analyses. The methods utilized were Fast Atom Bombardment mass

spectrometry, 1¡¡, 136 and 3lP nuclear magnetic resonance spectroscopy and Fourier
Transform infrared spectroscopy. X-ray crystallographic techniques were performed on two

complexes, [Ph3PAu(6-MP)].C2H5OH and [(o-Tol)3PAu(6-MP)].C2H5OH, in order to

confirm the precise nature of the products and to determine what effect the Au-S coordination

has on the electronic structure of the 6-mercaptopurinate moiety.

The X-ray crystal structure determination of the complex 6-n-propyl-2-

thiouracilato(tricyclohexylphosphine)gold(I), ICycl3PAu(6p2-TU)], is given, which, along
with data from a variety of other triorganophosphinegold(I) thiolates, is utilized in a cone-angle

correlation to determine the effect of the phosphine ligand on the P-Au-S chromophore.

A selection of the complexes prepared were for their anti-arthritic activity using the
assessed
oF
commercially available drugs as standards. The resultsthese tests are given, where available,

with comments on the possible structure / activity correlations. The conclusion summarizes

what the characterizations and crystallographic analyses have revealed about the new

complexes.
 CHAPTER 2

Experimental

2.1Introduction

This chapter comprises three main sections: 1) a description of the experimental methods used

in the prepararions of the triorganophosphinegold(I) chloride and 6-mercaptopurinate

complexes, including the melting points, yields and microanalytical data - examples for the

prepararion of [Ph3PAuCl] and [Ph3PAu(6-MP)] are given; 2)bnef notes on the reagents and

the instrumentation used for the characterizations; and 3) a general discussion of the
instrumentation used and the methods employed in solving the crystal structures detailed in later

chapters via an example, namely [(o-Tol)¡PAu(6-MP)]. C2H5OH.

2.2 Preparation of the complexes

The preparation of all the complexes was based on a procedure adapted from ref. [19] for the

prepararion of the compound 2-thiouracilato(triphenylphosphine)gold(I). The procedure

involved the equimolar metathetical reaction between triphenylphosphinegold(I) chloride and

2-thiouracil in the presence of a base in an ethanolic solution. This reaction has since been

found to be generally applicable for the preparation of analogous complexes containing a variety

of phosphines and thionucleobasesl0, and so was utilized to prepare the complexes reported in

this thesis. General reaction schemes for the preparation of the complexes with the general
formulae of [R3PAu(6-MP)] (where R3P = Et3P, Cycl3P, PhMe2P, Ph3P, (o-Tol)3P,
 13

(m-Tol)3P or (p-Tol)3P), [(PhzP(CHz)nPPh2)(AuCl)(Au(6-MP))] (where n = 2 or 3) and

[(PhzP(CH)¡PPh2)(Au(6-MP))z] (where n = 1, 2 or3) are shown in Figure 2.2.1.

R3PAuCl + 6-MPH + KOH R3PAu(6-MP) + KCI + H2O

Ph2P (CH2)nPPh2(AuCl) (Au(6- MP))

1)

Ph2P(CHtnPPhz(AuCl)2
1)+6-MPH+KOH 2)
Ph2P(CH2)nPPh2(Au(6-MP))2
2)+2(6-lvlPH)+2KOH

Figure 2.2.L: General Reaction Schemes For The Preparation Of The Complexes

In this thesis, for reasons of brevity those compounds of the general formulae

t(PhzP(cH2)nPPh2)(AuClXAu(6-MP))l and [(Ph2P(CHz)nPPhzXAu(6-MP))z] will be given

the abbreviations for the Ph2P(CH2)¡PPh2 phosphine ligand of dppm, dppe and dppp for

n = 1, 2 or 3, respectively. A detailed example of a preparation is given later.

The triorganophosphinegold(I) chloride complexes of the general formulae [R3PAuCl] (where

R3P is as defined previously) and [Ph2P(CH2)¡PPh2(AuCl)2] were prepared by a procedure

based on an example found in the literature20'2l. This method basically involves the reduction

of tetrachloroauric acid ([HAuCl¿].3HzO)zz by thiodiglycol followed by the addition of the

desired phosphine species in molar quantities. What follows is an example of one such

preparation.

Example: Preparation of I P hsPAuCI] .

1) 3(HOCHzCHÐzS
HAuCla.3H2O 2) Ph3P
Ph3PAuCl

Figure 2.2.22 Reaction Scheme For The Preparation Of [PhsPAuCl]

To a stirred solution of acetone (1 cms¡ and H2O (3 cm3¡ heici rn an ice bath uncier a nitrogen

atmosphere was added HAuCla.3HzO (0.600 g, 1.52 mmol). Thiodiglycol (0.56 g, 4.57
 t4

mmol) was then added dropwise to the yellow-orange solution over a period of 2 h. Extra

drops were added until a clear solution was obtained. The solution was then filtered under

nitrogen to remove undissolved solids. Ph3P (0.417 g,1.52 mmol) dissolved in hot acetone

@a 5 cm3) was added dropwise over a period of 10 min to the stirred solution. The resultant

white solid that formed immediately was collected via vacuum filtration and washed with a

small quantity of acetone. The solid product was air-dried for 5 min and recrystallized from hot

ethanol. The resultant crystalline material was dried for 12 h over anhydrous phosphorus
pentoxide under vacuum. Yield = 0.678 E; Vo yield = 90.07o; m.p. (dec.) = 233 - 234" C.

All the other compounds were prepared in an analogous manner using the appropriate molar

quantiries. The only variation to this procedure was for the preparation of [Et3PAuCl]; Et3P is a

liquid at room temperature, and so was added as such via a syringe over a 5 min period.

The transparent crystalline products are all air stable at room temperature. For the most part,

this procedure gave good yields: percentage yields based on 0.500 g HAuCla.3HzO used are

shown in Table 2.2.1, along with melting points and the corresponding literature values where

available.

Example: P reparatio n of I P hjP Au(6-M P ) ]

Ph3PAuCl + 6-MPH + KOH Ph3PAu(6-MP) + KCI + H2O

Figure 2.2.32 Reaction Scheme For The Preparation Of [PhjPAu(6-MP)]

To a stirred ethanolic solution (ca 30 cm3) of [Ph3PAuCl] (0.200 g, 0.405 mmol) and

6-mercaptopurine (0.062 g, 0.405 mmol) aqueous potassium hydroxide (0.200 mol dm-3,

0.405 mmol) was added dropwise over a few minutes. After 15 min of stirring, a pale yellow

solid started to form in the clear solution. The solution was left to stt for a further t h, then left

in a fumehood until the solvent evaporated. The solid residue was dissolved with stirring into

boiling acetone (ca 100 cm3), then vacuum hltered to remove undissolved solids. The filtrate

was left to stand until the acetone evaporated, and the off-white product was
 15

Table 2.2.1: Melting Points AndYields For Triorganophosphinegold(l) Chloride

Complexes.

Compound m.p. ('C) yield (e) 7o yield literature values ("C)

lEt3PAuCll 68-69 0.405 9 r.0 84 - 86 123)

ICycl3PAuCl] 117 - 118 0.379 58.2

lPhMezPAuCll r32 - r33 0.308 65.4

lPh¡PAuCll 242 - 243 0.590 94.0 242 t24l

[(o-Tot)¡PAuCl] (274 -27s) 0.619 90.8 283 - 285 Í2sl

[(n-Tol)¡PAuCl] t52 - r53 0.590 86.6

[(p-Tol)¡PAuCl] (186 - 187) 0.578 84.7

Idppm(AuCl)2] 270 - 271 0.407 7 5.5 273 126l

ldppe(AuCl)zl (288 - 28e) 0.56s 96.4 290 - 292 lztl

[dppp(AuCl)2] (2ss - 2s6) 0.358 64.3 2s6 - 257 t28l

Note: Brackets around the melting point value indicates decomposition point.
 r6

recrystallized nvice from a small quantity of 1:1 ethanol / dichloromethane to give a pale yellow

microcrystalline product. Yield : O.23I g; Vo yleld = 93.7Vo; m.p. (dec.) = 254 - 255" C.

This procedure was adapted to prepare all the complexes for this project. They are all air-stable

solids, and vary in colour from very pale to bright yellow. The melting points, Vo yields (based

on 0.200 g of [R3PAuCl] or [Ph2P(CH2)nPPh2(AuCl)2] used), colour and microanalytical

results are shown in Tables 2.2.2 and2.2.3.

2.3 Instrumentation

All melting points were determined using a Gallemkamp melting point appilatus calibrated
with benzil.

Infrared spectra for all complexes were recorded on a Perkin-Elmer 1720X FT spectrometer

calibrated with the polystyrene absorption at 1601 cm-l, as KBr discs in the range of
400 - 4000 cm-l.

Proton and carbon-l3 NMR spectra were recorded on a Bruker ACP-300 NMR spectrometer

with d6dimethylsulphoxide as the solvent. The recording frequencies used were 300.13 MHz

for lH NMR and75.4l MHz for l3C NMR. The internal reference used was SiMe4 (TMS).

Phosphorus-3l NMR spectra were recorded on a Bruker CXP-300 NMR spectrometer at

ex-lerrraì
l2I-5 MHz, also as d6-dimethylsulphoxide solutions, with thejntenr¿treference being 857o

H3POa in D2O.

FAB mass spectra were obtained using a VG ZAB-2Iß spectrometer. The excitation gas was

argon at a source pressure of typically 10ó mbar. The FAB voltage was 7 kV with a current of

1 mA, the ion accelerating potential being 8 kV. A drop of a ca 0.5 mol dm-3 solution of the

complex in dichloromethane was added to a drop of 3-nitrobenzyl alcohol matrix and applied to

the probe tip. The spectra were recorded as a mass to charge raÍio, m/2. Relative abundance was
 t7

Table 2.2.2: Melting Points,Yields AndColours ForTheTriorganophosphinegold(I)

6 -mer c ap topuri nate C omp lexes .

Compound m.p. ('C) yield (g) Vo yreld colour

[Er3PAu(6-MP)] 102-103 0.264 99.2 pale yellow

ICycl3PAu(CMP)] 139-t40 0.228 93.2 light yellow

lPhMezPAu(6-MP)l 173-175 0.2r2 80.6 yellow-green

lPh¡PAu(6-MP)l 254-255 0.231 93.7 off white

[(o-Tol)¡PAu(6-MP)] (2s3-2s4) 0.235 96.7 pale yellow

[(z-Tol):PAu(GMP)] 108-109 0.238 97.9 pale yellow

[(p-Tot)3PAu(6-MP)] 105-106 o.238 98.1 pale yellow

[dppe(AuClXAu( 6-MP) )] (183-18s) 0.215 94.8 pale yellow

[dppp (AuClXAu(6-MP) )] (2O3-2O4) 0.212 93.6 pale yellow

[dppm(Au(6-MP))z] 179-180 0.1 89 7 4.3 off white

[dppe(Au(6-MP))z] 150-r5r 0.209 82.4 off white

[dppp(Au(6-MP))z] r6t-162 0.2t1 83.5 off white

Note: Brackets around the melting point value indicates decomposition point.
 18

Table 2.2.32 Miuoanalytical Data ForTheTriorganophosphinegold(l) í-mercaptopurinate

Complexes.

Compound VoQ^L ToCround VoH¿¡ç Vo}l¡s¡,n¿

lEr3PAu(GMP)l 28.33 28.r9 3.89 4.06

ICycl3PAu(6-MP)] 43.95 44.02 5.77 6.03

lPhMezPAu(GMP)I.O.5EIOH 33.02 33.t5 3.36 3.11

lPh¡PAu(6-MP)l 45.26 45.r9 2.91 2.98

[(o-Tot)3PAu(6-MP)] 47.86 47.7r 3.11 3.90

[(ln-Tol)¡PAu(6-MP)] 47.86 47.82 3.7 | 3.94

[(p-Tol)sPAu(6-MP)].HzO 46.86 46.8s 3.1| 3.81

Idppe(AuClXAu(GMP))] 38.03 38.12 2.18 2.75

ldppp(AuCl) (Au(6-MP))l .Hzo 38.02 37.87 3.09 3.08

I dpp m(Au ( 6 -tvtP)) z\2IlzO 37.63 37.12 2.87 2.46

ldpp e (Au ( 6 -tvtP))zl.2HzO 38.24 38.1 5 3.03 2.60

[dppp(Au(6-MP))z]. CHzClz 38.24 38.07 2.87 2.63

Note: Microanalysis performed by Chemical And Microanalytical Services Pty. Ltd.

 t9

calculated by designating the most abundant peak as l00%o and determining the abundance of
the other peaks based on their relative heighs in the spectra to this peak.

2.4 Chemicals

The chemicals utilized in the synthesis of the complexes and their sources were:

triphenylphosphine (B.D.H.), triethylphosphine (Fluka), tricyclohexylphosphine (Strem),

tri(o-tolyl)phosphine (Aldrich), tri(m-tolyl)phosphine (Aldrich), tri(p-tolyl)phosphine

(Aldrich), ffbis(diphenylphosphino)methanel (Strem),\¡y'-t,Z-Ais(diphenylphosphino)ethanel

(Strem), [¡1-1,3-bis(diphenylphosphino)propane] (Strem), thiodiglycol (Aldrich) and

6-mercaptopurine (Sigma). All the solvents employed were of analytical grade.

2.5 C ry s t al I o g r ap hy : I rc tr ume nt ati o n a nd rne t ho ds

All the crystals were grown from the vapour diffusion of diethyl ether into an ethanolic

solution of the compound. The colourless crystals were collected and their identities conhrmed

by specral and melting point comparisons with the bulk material. The dimensions and

crystallographic parameters are given in later chapters where the results are presented. The

following description concerns the data collection and structure solution for
[(o-Tol)¡PAu(6-MP)].CZHSOH; the methods utilized for the other crystal structure
determinations were similar.

The crystal was mounted on a glass fibre using cyanoacrylate glue, and then placed on the

goniometer of a Rigaku AFC6R diffractometer fitted with graphite-monochromatized MoKo

radiation, ì. : 0.7107¡ Ä.. fne unit cell dimensions were determined from the least squares

refinement of 25 well-centred reflections in the range of I .7 < 0 < 12.8', and, with the aid of

Delauney reduction and a Laue symmetry check, was found to be monoclinic primitive with the

Laueclass of 2lm.Intensitydatawasthencollectedat23" Cintherangesof 0< h<12,0<k

< 13 and 0 < / < 33, to a maximum Bragg angle of 28 = 55.8". The intensities of 6280
reflections were measured using the t¡:20 scan technique, of which 5913 were unique. 'l'he
 20

value for R¿¡1¿1was 0.025, where

n m

I
t rj T
1
I . F2¡ ,- Pzii I

Rr-¿
n
I, m x <F2 i>
I I

n = the number of unique reflections that were observed more than once

m = the number of times a given reflection is observed

<f,¡> = the average value of P for the unique reflection i

No significant decomposition of the crystal occurred during the data acquisition. The data set

was processed and corrected for Lorentz and polarization effects, and the space group

determined to be P2y/n, based on the analysis of systematic absences. A total of 4183

reflections satisfied the criterion of observability of I > 3.0o(Ð and were used in the subsequent

analysis.

The structure was solved by direct methods using the SFIELXS8629 program and ref,rned by a

full matrix least-squares procedure based on F30. The function minimized was

n
I w¡(lFo6rlj-lF rarl¡)2
I 1

where ¿ is the number of reflections, and

\)
oz(F our)

The non-hydrogen atoms were refined with anisotropic thermal parameters, and the hydrogen

atoms were included in the model in calculated positions of C-H = 0.97.Å and N-H = 0.95 Ä,.

The absorption correction used was DIFABS3I. A weighting scheme was introduced based on
.:--^
ù¡6rr¡4 .',-i-kt.
w9¡6r¡lù. fÂrL+ vvrlvv¡õv¡¡wvr
^^-',o--an¡a tLo
t¡¡v .,ol',ac D 4rrs
^f ¡\
Y4rsvù v¡ o-.1 D
¡\w ,rrcrc fì fìl.1ì qnrl O O/'1
t ' rccnecfivelv
^vrYev"'-'J,
"Yv^v
 2I

where

n
tI (l F"øJ t-l F"o¡l ¡)
ft= n
I, I Fobsl i
I =I

and

t/2
n

i =1
Rw
n
t w¡l Fo6rlz
.'_1
L _L

The maximum and minimum residual electron density peaks in the hnal difference map were

1.25 and -1.46 eÅ-3. Scattering factors for all the atoms were those incorporated in the texsan

software package3O which was installed on a Silicon Graphics Indigo computer system. Tables

of bond distances and bond angles, fractional atomic coordinates, anisoffopic thermal and

hydrogen atom parameters and mean plane data are found in Chapter 3 for [PhMe2PAuCl],

Chapter 5 for [Ph3PAu(6-MP)].CzHsOH and [(o-Tol)¡PAu(6-MP)].CzHsOH and Chapter 6

for [Cycl3PAu(6p2-TU)]. Structure factors for all determinations a¡e located in the Appendix.

The expression for the anisotropic thermal pammeter of the non-hydrogen atoms is

Taniso = expf-2¡2(h2ax2lJ¡ ¡ y26*2922 l-12"*2933 + 2hka*b*Urz + 2hla*c*U13 +

2klb*c*Uz¡)l

and the expression for B(eq) for the hydrogen atoms is

B(eq) : 8n2(Urr + tJzz + Un)/z

 22

CHAPTER 3

Characterization of Triorganophosphinegold(I) Chloride and

[¡r-1,n-bis(diphenylphosphino)alkane]bis(gold(I) chloride)
Complexes

3.1Introduction

This chapter discusses the characterization of the complexes of the general formula [R¡PAuCl]

(where R3P = Et3P, Cycl3P, PhMe2P, Ph3P, (o-Tol)3P, (n-Tol)3P or (p-Tol)3P) and those of

the general formula t(PhzP(CHz)nPPhzXAuCl)21 (where n = 1, 2 or 3). While complexes of

this type are well known, documentation of their spectroscopic cha¡acteristics is not readily

available and hence this Chapter. The discussion consists of three main parts: 1) the spectral

characterization via infrared and multinuclear nmr techniques, 2) the crystal structure

determination of the [PhMezPAuCl] complex, and 3) a comparative study of

triorganophosphinegold(I) chlorides found in the literature with respect to phosphine cone-

angles and the P-Au and Au-Cl bond lengths. The last study will aim to determine whether a

correlation exists between the cone angles of the triorganophosphine ligands and the lengths of

the P-Au and Au-Cl bonds. The spectral characterization will be discussed in terms of how the

data relate to analogous information found in the literature, what it describes about the chemical

nature of these complexes, and how the information is useful for the characterization of the

triorganophosphinegold(I) 6-mercaptopurinate complexes discussed in Chapter 4.

 23

3.2 Sp e c tr al c har a c t e ri zat io n of t he t r io r g a nop ho s p hi ne g o I d( I ) c hlo r i de c o mp I ex e s

3.2.1 I nfrared spectros c opy

The spectra were recorded as described in Chapter 2.'lhe appearance of all the spectra were

fairly simple, containing a few strong absorptions with a number of very weak ones. These
absorptions are due to the vibrational modes associated with the phosphine ligands, since the

modes involving the gold(I) and chloride atoms, such as v(P-Au) and v(Au-Cl), occur below

400 cm-l and were not recorded owing to the limitations of the instn¡mentation. Table 3.2.1 lists

the major absorptions found in each spectrum and the functional group vibrations to which they

have been assigned. Infrared studies of these compounds in the literature are usually concerned

with the P-Au and Au-Cl stretching -o¿s532'33, so the assignments are based on comparisons

with the spectra of free phosphines. Figures 3.2.1 a) - d) show the infrared spectra of some

selected compounds, and it is clear that by comparing, for example, the spectra of [Et3PAuCl]
and [Ph3PAuCl], the absorption peaks found at 1586 cm-l and at 1480 cm-l for [Ph3PAuCl]

and not found for [Et3PAuCl] must be due to aromatic ring vibrations. The main peaks found
below ca 1450 cm-l are due to v(C-C), v(P-C) and 6(C-H) vibrations. These latter absorptions

a¡e listed together, as it is not possible to assign them unambiguously due to their overlapping
absorption ranges34,35. Comparison with the infrared spectra of the free phosphines36 shows

that, for Ph3P, the v(P-C) vibration occurs at 1430 crn-I, but it is unclear how the stretching

frequency of this bond is affected when the phosphorus atom binds to the gold(I) atom. The

aromatic absorptions for Ph3P36 occur at cø 1580 cm-1 and 1480 cm-1, indicating a slight

change upon coordination, related to the change in electron density about the gold centre. The

v(C-H) absorptions for alkyl C-H groups are more intense than those for aryl C-H groups in

the complexes, an observation that has been made before34, which is due to the hydrogen atoms

being more tightly bound to the aromatic rings than to alkyl carbon atoms. This is also the

reason why the aryl C-H absorptions occur between 50 and 100 wavenumbers higher than alkyl

U-ti
¡'\ Tr
afrsOrptiOns.
-L^^--.:^-^ i he aiKy'i
TL^ ^ll---l ^L^
absOrpiiOnS are mosi
. :-.^-^^
iniense in +L^
:-
tnc Spccirum
^ñ^^+'rrñ ûi
^f
 24

Table 3.2.1: Infrared Data For The Triorganophosphinegold(I) Chloride Complexes.

v v ô C_

lE13PAuCll 2962s,2932m, - 1456s, 1413m,1384m,

2905m,2874m 1259w,br,sh, 1044vs

ICycl3PAuCl] 2922vs,2852s 1447 s, I776m, 1040w

[Ph3PAuCl] 307lw, 3058w,br 1586w, 1480m 1435s, 1180w, 1103s

[(o-Tol)¡PAuCl] 3054w,297tm, 1589m, 1565w, 1448s, 1376m,1163m,

3023w,2930m 1468s 1133s, 1070w

[(ln-Tol)¡PAuCl] 3050w,br, 29llw 1593m, 1578w, l$ls, 14O4m,1383m,

1478s 1309w, 1108s, 1045w

[(p-Tol)¡PAuCl] 3014w, 2963w, 1598m, 1559w, l447w,br, 1397m, 1384w,

2917w 1498m 1310w, 1188m, 1103vs

[PhMe2PAuCl] 3056w, 3041w, 1587w, I573w, 1437s, 1426m, 1413s,

3023w,2990m,sh, 1507w, 1490w, 1384m, 1190m, 1161m,

2850m,br 1473w 1112s,1073m

Idppm(AuCl)2] 3050w,br, 29I6m, 1483w 1436vs, 1385m, 1185w,

2853w I 160w, 1 103s, 1069m

ldppe(AuCl)zl 3053m,br,2906m 1587w, 1573w, 1435s, 1411m, 1173s,

1482m 1106vs,1071m

Idppp(AuCl)2] 3049m,br,29I7m, 1586m, 157lw, l434vs, 1405s, 1385s,

290Im,2851m 1481s 1184m, 1158m, 1104vs,

1069m

Note: Units are wavenumbers (cm-t¡.

 25

[Cycl3PAuCl], in Figure 3.2.3. Figure 3.2.1 d) shows the relative intensities of aryl to alkyl
absorptions in the [dppm(AuCl)2] complex.

The data listed here will be useful in Chapter 4 as it can help assign those absorptions due to

the phosphine group in the spectra of the complexes, simplifying the analysis. There are

significant differences between the spectra of the triorganophosphinegold(I) chloride complexes

and the free phosphines to suggest product formation. However, the respective absorptions

between the gold(I) complexes are similar, indicating that the constituent absorptions are largely

independent of ttre nature of the rest of the molecule, as expected.

3.2.2 1H NMR spectroscopy

The proton NMR spectra were obtained as described in Chapter 2. Although soluble in

chloroform, for reasons of consistency the solvent used for these complexes was
d6-dimethylsulphoxide, as this was the solvent utilized for the 6-mercaptopurinate complexes in

Chapter 4. Figure 3.2.2 a) shows the labeling scheme adopted for the carbon atoms and the

protons bound to them.

v
ßo
E
d"
P-Au-Cl H3C-CH2-P
-Au-Cl
5

ô d.
aba
P P

I
-cH2-cH2-cHz- l
eõ Au Au

cl cl

Figure 3.2.2 a)z I'abeling Scheme Adopted For NMR Assignments

 26

Table 3.2.2 lists the assignments for the protons in each complex, including the multiplicity

and coupling constants. The methyl group of the tolyl phosphine complexes and of
[PhMezPAuCl] are designated by a CH3 subscript. The resonances for aromatic protons occur

as complex multiplets due to the complicated proton-proton and phosphorus-proton coupling

combinations, so are given as a range. This range is typical of triphenylphosphine absorptions

e.g. as found in [Ru(6-MP)z(PPhùz]2+ and Ph3P37'38. These resonances occur downfield at c¿

7.5 ppm because of the deshielding effect of the delocalized electrons in the a¡omaúc moiety. As

expected, there is little difference between these regions in the spectra of all the complexes

conraining this type of group. A similar but broader complex multiplet occurs for the cyclohexyl

protons of [Cyct3PAuCl], also due to complex coupling patterns, but upfield due to their alkyl

nature. Broad multiplets have been assigned to each proton type, but no coupling could be

resolved.

Two-bond indirect spin-spin coupling between the phosphorus atom and the protons was

observed for the resonance of the alpha protons in [Et3PAuCl], giving rise to two overlapping

quartets, where 3JHH = 7.7lHz, but 2Jpg was unresolved. The value of 3Jp¡q = 18.89H2 for
the beta protons results in a doublet of triplets, which is shown in Figure 3.2.2 b). The
uniformity of the shapes of these resonances suggests free rotation about the C-C and P-C

bonds in the phosphine groups. Phosphorus to proton coupling was manifested in the resonance

of Hu for [dppm(AuCl)Z], appearing as a triplet due to coupling with the two magnetically

equivalent phosphorus nuclei. It was not, however, distinguished for the Hu and H6 protons in
rhe spectra of the [dppe(AuCl)Zl and [dppp(AuCl)2] complexes, the resonances being broad and

featureless. The reason for this is that the protons involved couple to two phosphorus atoms,

and, in the case of H", the signs of the coupling constants are opposite, hence giving a net

coupling which is unresolved in the spectra, and further complicated by proton-proton

coupling. This corresponds with the resonance in the free phosphines, e.B. Ha in dppe is just

resolved as a triplet centred at ô 2.10 ppm38, compared to 6 2.97 ppm in [dppe(AuCl)z]. The

Iatter observarion is consistent with the deshielding effect expected at these nuclei upon

complexation to the gold centre.

 27

Table 3.2.22 1n ¡,1¡'tn Chemical Shift Values (ppm) For Triorganophosphinegold(l) Chloride

Complexes.

Complex H¿¡ H6 Hv H6 H-Cs¡ Ha H6

1.94(m) 1.10(dÐ
[E13PAuCl]
(7.tr) (7.3e)
(18.8e)

[Cycl3PAuCl] 2.13(m) 1.79(m) 1.35(m) 1.26(m)

[Ph3PAuCl] 7.63 - 7.51(m)

[(o-Tol)¡PAuCl] 7.64 - 6.87(m) 2.59(s)

[(ln-Tol)¡PAUC! 7.52 - 7.23(m) 2.34ß)

[(p-Tot)3PAuCl] 7.42 - 7.39(m) 2.38(s)

1.e4(d)
lPhMezPAuCll 7.86 - 7.56(m)
(11.35)c
4.70(t)
[dppm(AuCl)2] 7.77 - 7.44(m)
(12.58)c

ldppe(AuCl)zl 7.79 - 7.59(m) 2.97(m)

ldppp(AuCt)zl 7.76 - 7.51(m) 3.05(m) 1.71(m)

Note: All coupling constants, in parentheses, are in uniS of hertz: a = 3JHH, b = 3JPH, c =2JPH.
Figure 3.2.2 b)z 1H ¡'lØn Spectum Of Trietlrylphosphínegold(I) Chloride, IEBPAUCI] . Ref.

r4 (dÐ

rL (m)

2.0 1 u 1.6 1.4 t.a 1.0 B 6 4 2 00

PPM
 28

The data for the proton nmr studies on the complexes is consistent with literature values for the

free phosphines and analogous complexes, and are useful for comparison with the
Gmercaptopurinate complexes in the next chapter.

3.2313C {ta} tlun spectroscopy

The carbon-13 chemical shifs and phosphorus to carbon coupling constants are listed in Table

3.2.3- The phenyl-type carbon atoms are seen to resonate downfield, owing to the deshielding

effect of the delocalized electron density in the ring. Of particular interest is the observation that

the beta and gamma ca¡bons in the [dppm(AuCl)2] and [dppe(AuCl)2] compounds appear as

multiplets, where they would normally be expected to appear as doublets due to coupling with

one phosphorus atom. This phenomenon has been noted before in the literature, the explanation

being based on the fact that the two phosphorus atoms in the complexes are chemically
13C atom in the
equivalent but magnetically inequivalent due to the isotope effect (where a single

molecule creates isotopic asymmetry)3g. tn¿ee¿, in the spectrum of [dppe(AuCl)2], the beta and

gamma carbon resonances resemble triplets, where the coupling value given represents the

separation between the peaks. This structure can clearly be seen in Figure 3.2.3. As with the

proton spectra, the C¿ resonances are seen only as multiplets, but for the spectra of

tdppp(AuCl)Zl a doublet of multiplets can be resolved. The problems with the resolution are
more than likely due to the isotope effect.

As expected, the phenyl-region chemical shifts for the [(U - 1,n-(diphenyl-

phosphino)alkane)bis(gold(I) chloride)l complexes are similar to those found for [Ph3PAuCl]

and the tolyl compounds, the assignments of which were based on analogous complexes found

in the literature. The alpha, beta, gamma and delta resonances for Ph3P are I3J.2,133.6,128.5

and.l2S.4respectivel/0, ro it is apparent that coordination to the gold results in a major shift in

the Co shift value but only minor shifts in the others4l. The former shift is likely to be a

reflection of the change in electron density about the phosphorus atom when the P-Au bond is

formed: the lJpç value increases from 1l.3Hz in Ph3P to 61.03 Hz in the [Ph3PAuCl]

complex. Similar trends can be observed for the alpha carbon in all phenyl containing
 29

Tabte 3.2.32 13C Chemical Shifts Values (ppm) For The Triorganophosphinegold(l) Chloride
Complexes.

Complex Co Cß C. Cs C€ Cr -CH¡ Ca C6

[Er3PAuCl] 16.e(d) 9.05

(36.23)î

[Cycl¡PAuCl] 32.3(d) 26.2(d) 30.3 25.7 30.3 26.2(d)

(3 r.55)a (12.08)b (12.0S)b

[Ph¡PAuCl] 128.3(d) 133.e(d) 129.8(d) r32.4 12e.8(d) 133.e(d)

(61.03)a (13.3Ob (10.49)c (10.49)c (13.36)b

[(o-Tol)3PAuCl] r24.2(d) r4t.9 ß2.qd) 132.4 t27.2(d) 133.0(d) 22.3(d)

(&.70)z (11.93)b (8.91)c (10.57)c (9.66)b (11.02)c

[(lrr-TolþPAuCl] r28.2(d) 139.2(d) r30.9(d) 133.1 r29.qd) 134.1(d) 2r.0

(6l.3Oa (12.15)b (12.83)c (12.08)c (14.87)b

[(p-Tol)¡PAuCl] 125.3(d) 133.7(d) 130.2(d) 142.s(d) 130.2(d) 133.7(d) 21.0

(&.53)z (r4.zTb (12.15)c Q.re) (12.15)c (r4.n)b

[PhMezPAuCl] Obs. 131.8(d) 129.1(d) 13l.qd) 129.1(d) 131.8(d) 14.4(d)

(12.19)b (t 1.10)c (1 1.10)c (12.19)b (39.78)a

ldppm(AuCl)z] 128.7(m) 133.4(m) 129.3(m) r32.3 129.3(m) 133.a(m) 24.6(m)

tdppe(Aucl)d 128.7(d) 133.3(Ð t29.s(r) r32.2 l2e.s(Ð 133.3(Ð 22.4(m)

(58.60)a (6.42) (5.2e) (s.2e) (6.42)

ldppp(AuClhl 128.8(d) 133.1(d) r29.s(d) r32.2 rze.s(d) 133.r(d) 26.s(d) 20.3(m)

(59.85)a (13.3Ob (l 1.85)c (1 1.85)c (13.36)b (52.4Ða

Note: 31p-13ç coupling constants, in parentheses, are in units of hertz: a =

lJpc, b = 2Jpc and

c = 3Jpc.
 Figure 3.2.3 : 13C NUR Spectrum Of IU-1,2-bis(diphenylphosphino)ethane]bis(gold(l)
chloride ), [ ( P hzP ( C H z) zP P hù ( AUC I) z ] .

ic
i\'' c6
cy

-\-¡-'\ --.,^v'-

llo 124
132-
PPA
 30

phosphines in going from the free phosphine to the complex, although the same was not
necessarily true for the proton resonances. It should be noted that for [(o-Tol):PAuCl] and

[(llr-Tolyl)¡PAuCt] the assignments made for the six aromatic ca¡bons are tentative due to the
closeness of the resonance values4O. Assignments in the spectrum of [Cycl3PAuCl] a¡e based

on the data for the free phosphine42,43; the Co chemical shift remains static, but the Upg value

increases from 18.6 Hz to 31.55 Hz in the complex. The other ring carbons altered very little in

terrns of chemical shifts and coupling constants. A similar result is observed for Et3P and
[Et3PAuCl]42. Th's suggests that the chemical shifts of phosphorus-bound carbons in an
aromatic environment are more sensitive to coordination effects at the phosphorus atom than are

alþl-type carbons.

The specroscopic data confîrm the stoichiometries of the triorganophosphinegold(I) chlorides

and provide an essential reference for the interpretation of the spectra for the

triorganophosphinegold(I) 6-mercaptopurinate complexes.

3.3 Crystal structure determination of the [PltMezPAuCI] complex

The general details concerning the data collection procedure used in the crystal structure

determination of this complex have already been given in Chapter 2. What follows here is a

discussion of the unit cell and the molecular structure obtained by refinement of this data.

Crystals of the complex were gïown from the slow evaporation of a concentrated ethanolic

solution of the compound. The [PhMezPAuCl] complex crystallizes in the achiral space group

P2pQ1(Df, No. 19)44 and the absolute configuration was determined on the basis of the

differences beween high-angle Friedel pairs included in the data set. Crystal and refinement data

are listed in Table 3.3.1 and crystallographic results a¡e summarized in Tables 3.3.2 to 3.3.7 . A

list of the observed and calculated structure factors is given in the Appendix. The

crystallographic numbering scheme drawn with the ORTEP45 program is shown in Figure

3.3.1.
 31

Table 3.3.1: Crystallographic Parameters for the IPhMeZPAuCl] Complex

Data [PtrMezPAuCl]
Formula CsHrrAuClP
Formula weight 370.6
Crystal shape block
Crystal dimensions (mm) 0.27x0.14x0.14
Crystal system orthorhombic
Space goup P2p121çOf, No. tl¡
4 (Å) 12.639(4)
å (Å) 16.931(6)
c (Å) 9.458(3)
a (') 90

þ (") 90
y (") 90
v (År¡ 2024(r)
Z 8

pc¡c G cttt-3) 2.432

F(000) 1360

F (cm-l) 148.55
0limits, cell (') 8.0 to 12.8
0 limits, data (') 1.5 ro 25.4
hkl range 0 to 15,0 to 20,0 to 11
Range of transmission factors 0.945 to 1.058
Scan technique r¡:20

No. of data measured 3015

No. of unique data 2143
Ramal 0.046
No. of unique data used 1608

Criterion of observability 1> 3.0o(/)

No. of parameters 199

R 0.035
Rw 0.039
Residuat electron density (e Å-3) -0.99 to 0.94
Table 3.3.22 Fractional Atomic Coordinates ForThe [PhMe2PAuCl] Complex

Atom x v z

Au(1) 0.s4801(7) 0.3s61s(s) 0.s2s08(10)

Au(2) 0.463e3(7) 0.322rr(s) 0.21977(rO)

cl(1) 0.688e(s) 0.294e(4) 0.4228(8)

cl(2) 0.4269(s) 0.4s49(3) 0.1866(7)

P(1) 0.4rs2(s) 0.41s7(4) 0.6343(6)

P(2) 0.4450(5) o.1923(3) 0.2333(6)

c(12) 0.377r(r7) 0.37 r8(15) 0.8006(27)

c(13) 0.2956(18) 0.4t49(r4) 0.s424(32)

c(22) 0.4s90(1e) 0.1s40(13) 0.40s3(21)

c(23) 0.5613(18) 0.1s49(14) 0.rs20(23)

c(l11) 0.4417(r8) 0.s158(11) 0.6761(r8)

c(112) 0.3623(18) 0.5682(14) 0.7r2t(28)

c(113) 0.3843(22) 0.64r6(17) 0.7472(3r)

c(114) 0.4867(23) 0.6699(1s) o.74sr(24)

c(11s) 0.s677(20) 0.6198(1s) 0.7089(27)

c(l16) 0.s4s0(17) 0.544s(13) 0.6746(2r)

c(ztt) 0.3342(18) 0.1439(1s) 0.1s9 l(2s)

c(2r2) 0.3288(18) 0.0602(14) 0. r6s0(26)

c(213) 0.24s8(20) 0.0246(12) 0.0926(34)

c(zr4) 0.r736(20) 0.064s(1s) o.026e(37)

c(21s) 0.181e(19) 0.r470(r7) 0.0182(33)

c(216) 0.2618(17) 0.1840(13) 0.0777(3s)

Table 3.3.3: Anisotropic Thermal Parameters ForThe [PhMeZPAuCl] Complex

Atom urr Uzz U¡¡ Un Urc Uzz

Au(1) 0.038e(s) 0.0414(5) 0.0407(s) 0.0026(5) 0.0041(6) -0.0044(s)

Au(2) 0.0344(s) 0.0331(4) 0.0337(s) 0.0000(s) -0.0012(s) -0.002e(4)

cr(1) o.044(4) 0.0s4(4) 0.0e0(6) 0.007(3) 0.012(4) -0.01e(4)

c(2) 0.038(3) 0.031(3) 0.082(5) 0.001(3) -0.004(4) 0.001(3)

P(1) 0.03e(4) 0.049(4) 0.02s(4) -0.003(3) 0.00s(3) -0.001(3)

P(2) 0.032(3) 0.03s(3) 0.027(3) 0.003(3) -0.006(4) -0.001(3)

c(rz) 0.0s(2) 0.07(2) 0.0s(2) -0.00(1) 0.01(2) 0.02(2)

c(13) 0.0s(2) 0.07(2) 0.09(2) 0.00(1) -0.00(2) -0.06(2)

c(22) 0.07(2) 0.0s(1) 0.02(1) 0.01(2) 0.02(1) 0.01(1)

c(23) 0.04(1) 0.0s(2) 0.03(1) 0.00(2) 0.03(1) 0.00(1)

c(l11) 0.04(1) 0.04(1) 0.003(e) -0.01(1) 0.00(1) 0.007(e)

c(tL2) 0.0s(2) 0.0s(2) 0.03(2) 0.00(1) 0.02(2) -0.00(2)

c(113) 0.08(2) 0.06(2) 0.06(2) 0.02(2) 0.04(2> 0.o4(2)

o.o l(t)
c(l14) 0.10(2) 0.06(2) i-ggÉf -0.02(2) 0.00(1) 0.02(1)

c(11s) 0.0s(2) 0.08(2) 0.04(2) -0.03(2) -0.01(2) -0.01(2)

c(I16) 0.03(1) 0.0s(1) 0.02(1) -0.00(1) -0.02(1) -0.01(1)

c(211) 0.04(1) 0.04(1) 0.0s(2) -0.01(1) -0.02(1) 0.01(1)

c(2r2) 0.0s(2) 0.0s(2) 0.0s(2) -0.00(1) -0.02(2) 0.01(1)

c(213) 0.04(1) 0.03(1) 0.12(3) -0.01(1) -0.01(2) -0.01(2)

c(2r4) 0.06(2) 0.05(2) 0.12(3) -0.00(2) -0.0s(2) -0.03(2)

c(21s) 0.06(2) 0.08(2) 0.0e(2) 0.00(2) -0.0s(2) o.o2(2)

c(216) 0.04(1) 0.03(1) 0.15(3) 0.01(1) -0.06(2) 0.02(2)

Table 3.3.4: Hydrogen Atom Parameters For The [PhMezPAuCI] Complex

Atom x v z B(eq)

H(12a) 0.323r o.4041 0.8451 4.6

H(12b) 0.3493 0.3t92 0.7840 4.6

H(12c) 0.4383 0.3685 0.8622 4.6

H(13a) 0.2435 0.4456 0.5940 5.8

H(13c) 0.2709 0.3609 0.5326 5.8

H(1sb) 0.3059 o.4378 0.4494 5.8

H(22a) 0.3998 0.1709 0.4630 4.O

H(22b) 0.4605 0.0967 0.4013 4.0

H(22c) 0.5245 0.t73r 0.4465 4.4

H(23a) 0.5604 0.0976 0.1553 3.8

H(23b) 0.s639 0.r722 0.0543 3.8

H(23c) 0.6230 0.174/' 0.2019 3.8

H(112) 0.2892 0.5507 0.7r12 4.3

H(113) 0.3272 0.6766 0.775r 5.7

H(114) 0.5012 0.7246 0.7689 5.1

H(1rs) 0.6403 0.6384 0.7081 5.1

H(l16) 0.602r 0.5093 0.6478 3.6

H(2t2) 0.3804 o.0293 0.2r70 4.6

H(213) 0.24t9 -0.0326 0.0912 5.3

H(zt4) 0.1140 0.0376 -0.0160 7.1

H(21s) 0.1283 0.t769 -0.032r 6.8

H(216) 0.2698 0.2404 0.0639 7.0

Table 3.3.5: Bond Distances (A) For The [PhMe2PAuCI] Complex.

Atom Atom Distance Atom Atom Disunce

Au(1) c(1) 2.277(6) c(l11) c(l16) 1.3e(3)

Au(1) P(1) 2.2r4(6) c(l12) c(113) 1.32(4)

Au(2) cl(z) 2.273(s) c(1r3) c(114) 1.38(3)

Au(2) P(2) 2.20s(s) c(l14) c(11s) r.37(3)

P(1) c(r2) 1.81(2) c(115) c(l16) 1.3s(3)

P(1) c(13) r.74(2) c(2Lt) c(2r2) r.42(3)

P(1) c(111) r.77 (2) c(211) c(zr6) 1.38(3)

P(2) c(22) r.76(2) c(212) c(2r3) 1.3e(3)

P(2) c(23> r.77 (2) c(2r3) c(zr4) 1.30(3)

P(2) c(211) t.77(2) c(214) c(21s) 1.40(3)

c(I11) c(r12) 1.38(3) c(2rs) c(zr6) 1.31(3)

Table 3.3.6: Bond Angles ( ) For The [PhMe2PAuCI] Complex

Atom Atom Atom Atom Atom Atom

c(1) - Au(l) P(1) r77.2(3) P(1) c(l11) c(116) 12O(2)

cr(z) - Au(2) P(2) rt s.4(2) c(il2) c(l11) c(l16) rr7(2)

Au(1) - P(1) c(12) 114.9(9) c(I11) c(l12) c(113) tzr(2)
Au(1) - P(1) c(13) 114.e(e) c(|12) c(r l3) c(r 14) 122(3)

Au(1) - P(1) c(l11) 113.4(8) c(r 13) c(l14) c(1r5) tLe(2)

c(rz) - P(1) c(13) 102(1) c(114) c(11s) c(116) r19(2)

c(12) - P(1) c(111) 104(1) c(l11) c(116) c(115) 122(2)

c(13) - P(1) c(lr l) 106(l) P(2) c(211) c(212) t19(2)

Au(2) - P(2) c(22) tts.2(7) P(2) c(2tr) c(2r6) tzr(2)

Au(2) - P(2) c(23) 111.6(8) c(212) c(211) c(zr6) rr9(2)
Au(2) - P(2) c(zrr) 113.7(8) c(211) c(212) c(2r3) 1r7(2)

c(22) - P(2) c(23) 101(1) c(212) c(213) c(zr4) 123(2)

c(22) - P(2) c(211) 106(1) c(2r3) c(214) c(zrs) 120(2)

c(23) - P(2) c(211) 10e(1) c(zr4) c(2rs) c(zr6) 120(2)

P(1) - c(lr1) c(l12) 1,22(2) c(211) c(zt6) c(zrs) r21(2)

Table 3.3.72 Mean Plane Data For The [PhMe2PAuCl] Complex.

Plane number 1: Least-squares plane through the phenyl ring defined by atoms C(111) to

c(1r6).

Atoms Dehning Plane Distance (Å) eø (,&)

c(l11) 0.0057 0.0171

c(t12) -0.0124 0.0263

c(113) 0.0081 0.0274

c(114) -0.0008 0.0222

c(11s) 0.0006 0.0255

c(l16) -0.0030 0.0200

Additional Atom Distance (Ä.)

P(1) 0.0323

Mean deviation from plane is 0.0051 Å.

Chi-squared: 0.4.

Plane number 2: Least-squares plane through the phenyl ring defined by atoms C(211) to

c(2r6).

Atoms Defining Plane Pistance (.&) eø (Å)

c(zrt) -0.0241 0.0246

c(212) 0.0434 0.0327

c(2t3) -0.0144 0.0323

c(zr4) -0.0305 0.0346

c(215) 0.0234 0.0301

c(zr6) 0.0022 0.0251

Additional Atom Distance (Å)

P(2) 0.1208

Mean deviation from plane is 0.0230 Å.

Chi-squared: 4.3.
 czr4 czr5

c213
c7r6

cz12 cztr

Au2
g2
P2
cz3

c27 c13

CT12
cll Aul p
cl l3
clll
c12
cl l6
cl l4
cl 15

Figure 3.3.1: Molecular Structure And Crystallographic Nwnbering Scheme For

IPhMe2pAuCt].
 32

A diagram of the unit cell is shown in Figure 3.3.2. The unit cell is comprised of eight

molecules, the asymmetric unit therefore contains two molecules, labeled molecules 1 and 2

respectively; see Figure 3.3.1. The molecules are arranged in the unit cell in what appears to be

a dimeric relationship, known as head-to-tail dimers. Such interactions have been observed

before for triorgariophosphinegold(I) chlorides where the phosphine is relatively small in size,

and are attributable to the presence of close gold to gold interactions in the lattice46. The

Au(1)...4u(2) interaction is at a distance of 3.262(l) Å, which is less than the sum of the van

der Waals radii of 3.40 .À, but is due more to relativistic effects than a significant bonding

interaction46.

Both Au(1) and Au(2) exist in the expected linear geometry, clearly demonstrated in Figure

3.3.I, with P-Au-Cl angles of I77.2(3) and 175.4(2)" respectively, comparable with
179.63(3)" for [Ph3PAuCt147. The respective P-Au bond distances are 2.214(6) and
2.205(5) Å, which are equivalent within standard deviation. The Au-Cl bond distances of

2.277(6) and 2.273(5) ,Å, respectively are also within standard deviation range. The bond

distances of P(IFC(I11) and P(2YC(2I1) are both 1.77(2) L, a value lower but consistent
with those observed for [Ph3PAuCl]. The phosphorus to methyl group bond lengths in the
range of 1.76(2) to 1.81(2) Å are comparable to those found for [Et3PAuCl1a8. Analysis of

Tables 3.3.5 and 3.3.6 reveals that all the remaining corresponding innamolecular parameters

between molecules I and2 are identical to within standard deviation.

The phenyl rings are planar for both molecules, with mean deviations from planarity of 0.01(2)

and 0.02(3) Ä for molecules I and 2 respectively. The internal carbon to ca¡bon bond distances

range from 1.32(4) to 1.39(3).4. for molecule 1 and from 1.30(3) to 1.42(3) Å fo. molecule 2.

These values are typical for phenyl ring systems and a¡e indicative of electron delocalization.

The main difference ben¡¿een the two molecules in the asymmetric crystallographic unit is in the

geometry of the gold atoms as manifested by the respective values for the P-Au-Cl angle. This

difference might be attributable to the presence of the dimer in the lattice, where the
Au(1)...Au(2) interaction gives rise to unequal distortions in the ideal linear geometries about
 +b
0

Figure 3.3.2: Unit Cell Diagram For IPhMezPAuCI]

 33

the wo gold atoms46. The two independent molecules also differ from each other in the relative

orientations of the phosphine-bound substituents, as shown in the values of the torsion angles

Cl(n) / Au(n) / P(n) / C(n2), C(n3), C(nl1) of -47, -165 and 72" fot n = 1 and -178, 68 and
-56" for n = 2, respectively. The next section investigates whether the size of the phosphine as

represented by the cone-angle has any effect on the intramolecular parameters associated with

the gold atom.

3.4 Cone-angle correlatíonfor tríorgarcphosphinegold(I) chloride cornplexes

The cone-angle of a phosphine is a structural property flust introduced by Tolman49, and is

useful in defining the volume of space about a phosphine complex within which steric (van der

V/aals) interactions are likely to occur. Tolman's original work was centred on phosphinenickel

carbonyl compounds, in which the nickel atom formed the fourth substituent on the phosphorus

atom, to give this centre an approximately tetrahedral geometry. The substituents on the

phosphorus can sweep out a maximum volume of space about the P-Ni axis in the shape of a

cone whose apex lies on the metal centre, and the angle between the edge of this cone and a line

extended from the P-Ni bond axis (the apical axis) is defined as half of the cone-anglesO. Cone-

angles can usually be determined from crystallogaphic data, although for phosphines containing

mixed substituents, further mathematical treatment is required, resulting in a weighted cone-

angle. The Tolman cone-angles are hence dependent on the spatial size of the substituents and

on the lengths of the P-Ni bonds. Tolman's analysis assumed this bond length to be of a

constant value, but in reality the bulkiness of the substituents and the P-Ni bond length is likely

to be interdependent4g.

A recent publication by Brownsl inroduced a new parameter that complements the cone-angle

concept. Known as the ligand repulsive energy, Ep, this quantity results from energy-

minimization studies on phosphinechromium carbonyls, and represents the van der Waals

interactions between the phosphine substituents and moieties along the P-Cr bond axis. The

main advantage of the Ep quantity is that it distinguishes stenc ettects trom eiectronic effects,

and is more easily applied to phosphines bound to other elements. Using Tolman's calculated
 34

cone-angles (0) for the nickel compounds, Brown found that the Ep parameter correlated

surprisingly well with the cone-angle; i.e. the relationship between Ep and 0 was found to be

linear for analogous Cr and Ni compounds to within a small margin of error5l.

This study is concerned with the application of 0 and E¡ to triorganophosphinegold(I) chloride

complexes of the general formula [RgPAuCU. Complexes of this type invariably possess a gold

atom of linear geometry i.e. the P-Au-Cl bond angle is close to 180'. Hence the purely steric

effects on the chlorine atom that arise from the size of the phosphine are likely to be minimized'

Since the cone-angle parameter encompasses electronic effects d5s49'50 (the electronic nature of

the groups bound to the phosphorus atom will influence the length of the phosphorus to metal

bond and thus the magnitude of the derived or calculated cone-angle), then variations in the

P-Au and Au-Cl bonds with a change in 0 are likely to be attributable to electronic rather than

steric effects. Therefore, a correlation may be drawn between these parameters. The quantity of

Ep, which should describe only van der Waal or purely steric effects, should thus conelate less

well with the intramolecular parameters if electronic effects are significant. The parameters for a

range of triorganophosphinegold(I) chlorides have been collated from literature reports and are

shown, together with calculated 0 and Ep values, in Table 3-4"

Both 0 and Ep have been plotted against the P-Au and Au-Cl bonds; the results are shown in

Figure 3.4. At f,rrst inspection there seem to be no linea¡ relationships present between the

parameters and bond lengths. However, closer analysis of some of the plots reveals that a

common trend does exist, albeit with some exceptions. The plot of P-Au versus cone-angle

contåins points that appear to form a linea¡ distribution, with the anomalous points representing

t(phO)3PAuCll and [PhMeZPAuCl]. The analogous plot against Ep demonstrates the same
linear appearance, with the same two exceptions. The values of P-Au for those complexes on

the linear progression are in fact all equivalent within experimental error. Hence, there is no

noriceable electronic effect due to the phosphine ligand on the length of P-Au. The values for 0

can thus be regarded as absolute, similarly to Tolman's assumption of a constant P-Ni bond for

va¡ious phosphine ligands. Theplot of P-Au versusEpdisplays a simila¡ appearance tothe

 35

Table 3.4: Cone Angles (0), Ligand Repulsive Energies (ER) An¿ Intramolecular Parameters

Of The I Rf AuCl] Complexes.

RrP 0 (') En ftcal mol-r) p_Au_Cl (.) p-eu (Å) Au-Cl (Å) Ref.

Et3P r32 6r 178.s(3) 2.232(e) 2.305(8) t48l

178.9(3) 2.23r(8) 2.306(8)

Cycl3P 170 116 t77.0(2) 2.242(4) 2.27e(s) ts2l

Ph3P 145 75 179.63(8) 2.23s(3) 2.27e(3) Í471

Cycl2PhP r62 105 r78.3(1) 2.234(2) 2.28r(3) ts3l

(Pho)¡P r28 65 178.s(2) 2.192(s) 2.273(s) ts4l

(o-Tot)3P 194 113 179.4(r) 2.243(2) 2.281(3) l55l

(n-Tol)3P r45 79 175.1(1) 2.23s(2) 2.288(2) ts6l

PhMe2P r22 44 r77.2(3) 2.2r4(6) 2.277(6) This

work
17s.4(2) 2.20s(s) 2.273(s)

Note: Their ate two molecules in the asymmetric crystallographic units for each of [Et3PAuCl]
and [PhMezPAuCl].
 2.25

2.24

tr tr

2.23

2.22

I
È E

2-21 PhMe2PAuCl
EI

2.20

(PhO)3PAuCl

2.19
120 140 160 180 200

Cone Angle (")

2.31

2.30

2.29
õ I
o
f,

tr
2.28

2.27
120 140 160 180 200

Cone Angle (')

Figure 3.4: Plots Of The Parameters 0, And Ep Versus P-Au, Au-CI And P-Au-CI
 2.2s
ì

I
't 2.24
-l
I
,l
I tr
i

I
2.23
I
.t-t
I

J 2.22
I
fL
2.21
PhMe2PAuCl
o

2.20

(PhO)3PAuCl
o
2.19
40 60 80 100 120

Er (kcal/mol)

2.31

tr
tr

2.30

2.29

õI
J
E tr
2.28
o
o

GI

2.27
40 60 80 '100 120
I

Er (kcal/mol)
I
I

Figure 3.4 (continued)

 180
E
E

179 o

GIE

178
o

õ
f
I
E
¡
177
o-

176

EI

17s
40 60 80 100 120

Er (kcal/mol)

180
GI

179

EEI
E

178
o

õ I
f E
a
177 E
o.

176

175
120 140 160 180 200

Cone Angle (")

Figure 3.4 (continued)

 36

P-Au versus 0 plot, indicating that steric effects on the P-Au bond in the [R3PAuCl] complexes

are also negligible.

The two exceptions to the general trends were found for the [(PhO)¡PAuCl] and

[PhMe2PAuCl] complexes. In the paper by Brownsl, phosphite ligands were noted as

exceptions due to the flexibility of C-O-P linkages, which can easily 'absorb' steric effects by

adopting a variety of conformations not available to phosphines. Hence, neither 0 nor Ep can

adequately express the steric or electronic factors of the (PhO)¡P ligand. PhMe2P is classed as a

small phosphine, and gold(I) chloride complexes of these phosphines often crystallize in such

an arrangement to allow the closest Au...Au interaction possible in the lattice, usually resulting

in dimers46. As discussed earlier in this chapter, the structure determination of [PhMezPAuCl]

revealed that such dimers were present, with an Au(1)...4u(2) interaction .of 3.262(l¡ Å, less

than the sum of rhe van der Waals radü (3.40 Å¡. Suctr a small distance ir1}*#observed for

complexes of larger phosphines, and so in this complex the intermolecular interaction may be a

determining factor for the anomalous P-Au bond length. [Et3PAuCl] also contains a small

phosphine4S, but the cone angle is considerably greater. The closest Au...Au interaction here is

3.615(2)Å, signifrcanrly larger than 3.40 Å, and [Et3PAuCl] is consistent with the linear trend

of the graph.Thus, it can be postulated that, since [PhMezPAuCl] is anomalous for both Ep and

0, electronic factors from intermolecular Au...Au interactions tluueprignificant influence on the

length of the P-Au bond in complexes of small phosphines. Neither Ep nor 0 are adequate

quantities for accommodating such intermolecular interactions.

The Au-Ct bond length should manifest elecronic effects of the phosphine ligand on the
..r'tsielq
p-Au-Cl ch¡ã på€-e more than steric effects, as it occupies a position trans to the phosphorus

atom. The plots involving Au-Cl (i.e. Figure 3.4) show that there is no clea¡ trend' In fact, all
the values lie within experimental error. This indicates that, even in complexes with significant

intermolecular interactions in the lattice, the Au-Cl bond length is largely independent of the

steric and electronic effects of the phosphine ligand.

 37

The P-Au-Cl bond angle displays a relatively large spread of values. However, there is no

noticeable trend based on the nature of the phosphine ligand coordinated to the gold centre. The

values for [(PhO)¡PAuCl] and [PhMezPAuC[ are not exceptional, indicating that conformations

and intermolecular interactions do not affect this aspect of the chromophore in any special way.

Based on the examples studied, the important results are: 1) the P-Au bond length is

independent of the steric and electronic effects of the phosphine ligand, but can reflect the

electronic environment about the gold atom if significant intermolecula¡ Au...Au interactions are

present; 2) the Au-CI bond length remains invariant, regardless of intermolecular interactions

and the steric or electronic profiles of the phosphine ligand; 3) the P-Au{l bond angle shows a

range of values, but this angle is not clearly related to any steric or electronic property of the

phosphine ligand; and 4) the ligand repulsive energy, Ep, as calculated by Brown from energy-

minimization models, has a good correlation with the cone-angle of phosphines but is no better

than this angle for observing how the steric nature of a phosphine affects the intramolecular

characteristics of triorganophosphinegold(I) chlorides.

 38

CHAPTER 4

Spectroscopic Characterization of the Triorganophosphinegold(I)

6-mercaptopurinate Complexes

4.L Introduction

In this chapter the results obtained from the spectroscopic analysis of the complexes with the

general formulae [R3PAu(6-MP)] (where R3P = Et3P, Cycl3P, PhMe2P, Ph3P, (o-Tol)3P,

(m-Tol)3P or (p-Tol)3P), [(Ph2P(CH2)nPPhzXAuCl)(Au(6-MP))] (where n = 2 or 3) and

[(Ph2P(CHz)nPPhzXAu(6-MP))2] (where n = 1, 2 or 3) will be tabulated and discussed, with

emphasis on how these results indicate product formation and what they reveal about the

coordinated Gmercaptopurinate ligand. A general introduction concerning the 6-mercaptopurine

ligand itself and its chemistry as related to this project will be given first to help illustrate the

points discussed later.

4.2 An overview of the 6-mercaptopurine lígand

6-Mercaptopurine, 6-MPH, shown in Figure 4.2.I, is a member of the class of nucleobases

known as purines. These compounds consist of a six-membered heterocyclic ring fused to a

t
6 7
5 NH
HN
8

2 (
N 4 N
9
J

Figure 4.2.1: Labelling Scheme For í-mercaptopurine

 39

Irve membered ring at the 4 and 5 positions, as shown in Figure 4.2.I, thus resulting in a nine

membered skeletal structure. Purines are characterizeÀ,by the 1, 3,7,9 substitution pattern of

nitrogens for carbons.

The systematic name for 6-MPH is 1,7-dihydro-6H-purine-6-thione, which indicates that the

two protonated nitrogens are at positions I and 7. This finding is based on crystal structure
determinationssT,5S, but determinations on complexes containing 6-MP show that it is possible

for the protons to be bound to the other nitrogens alternatively. Tautomeric studies on the free

ligand in solution59 have shown that the most dominant tautomer is in fact the 1,9-dihydro-

form, suggesting the protons may be sufficiently labile to suit the requirements of a given

reaction mechanism: four tautomers of 6MPH are shown in Figure 4.2.2.It is therefore also

possible for the 6-thione group to exist as the thiol, although in a proportionately low
quantity59.

SS
NH

t
NH
HN N

(
N
N N
H

S SH

N NH
HN N

N NH
) l( N
N

Figure 4.2.2: Tautomeric Stuctures For í-mercaptopurine

For the prepilation of the compounds in this thesis, a metathetical reaction involving base was

utilized. This involves the exchange of a chloride ion for the 6-MP ligand, though it is not clea¡

whether the reaction is S¡1 or S¡2. In either mechanism, the 6-MPH molecule must be
 40

deprotonated. Studies on the pK" values for the protonated nitrogen centres indicate that Nl is

the more acidic atom59. Deprotonation here can result in the formal negative charge being

located on the sulphur atom through resonance (see Figure 4.2.3), thus leading to coordination

to the gold centre. This is verified by the crystal structure determinations presented in Chapter 5.

SS
NH
N N

( r( N
N N

S S

NH NH

t
N N
<---+
N
L N

Figure 4.2.3: Resonance Contributors To The í-mercaptopurine Anion.

The elecüon density in the 6-mercaptopurine ring system is likely to be altered when gold(I) is

coordinated by the sulphur atom, leading to greater delocalization of electron density in the six-

membered ring system. The changes in electron density should be detectable via spectroscopy.

4.3 [ nfrared spectros copy

The heterocyclic, aromatic nature of the 6-mercaptopurine ring system lends itself to a great

many possible absorptions in the infrared spectrum. Chromophores such as C=N, C=C and

other groups have all been observed to absorb strongly in purines and related
thionucleoþa5s560,61,62. Due to the overlapping of many of the absorptions, coupling effects,

as noted by Thakur and Singh63, -e likely to occur in 6-mercaptopurine and its complexes,

leading to complicated spectra. Reports in the literature often conflict with each other as to

where certain absorptions occur in the spectra, and on the identities of certain strong
 4l

absorptions64'65. The 'thioamide bands'63,ó6, which result from the coupling of various
absorption modes of delocalized N-C-S groups, have not been generally reported for
complexes of 6-mercaptopurine, although they are noted for other thionucleobases6O,6l,62.Tlne

thioamide absorption is usually divided into four bands (I, II, III and IV¡63, which differ in
their frequency ranges due to the constituent absorptions that are coupled. Bands III and fV are

usually observed at lower wavenumbers, around the finger-print region, and thus they are not

considered here as their assignments would be too tentative. The major contribution to band I is

from the u(C=N) vibrational mode, and band II from v(C=S). Hence coordination of
6-mercaptopurine to gold via sulphur should be observable through changes to the absorption

frequencies of these two bands.

The lack of definitive data in the literature has resulted in uncertainty as to how the infra¡ed

data for the complexes in this thesis should be presented. The scheme thus chosen is to list the

data in two tables: 1) Table 4.3.1 presenting the absorptions due to the phosphine moieties

(from comparisons with the spectra of the corresponding triorganophosphinegold(I) chloride

species); and 2) Table 4.3.2 presenting the absorptions due to the purine group. In the latter

table, the absorptions for the thioamide bands I and tr, v(f{-C-S), have been resolved from the

phosphine peaks by comparison with the spectra of the corresponding gold(I) chloride

complexes, but the other absorptions are listed together under the classification of 'purine ring

vibrations'. Bands I and II assignments are those peaks occuring in the range where this

absorption is observed for analogous heterocycles e.g. for thionucleobase gold(I)

complexes60,6r,62. These should not be regarded as definitive assignments, but they are likely

to be representative of the important thioamide chromophore.

A broad absorption band occurs in many of the spectra at ca 3400 cm-l, due to water

molecules of hydration, or moisture in the sp€ctrometer environment. This band, when present,

overlaps with that of the N-H stretching mode. The v(N-H) absorption in all the spectra occurs
over a broad range of approximately 3300 to 2200 cm-l of medium intensity; such a wide range

has been observed before in complexes of 6-MP via sulphur coordination&'65. However, the
v(C-H) absorption also occurs in this range34,35, so the broad absorption in this region should
 42

Table 4.3.1: Infrared Data For The Pfutsphine Moieties.

v(P-C), v(C_C)
v(C-H) v(C=C)
and

[Er3PAu(6-MP)] 3099m, 3055m, L456m,1418m,

2964s,2931s 1384m, 1268m
[Cycl3PAu(GMP)] 3099w, 304lw, 1446m, L4I7w,
2926vs,2853s 1385s, ll76w
[PhMe2PAu(GMP)] 3053s, 2952s, 1465w 1436m, L4I9m,
2925s 1384m, 1110w
[Ph3PAu(6-MP)] 3054m,2967m, 1479m l434vs, l42lm,
2929m 138 1s, 1 181w,
1 100s

[(o-Tol)3PAu(GMP)] 3054m,2964m, 1590s, 1470m 1449s, 1410m,

2927m 1384s

[(ln-Tol)¡PAu(6-MP)] 3035m,2921m 1477m 1447m,1418m,

1384m, 1108m
[(p-Tol)¡PAu(GMP)] 3097s,3035s, 1597s, 1497s l44Im, 1418s,
2917s 1397s, 1384s,
1 187s, I 102vs
[dppe(AuClXAu(6-MP))] 3055m,2924s 1575m, 1481m 1435vs, 1384s,sh,
ll73s, I 104s

[dppp(AuCIXAu(GMP))] 3056m, 2924s, 1481m l434vs, 1404m,

285lm 1384s, 1104s
[dppm(Au(6-MP))z] 3050s, 2927s, 1483m, 1467m l436vs, l42ls,
2923s,2853s 1384vs, 1191m,
1 102s

[dppe(Au(6-MP))z] 3050m,2972m 1481w, 1468w 1436s, 1410m,

1384vs, I 171w,
1 104m

[dppp(Au(GMP))z] 3050s, 2924s, 1482m 1436vs, I420s,

2852m 1384s, 1186m,
1 104s

Note: Units are wavenumbers (cm-t¡.

 43

Table 4.3.2: Infrared Data ForThe í-mercaptopurinate Moieties.

v(N-C-S) Purine

C-omplex band I band II vibrational modes.

6-MPH 1615s, 1575s, 1346s 7224s, 1 156m, lI47 m, ll23m,

1558m I27 6m, 1529s, t472m, 1409vs
[Er3PAu(6-MP)] 1586s, 1557vs 1320m 1238m, 1208m, 1 155w, Il32w
[Cycl3PAu(GMP)] 1585m, 1554s 1320m 1269w, l2l4w, 1207w, 1176w,

I132w,1113w
[PhMe2PAu(GMP)] 1586m, 1558s 1319s 1269w, L238w, 1208w,I l32w
lPh:PAu(6-MP)l 1591s, 1559vs 1321s I244s, 1236s, I2I0m, 1157w,
1 133w

[(o-Tol)¡PAu(6-MP)] I6I7m,1554vs I322m 1277 w, l24lm, 1229m, I2lIm,

ll64w
[(rn -Tol):PAu(6-MP)] I268w, L234m,1207m
1587m, 1555s 1319m
[(p-Tol)¡PAu(GMP)] 1585s, 1556vs 1319s 1269m, 1234s, 1208s, IlZOw
[dppe(Au CIXAu (6-MP) )] 1616s, 1595s, 1335m 131 1m, 127 6m, l2l7m, 1 159m,

1558m ll22m
ldppp(AuClXAu(GMP))l 1594m, 1558m 1318w I347w, 1274w, I240w, 1209w
[dppm(Au(6-MP))z] 1586s, 1558vs 1320s I27 0m, 1236s, 1201 m, 1 161 w

[dppe(Au(6-MP))z] 1587s, 1558s 1319m 127 5w, l236m,br, I209m,

l1'22w
[dppp(Au(GMP))z] 1585s, 1558vs 1319s 1269m,1238s, 1208m

Note: Units are wavenumbers (cm-l).

 44

be assigned to the overlapping vibrational modes of both v(N-H) and v(C-H). This absorption

can be seen most clearly for 6-mercaptopurine in Figure 4.3.1 and for [Ph3PAu(6-MP)] in
Figure 4.3.2.In the latter spectra the v(C-H) absorptions from the phosphine moiety can also

be observed as sharper peaks around 3000 to 2900 cm-I, an observation that is suggestive of
product formation. Further confrrmation arises from inspection of the thioamide peaks in these

two spectra; the differences in absorption frequencies for band I at l5l5 cm-l for 6-MPH and

l59l cm-1 for [Ph3PAu(6-MP)] for example. This suggests an increase in bond order of the

C=N chromophore, which is expected since the electron density in the aromatic system

increases upon coordination. The C=S bond approaches single bond character when the

sulphur atom coordinates to gold, and this is observed via band II; the 1346 cm-l peak moves
down to l32l cm-l in the [Ph3PAu(6-MP)] complex. Similar trends are observed for these

peaks in all spectra, suggesting product formation in all cases. The deduced changes in bond

lengths will be verified in the crystallographic examples in Chapter 5; N(ltrC(6) undergoes a

decrease in length of around 0.040 to 0.045 Ä., and C(6)-S(6) increases by approximately
0.039 to 0.052 Å upon coordination.

As expected, the frequencies of the phosphine vibrational modes are observed to be

independent of the coordination of the purine molecule to the gold atom. From the foregoing

discussion, infrared spectroscopy confirms product formation via the appearance of both
phosphine and 6-mercaptopurine absorptions in the spectra, and by the frequency shifts of the

thioamide absorption bands, which also confirm the expected increase in electron density in the

ring system upon complexation.

4.4 1H NMR spectoscopy

The data obtained from the proton NMR spectra of the complexes studied in this thesis are

reported in Tables 4.4.1 and 4.4.2. The solvent utilized was d6-dimethylsulphoxide as this

proved to be the only common solvent into which 6-mercaptopurine and the gold complexes

would dissolve. NMR studies on these and other analogous complexes were also performed in

other solvents (e.g. (CD3)2CO and CDC13) which showed that there was no obvious solvent
 1558

1615 \
v(N-H) + v(C-H) ßt5 \
1346

4000 3200 2400 2000 r600 f200 800 400

cH-l
Figure 4.3.1: IR Spectrum Of í-mercaptopurine, 6-MPH

r 591
v(N-H) + v(C-H)

1 559
t32t
- -)-
4000 3200 2400 2000 1500 1 200 400 4Or)

Figure 4.3.2: IR Spectrum Of 6-mercapiOurino¡9¡triphenylphosphine)gold(l),

fsr*P^ a&.,.?))'
 45

Table 4.4.121A Nntn Chemical ShiftValues (ppm) ForThe [RsPAu(6-MP)] Complexes

RrP 112 rI9 ¡¡8 Hc H6 Hy H6 FLcH¡

6-MPH 8.45(s) 13.62(br,s) 8.26(s)

Et3P 8.41(s) 13.21(br,s) 8.31(s) 1.95(m) 1.1e(dÐ

(7.68)a
(18.35)b

Cycl3P 8.34(s) 13.l2(br,s) 8.19(s) 2.r7(m) 1.89(m) 1.57(m) 1.32(m)

Ph3P 8.51(s) 13.35(br,s) 8.31(s) 7.13 - 7.64(br,m)

(o-Tol)3P 8.35(s) 13.14(br,s) 7.87(s) 7.61 - 7.02(br,m) 2.64(s)

(ln-Tol)¡P 8.45(s) 13.32(br,s) 8.25(s) 7.53 - 7.38(br,m) 2.28(s)

(p-Tol)3P 8.46(s) 13.32(br,s) 8.32(s) 7.58 - 7.40(br,m) 2.31(s)

PhMe2P 8.45(s) 13.20(br,s) 8.33(s) 8.02 - 7.58(br,m) 1.9s(d)

(10.63)c

Note: Coupling constants, in parentheses, are in units of HerZ: a: 3J¡1-¡1, b: 3Jp-H and c: ZJp-tl

Table 4.4.22 1H N¡øn Chemical Shift Values (ppm) For The [(PhzP(CH)nPPh)-
( AuC I ) ( Au( 6 -M P ) ) I And [ ( P hzP ( C H z ) nP P hù ( Au( 6 -M P ) ) z ] C omp I exe s'

Complex ¡12 q9 g8 Phenyl Protons Ha H5

6-MPH 8.45(s) 13.62(br,s) 8.26(s)

ldppe(AuClXAu(GMP))l 8.36(s) 13.12(br,s) 8.17(s) 7.95 - 7.37(br,m) 3.04(m)

ldppp(AuClXAu(6-MP) )l 8.36(s) 13.25(br,s) 8.09(s) 7.87 - 7.47(br,m) 3.02(m)

[dppm(Au(6-MP))z] 8.37(s) 13.13(br,s) 8.24(s) 7.89 - 7.49(br,m) 4.64(m)

ldppe(Au(6-MP))zl 8.40(s) 13.22(br,s) 8.20(s) 1.14 - 7.50(br,m) 3.07(m) 1.73(m)

[dppp(Au(6-MP))z] 8.38(s) 13. 18(br,s) 8.19(s) 1.83 - 7.42(br,m) 3.16(m) 1.89(m)

Note: Coupling constants, in parentheses, Íìre in units of Hertz: a: 3J¡¡-¡1, b: 3Jp-¡¡ and c: 2Jp-¡1
 46

effects62. The labelling scheme adopted is the same as that described in Chapter 3 for the
4.2,t
phosphine moieties, and the protons of the GMP moiety a¡e labelled as in FigureA.m, Crystal

structure determinations on [Ph3PAu(6-MP)].C2H5OH and [(o-Tol)¡PAu(6-MP)].C2H5OH

(see Chapter 5) revealed that the protonated imadazole nitrogen in these complexes is H9,

whereas it was H7 in 6-mercaptopurine. Therefore the ¡¡9 resonance given for

6-mercaptopurine in Tables 4.4.I and 4.4.2 conesponds to H7.

As for the triorganophosphinegold(I) chloride analogues, the phenyl regions are not very

informative due to the complicated coupling patterns which lead to broad multiplets. This

applies also to the spectrum of [Cycl¡PAu(GMP)], where broad and complex multiplets are still

observed. If there is an effect on coupling and chemical shifts in the phosphine ligand when

6-MP substitutes for the chloride on the gold centre, then it would best be observed in the

spectrum of [EI3PAu(6-MP)], where phosphorus-proton coupling is most clearly illustrated.

Table 4.4.3 shows the coupling constants involved with [Et3PAuCl] and [EI3PAu(6-MP)].

Table 4.4.32 Coupling Constants (Hz) AssocíatedWithThe EtjP Moiery

Complex 3Jpl¡ 3Jlrn ôH.' 6Hn

[Et3PAuCl] 1 8.89 7.71, 1.94(m) 1.10(dt)

[Er3PAu(6-MP)] 18.35 1.68 1.95(m) 1.19(dt)

It was not possible to determine clearly the values for 2Jpn (which are typically in the order of

10-11 Hz¡60'62, but the data from the table suggest there is little effect on the coupling and

shielding factors of the phosphine moiety between chloride and 6-MP substituted complexes.

Hence, the phosphine chemical shifts between the corresponding chloride and 6-MP substituted

complexes are fairly similar.

The proton resonances arising from the 6-mercaptopurine moiety give rise to simple peaks in

the spectra. The free tigand contains two N-H protons, nominally defined as Hl and H7, which

occur together as a very broad resonance centred at 6 13.62 ppm. This phenomenon has been
 47

reported in the literature before, at ô 13.5 ppm in d6-dmso67. On complexation Hl is removed,

but the single N-H resonance for H9 is still broad, and is indeed almost unresolved in some of

the spectra. Where observed, it resonates in the approximate range of ô 13.10 to 6 13.35 ppm.
An example in the literature where GMP is complexed via the sulphur atom to a tungsten atom,

lW(CO)S(6-tvtl¡10S, gives this proton resonance at 6 14.37 ppm. The high value of the

chemical shift is indicative of both the aromatic environment and of the electronegative nirogen,

which both give rise to a deshielding effect. The H2 and H8 resonances in the free ligand occur

as singlets at ô 8.45 and ô 8.26 ppm respectively (the literature example gives ô 8.35 and

ô8.15 ppm)67, with the H8 resonance being slightly broader and smaller. This is illustrated in

Figure 4.4.1 for [(rn-Tot)¡PAu(6-MP)], where the broad appearance of H9 and the complex

phenyl region can also be observed. The small difference in shape allowed identification of

these peaks in the complexes, where the H2 resonance was still observed to be further
downfield (the tungsten complex has values of 6 9.23 and ô 8.60 ppm, respectivelY). Tne

values for both these protons vary between the complexes, and so is no real guide as to whether

complexation has occurred; however, the appearance of both phosphine and purine resonances

in each spectra and the resultant integration allowed the confirmation of product formation.

4.5 I3C {1n} Nun spectroscopy

The labelting system used is the same as that for the triorganophosphinegold(I) chloride

precursors in Chapter 3 and that for the purine inrigureffiTables 4.5.1 and 4.5.2 show

the assigned resonances and coupling constants.

The resonances due to the phosphine moiety are consistent with those obtained for the

triorganophosphinegold(I) chloride precursors in terms of chemical shift values. In the

complexes, the alpha carbon resonates approximately 1 ppm further downfield when R
: Ph,

o-Tol, m-Tolorp-Tol, and around 0.4 ppm for the other complexes when compared with the

triorganophosphinegold(I) chloride precursors. The beta, gamma and delta carbon resonances

show no significant changes. However, it is still notable that C6 for the dppm, dppe and dppp

complexes experiences a general upfield shift of 0.5 to 0.7 ppm. The phenyl resonances in
 Phenyl

H2

H8

H9

t--
14 t, t-] .., t( ll ) 1L I 1
Dl)M

Figure 4.4.12 l tl Nptn Spectrum Of î-mercaptopurinatoItri(m-tolyl)phosphine ¡¡¡old(l),

[(m-Tot)f Au(6-MP)].
 Table 4.5.1: tsç ¡t¡71 ¡r¿ 3Ip¡L¡1¡ Chemical Shifts (ppm) For The Complexes Of The General Formula [RjPAu(6-MP)]

31P
ça ç5 ç6 C

Gmercaptopurine t44.6 151.0 r2',7.9 170.8 144.6

17.3(d)
[Et:PAu(6-MP)] 141.3 151.1 132.7 171.0 r49.r 8.92 37.52
(33.81)a

32.lld) 26.4(d) 30.1 25.5 30.1 %.4(d)

lCycl¡PAu(6-MP)l 140.8 150.8 132.7 170.8 r49.r 57.23
(28.53)a (12.08)b (12.08)b

r29.4(d) 133.e(d) 129.6(d) t32.0 12e.6(d) 133.e(d)

IPh¡PAu(6-MP)] 14r.6 r5t.4 132.4 170.1 149.2 37.53
(56.38)a (14.19)b (rr.z4)c (rr.24)c (14.19)b

rzs.4(d) r42.3(d) 132.3(d) 131.9 126.9(d) 133.1(d) 22.3(d)

[(o-Tol)3PAu(6-l"P) 140.6 150.6 Obs. 169.5 148.7 19.15
(60.99)a (12.53)b (8.30)c (9.66)" (9.43)b (10.94)c

r29.2(d) 138.8(d) 130.9(d) 132.5 r29.2(d) 134.1(d) 2r.o

[(n-Tol)¡PAu(6-Næ)] 141.3 151.0 132.4 170.2 149.0 37.36
(57.06)a (11.8Ðb (12.9r)c (l L85)c (14.94)b

126.3(d) 133.6(d) 130.0(d) 141.9 130.0(d) 133.6(d) 20.9

[þ-TolþPAu(6-MP)] 141.5 150.9 132.4 170.4 149.0 35.61
(59.70)a (14.19)b (11.93)c (l1.93)c (14.19)b

132.e(d) 131.9(d) 128.e(d) 131.3(d) 128.9(d) 131.9(d) 14.8(d)

[PhMe2PAu(6-l"P)] l4L4 150.9 Obs. 170.4 149.2 9.21
(56.15)a (13.21)b (11.02)c (1.43)d (11.02)c (13.21)b (36.53)a

Note: 3lp-13çcouplingconstants,inparentheses,areinHertz,where:a=Upc;b=2Jpc;c=3Jpc;d=4Jpc.
 Table 4.5.2: t3ç ¡t ¡11 And 31P ¡I n¡ Cnemical Shifts (ppm) For The Complexes Of The General Formulae

[ ( P hzP ( C H z ) nP P hù ( AUC I) ( Au( 6 - M P ) ) ] And [ ( P hzP ( C H z ) nP P h) ( Au( 6 - M P ) ) z ]'

ça ç5 g6 c 31P

Gmercaptopurine 144.6 151.0 1279 170.8 144.6

tdppe(AuCl)(Au(CMP)l 141.5 150.6 Obs. 170.1 149.0 r29.2(d) 133.2(Ð 129.2(t) 131.9 22:t(t) 3r.6
(56.00)a (6.87) (5.66) (19.93)a

tdp'pp(AuCl)Au(CMP))l 142.0 150.9 Obs. 17r.3 150.9 129.1(d) 133.0(d) r2e.3(d) 131.9 2ó.5(dd) 19.9(m) 28.5

(56.83)a (13.13)b (1 1.10)c (36.08)a

(r2.76)c

tdppm(Au(GMP)þl 141.0 150.7 t32.5 170.5 149.r Obs. 133.s(t) 128.9(r) 131.6 24.9(m) 3 1.3

(6.72) (s.38)

tdp'pe{Au(óMP)d 142.s 150.3 133.0 169.0 149.0 129.3(d) r33.2(r) r29.2(t) 131.9 22.6(m) 33.6

(56.08)a (6.87) (5.5e)

tdppp(Au(GlvfP)D 141.3 150.9 132.7 170.4 149.8 129.0(d) 133.r(d) 129.1(d) 131.6 26.qd) 19.5(m) 3r.4
(55.85)a (13.28)b (1 1.25)c (30.5Ða

Note: 3lp-13ç coupling constants, in parentheses, are in Hertz, where: a = Upc; b = 2Jpc; c = 3Jpc. Obs. indicates obscured.
 48

these complexes again display the coupling pattern due to isotopic asymmetry observed for the

triorganophosphinegold(I) chloride precursors. It is also notable that the complex multiplet that

might have been expected in the [(PhzP(CH2)¡PPh2)(AuClXAu(6-MP))] complexes due to

overlapping phenyl regions is not observed, indicating that all the phenyl rings give equivalent

resonance values in solution, hence suggesting that the gold ligands are fluctional; this is
supported by evidence from the phosphorus-31 nmr studies (see later). The resonances for C¿

and C6 are usually observed as complex multiplets which, like the methyl groups on the tolyl

phosphine complexes, do not experience significant changes in chemical shift or coupling

constants after comPlexation.

The five carbon resonances for the 6-MP moiety occur as broad peaks at greater than

ô 130 ppm due to the deshielding environment of the aromatic system. The relevant spectral

region for [Ph3PAu(6-MP)] is shown in Figure 4.5J, which demonstrates how the purine

resonances have a small and broad appearance. This feature is due to the Nuclear-Overhauser

Effect69, and arises because the rigid structure of the ring system does not allow efficient

dissipation of the spin energies via thermal motion, causing these nuclei to have long relaxation

times and hence to occur as broad resonances. The reson¿ulces for 6-mercaptopurine are given

in Tables 4.4.1 and 4.4.2, and agree with the literature reports that indicate that C2 and C8

occur at the same chemical shift value, i.e. 6 IM.8 ppm70. These peaks are resolved in the
complexes as the resonance for C8 is shifted downfield and that for C2 is shifted upfield. The

chemical shifts of the Ca and C6 atoms do not change significantly upon complexation, whereas

C5 is shifted downfield in value by approximately 5 ppm. What follows is a rationalization of

the shifts in resonance values observed for each nuclei in going from the free purine to the

complexes.

Complexation of 6-mercaptopurine to the gold atom via the sulphur atom causes significant

delocalization within the six membered ring system, which results in C2 experiencing a greater

share of electron density, the effect being a slight shielding of the nucleus and so a shift upfield

in the spectra. The resonance for C6 might be expected to change for the same reasons,
however, the reduction of double bond character of the C=S bond has an opposing effect on
 tl

cy (d)
qr (d)

Figure 4.5.1: 13C ¡¡Mn Spectwn Of 6 -merc ap top urínato ( trip he ny I p ho sp hine ) g o ld( I )'

IPhsPAu{6-MP)].

C6

c" (d)

tc6 ó lct lçz c5

\

140 130
17C
PPM
 49

electron density, and so the chemical shift value undergoes no significant change. The

resonances for C and C5 will experience a similar even distribution of electron density,

however, although the C5 resonance is indeed observed to move upfield, the signal for Ca

remains fairly static. The delocalization of elecron density in the six-membered ring creates an

electron withdrawing effect on the atoms in the imadazole ring, thus resulting in a downfield

shift for the C8 resonance.

In fact, the shifts in resonance observed are really only minor, but are large enough to suggest

that complexation to gold via sulphur has occurred for all the complexes; the resonances for C5

and C8 are the most indicative of product formation. The occurrence of both phosphine and

purine resonances in the spectra is further verihcation for product formation.

4.631P {Ia} Nun spectroscopy

The chemical shifts observed in the 3lP proton decoupled spectra of the complexes are listed

in Tables 4.5.1 and 4.5.2. All the resonances are singlets, as coupling to carbon-13 nuclei is

not observed owing to the low natural abundance of this isotope. The spectra are also
diagnostic in terms of purity of the complexes.

The resonances can often appear broad: Figures 4.6.1 and 4.6.2 show the spectra of

[ph3pAu(6-Mp)] and [(n-Tol):PAu(6-MP)], the latter resonance having the

broader

appearance. The chemical shift values vary appreciably between the complexes, as
the

phosphorus nucleus is sensitive to changes outside the coordination sphers7l, such as the cone-

angle of the phosphine and the electronic environment of the adjacent atoms.

Of note are the spectra of the complexes [dppe(AuCl)(Au(6-MP))] and

tdppp(AuClXAu(6-MP))1, where two types of phosphorus nuclei occur

in the molecule but

only a single resonance is observed at ambient temperature. Low temperature NMR studies on
a

represenrarive molecule i.e. [dppe(AuClXAu(6-MP))] resolved this resonance into two

peaks

that differed by approximately 4 pp* at 190 K, suggesting that 6-mercaptopurinate and chloride
 Figure 4.6.1:3Ip Nptn Spectrutn Of 6-mercaptopurínato(tríphenylphosphine)gold(l),

IPhjPAu(6-MP)].

5
P

i Ref

l1

.,v\^y¡,,,2.^.iV,VJ',.r;,\..¡.r w\ .'.¡. . r,,¡' r' -, j.,,', *'

. . t-\^t
,- -.^ ;. tt,., ,.,-l-,r-.¡iu!r¡r, /,,..-\ij\,!\'-(¡',\?r',""r.*,r-.f','vjr'; rV

,_l
:C i0
FÊI'1
 Figure 4.6.22 3Ip N¡utR Spectrtnt Of í-mercaptopurinato(trí(p-tolyl)phosphine)gold(I),

[(p-Tol)sPAu(6-MP)].

Ref

l! 31p
I

:' _'r_21'\\'
1/ ,,,,^ !:^w/l/-/i!4vi^,.-# t.\','' r''¿- ?¿) 1''r-'1'""'^

l0 ù
FPI"
 50

ligands a¡e fluctional at ambient temperatures. The results from the carbon-13 NMR shrdies on

the phenyl regions of these complexes supports this hypothesis.

4.7 Fast Atom Bombardment mass spectroscopy

The technique of Fast Atom Bombardment mass spectroscopy (FAB-MS) involves the

bombardment of gaseous molecules by high energy particles, to produce a series of ions that

can be observed on a spectrum with respect to thefu mass/cha¡Be ratio and their intensity. The

positively charged ions produced a¡e accelerated through a magnetic field in a gaseous state,

and so collide with each other and fragment or aggregate according to the stabilities of the

resulting ions. The detector in the spectrometer records those ions that reach it as a peak on the

spectrum, the most intense of which is assigned an intensity of l00%o.

Previous work on monomeric triorganophosphinegold(I) thionucleobases of the general

formula [R3pAuSR'1û,62revealed that high nuclearity ag$egates involving phosphorus, gold

and sulphur can occur in relatively high abundance, indicating not only that such ions are stable

but also that both sulphur and phosphorus have an affinity for gold(I), as discussed in Chapter

1. Examples of the types of ions observed are given below:

[R3PAu]+ [(R¡P)zAu]+

[(R¡P)zAuS]+ [(R¡PAu)zS]+

[(R3PAu)2AuS1+ [(R3PAu)3S]+

Tables 4.7.1 and 4.7.2\istthe m/e values, intensity (as a percentage of the height of the most

intense peak) and the assignment of the most significant ions found in the FAB spectra of the

complexes. For those complexes of the general formula [R¡PAu(6-MP)] where R3P = Et3P,

Cycl3P, PhMe2P, Ph3P, (o-Tol)3P, (ln-Tol)3P or (p-Tol)3P, Table 4.7.1 shows that the

molecular ion, [M]+, is observed for all the complexes, suggesting product formation. A

selection of the type of fragments listed above are observed in these spectra, suggesting that the

binding force between the sulphur and gold atoms is independent of the nature of the

thionucleobase. However, fragments analogous to tß¡PAu)z(6-Ml;1+ were not observed for

 Tabte 4.7.I2 Mass Spectral Data For The Complexes Of The General Formula

IRfAu(6-MP)].

RrP [R¡PAu]+ M]+ [(R¡P)zAu]+ [@3PAu)2(GMP)]+ [@3PAu)2S]+ [(R3PAuþS]+

E13P 3r5,7170 466,96Vo 433, tAÙVo 780,7970 977, t310
Cycl3P 477,6070 628,90Vo 757, tNVo IIM,9OVO 1463,207o

PhMe2P 335,627o 486, r9to 702,870 ro37, r5vo

Ph3P 459,5970 610,lffi%o 72r,2770 1068,277o
(o-Tol)3P 50r,2470 652,3370 805, 10070 1152, lOTo
(rn-Tol)3P 50r, tao70 652,9070 805,51Vo tt52,6270

þ-Tol)3P 50r,4070 652,5170 805, 1007o rr52,670

Table 4.7.2: Mass Spectral Data For The Complexes Of The General Formulae
t F hzP ( C H z ) nP P h2 ) @uC I ) ( Au( 6 - M P ) ) I a nd [ ( P hzP ( C H z ) nP P hÐ ( Au( 6 - M P ) ) z ] .

Complex [doonAu]+ dpp¿AuSl+ tPhPr(CHr)r.+r¡Aul+ t(dppnAubl+ [dpp¿AuzS]+

ldppm(Au(GlvP)21 58r,87n

tdppe(AuclXAu(GMP))l 378,570 8?A,25Vo

ldppe(Au(GMP))zl 824,\Vo

tdppp(AuCl) (Au(GMP))l 609, rtvo 641,470 838,\Vo

tdppp(Au(6MP)D 6t9, t6%o 392,8770 r2t8,370

Table 4.7.2: (cont .)

+ +
Complex ldppnAuz(6MP)l tPh¡P(CHz)nAu2S (6-MP)l

[dppm(Au(GlvP))2] 929, 10010

tdppe(AuClXAu(6-MP))l 943, 10070 898,5Vo

tdppe(Au(6MP)Þl 943,10070

ldppp(AuClXAu(ClvfP)l 957, r00vo 9r2, tíVo

tdppp(Au(GMP))d 957,5670 9r2,6Vo

Note: The symbol n represents m, e, or p for the corresponding complex in that row. n+ I
indicates an extra methylene group. When used as a subscript, n = | for dppm complexes,
n = 2 for dppe complexes and so on.
 52

other thionucleobases, suggesting that the stabitity of the S-Có bond is higher for
6-mercaptopurine under the conditions of the spectrometer.

The results from Table 4.7.1 suggest, from inspection of the composition of the fragments,

that phosphorus forms a strong interaction with gold(I) more often in a 1:1 ratio, but that

sulphur has the ability to coordinate to as many as three gold atoms.

The spectra for the complexes of the general formula [(PhzP(CH2)¡PPh2)(AuClXAu(6-MP))]

and [(PhzP(CHz)nPPhzXAu(6-MP))z], the results of which are summarized in Table 4.7.2,

show a variety of peaks, the results having less in common between the compounds than

observed in Table 4.7.I. The molecular ion is never observed with any significant abundance:

for the mono-substituted complexes, this might be attributable to the chloride ion being readily

lost in the conditions of the spectrometer. Notable is the appearance of the [dppnAu2(6-Me¡1+

fragment in high abundance in all the spectra. This fragment is analogous to the

[(R3PAu)2(6-Ue¡1+ fragment observed in Table 4.7.1, perhaps indicative of a strong

interaction between the gotd atom and the Gmercaptopurine moiety.

The combined spectroscopic evidence presented in this chapter is in accordance with the data

for analogous compounds in the literature and suggests product formation for the complexes
with the general formulae [R3PAu(6-MP)1 (where R3P = Et3P, Cycl3P, PhMe2P, Ph3P,
(o-Tol)3P, (n-Tol)3P or (p-Tol)3P), [(PhzP(CHz)nPPhzXAuClXAu(6-MP))] (where n = 2 ot

3) and t(PhzP(CH2)¡PPh2)(Au(6-MP))21 (where n = 1, 2 or 3). The results also indicate the

presence of the P-Au-S chromophore with 6-mercaptopurine as the sulphur donor. This
chromophore is usually observed to be linear in related structures; the next chapter discusses the

structure determinations of two of the complexes listed above, and confirms the spectroscopic

results.
 53

CHAPTER 5

Crystallographic Investigations of the Complexes [Ph¡PAu(6-MP)].C2H50H

and [(o-Tol)¡PAu(6-MP)].CzH50 H

5.1Introduction

In this section the crystal structures of the complexes [Ph3PAu(6-MP)].C2H5OH and

[(o-Tol)¡PAu(6-MP)].CzHSOH and will be discussed. The methods concerned with the data
collection and refinement procedures for these structures have already been outlined in

Chapter 2. The effects of coordination to gold on the 6-mercaptopurinate moiety will be

discussed ¿ìs a separate section.

5.2 C ry s tal struc ture of I P h jP Au( 6 - M P ) ] .C z H 50 H

Crystals of the complex [PhfPAu(6-MP)].CZH5OH were grown from the slow evaporation of

a concentrated ethanolic solution of [Ph3PAu(6-MP)].The complex crystallizes in the triclinic

space group fi 1Cl, No.2¡++' crystal and rehnement data are listed in Table 5.2.1 and the

derived results are given in Tables 5.2.2 to 5.2.7 . Unlike the other structures featured in this

thesis, the structure was solved by Patterson methods, using the program DIRDIF92

PATTY72. Calculated and observed structure factors are listed in the Appendix. The
crystallographic numbering scheme as d¡awn with the ORTEP45 progmm is shown in Figure

5.2.r.

Figure 5.2.2 shows the unit cell contents with 15 Vo thermal ellipsoids. The triclinic space

group Pl is centrosymmetric, and this is demonstrated clearly in Figure 5.2-2. There are two
 54

Table 5.2.1: Crystallographic Parameters for the IPîSPAu(6-MP)].CzHsOH Complex

Data [Ph¡PAu(6-MP)1. CzHsOH

Formula CzsHz¿,AUSPON+
Formula weight 656.5
Crystal shape octahedral
Crystal dimensions (mm) 0.07x0.11x0.29
Crystal system triclinic
Space group PI (cl, No. 2)
4 (,&) 11.066(3)
å (,{) 13.ss2(3)
c (Å) 8.70s(2)
a (") er.sr(2)
B (') 113.06(2)
v (") 89.6e(2)
v (Å:¡ 1200.8(5)
Z 2
pc¡c. (g c--3) 1.816
F(000) 640

[ (cm-l) 63.27
0limits, cell (") 7.51 to 12.82
0 limits, data (") 1.5 to 28.1
hklrange 0 to 14, -18 to 18, -11 to l0
Range of transmission factors 0.964 to 1.016
Scan technique u:20
No. of data measured 6297
No. of unique data 5989
Ramal 0.033
No. of unique data used 3978
Criterion of observabiliry 1> 3.0o(I)
No. of parameters 298
R 0.034
Rw 0.029
Residual electron density (e Ä'-l¡ -0.98 to 0.72
Table 5.2.2: Fractional Atomic Coordinates For The IPhjPAu(6-MP)] .CzH5OH Complex.

Atom X v z

Au 0.10466(2) -0.229s9(2) -0.0000s(3)

s(6) -0.0319(2) -0.320s(1) -o.22tr(2)

P(1) 0.2ss6(2) -0.1366(1) 0.1981(2)

o(41) o.7se6) 0.4se3(3) 0.444s(s)

N(1) -0.201s(s) -0.464s(4) -0.2436(s)

N(3) -o.2628(6) -0.s303(4) -0.0324(6)

N(7) -0.0271(5) -0.3431(3) 0.1643(s)

N(e) -0.1475(5) -0.4520(4) 0.23s8(s)

c(2) -0.26s9(7) -0.s2st (s) -0.1846(8)

c(4) -0.1778(6) -0.46s1(4) 0.0697(7)

c(s) -0.1043(s) -0.398s(4) 0.0263(6)

c(6) -0.1182(5) -0.3987(4) -0.1382(6)

c(8) -0.0567(6) -0.3789(s) o.2828(7)

c(l1) 0.4109(5) -0.1e9s(4) 0.2864(6)

c(rz) 0.4960(7) -0.1823(s) 0.449e(7)

c(13) 0.6143(7) -0.2308(s) 0.511s(8)

c(14) o.e69Q) -0.2948(s) 0.4109(9)

c(15) 0.s622(7) -0.3118(s) 0.2s 1s(8)

c(16) o.4439(6) -0.2646(s) 0.1883(7)

c(zr) 0.290e(6) -0.0202(4) 0.1290(7)

c(22) 0.4141(6) 0.010s(s) 0. rs81(8)

c(23) 0.43ss(8) 0.1011(6) 0.1034(9)

c(24) 0.3327(e) 0.1s88(s) 0.0194(9)

c(2s) 0.2100(8) 0.1286(5) -0.0102(9)

c(26) 0.1878(7) 0,03e6(5) 0.0435(e)

Table 5.2.2 (co ntinued)

c(31) o.2123(6) -0.106s(s) 0.37r9(7)

c(32) 0.2333(8) -0.0148(s) 0.4489(9)

c(33) 0.2036(9) 0.0031(7) 0.58s8(10)

c(34) 0.1s34(9) -0.0708(8) 0.64s8(10)

c(3s) 0.1368(1 1) -0.1604(8) 0.s731(11)

c(36) 0.1639(9) -0.1781(6) 0.434s(e)

c(41) 0.s80s(11) 0.3773(8) a.2306(12)

c(42) o.6319(12) 0.4197(7) 0.3e23(rt)

Table 5.2.32 Anisotropic Thermal Parameters For The IPîSPAu(6-MP)].CzHsOH Complex

Atom urr Uzz U¡¡ Un Ur¡ Uzz

Au 0.0484(1) 0.0s00(1) 0.0367(1) -0.0138(1) 0.0100s(9) -0.00523(9)

s(6) 0.0s9(l) 0.064(1) 0.0324(7) -0.0208(8) 0.0102(7) -0.0o32(t)

P(1) 0.0s0(1) 0.048(1) 0.036e(8) -0.0140(7) 0.0137(7) -0.0072(7)

o(41) 0.093(4) 0.084(3) 0.04s(3) -0.02e(3) 0.025(3) -0.00s(2)

N(1) 0.067(3) 0.061(3) 0.036(3) -0.023(3) 0.010(2) -0.007(2)

N(3) 0.086(4) 0.06e(4) 0.044(3) -0.03s(3) 0.017(3) -0.003(3)

N(7) 0.064(3) 0.0s4(3) 0.032(3) -0.01s(3) 0.010(2) -0.007(2)

N(e) 0.070(3) 0.0s8(3) 0.03s(3) -0.010(3) 0.017(2) -0.001(2)

c(2) 0.08s(s) 0.072(s) 0.046(4) -0.047(4) 0.014(4) -0.010(3)

c(4) 0.062(4) 0.043(3) 0.037(3) 0.001(3) 0.01s(3) 0.002(3)

c(s) 0.047(3) 0.038(3) 0.033(3) -0.000(3) 0"006(2) -0.002(2)

c(6) 0.04s(3) 0.03e(3) 0.038(3) 0.000(3) 0.011(3) 0.003(2)

c(8) 0.070(4) 0.061(4) 0.03e(3) -0.003(3) 0.016(3) -0.00s(3)

c(11) 0.0s0(3) 0.044(3) 0.037(3) -0.014(3) 0.010(3) -0.001(3)

c(rz) 0.070(s) 0.0s6(4) 0.044(4) -0.007(4) 0.001(3) -0.013(3)

c(13) 0.071(s) 0.068(4) 0.04e(4) 0.002(4) -0.003(3) 0.00s(3)

c(14) 0.064(s) 0.0s7(4) 0.073(s) -0.002(4) 0.014(4) 0.006(4)

c(1s) 0.070(s) 0.062(4) 0.0s8(4) 0.001(4) 0.019(4) -0.00s(3)

c(16) 0.068(4) 0.0s6(4) 0.03e(3) -0.018(3) 0.017(3) -0.006(3)

c(zr) 0.0s6(4) 0.038(3) 0.03e(3) -0.010(3) 0.018(3) -0.007(3)

c(22) 0.057(4) 0.0se(4) 0.05e(4) -0.011(3) 0.021(3) 0.001(3)

c(23) 0.083(s) 0.066(s) 0.087(6) -0.024(4) 0.039(5) 0.001(4)

c(24) 0.r2r(7) 0.048(4) 0.080(s) -0.011(s) 0.0s9(s) -0.003(4)

c(zs) 0.0e4(6) 0.0s3(s) 0.087(6) 0.016(4) 0.037(s) 0.013(4)

c(26) 0.064(4) 0.061(s) 0.076(s) -0.004(4) 0.029(4) 0.001(4)

Table 5.2.3 (continued)

c(31) 0.0s4(4) 0.072(4) 0.03e(3) -0.01s(3) 0.016(3) -0.00e(3)

c(32) 0.107(6) 0.06e(s) 0.066(s) -0.019(4) 0.046(5) -0.01e(4)

c(33) 0.127(8) 0.101(7) 0.0e0(6) -0.014(6) 0.061(6) -0.033(s)

c(34) 0.126(8) 0.148(e) 0.066(s) -0.046(7) 0.0se(6) -0.034(6)

c(3s) 0.21(1) 0.17(1) 0.088(7) -0.12(1) 0.100(8) -0.0s2(7)

c(36) 0.165(e) 0.106(6) 0.068(s) -0.078(6) 0.071(6) -0.036(s)

c(41) 0.1e(1) 0.ls(1) 0.0e2(7) -0.083(8) 0.037(7) -0.02e(7)

c(42) 0.20(1) 0.120(8) 0.071(6) -0.078(8) 0.057(7) -0.035(s)

Table 5.2.42 Hydrogen Atom Parameters For The IPïSPAu(6-MP)]-CzHsOH Complex

Atom x v z B(eq)

H(2) -0.3228 -0.5735 -0.2649 6.4

H(8) -0.0163 -0.3550 o.3975 6.1

H(e) -0.1830 -0.487r 0.3041 12.4

H(12) 0.4724 -0.1366 0.52rr 6.0

H(13) 0.6743 -0.2192 0.6267 6.4

H(14) 0.7310 -0.3282 0.4538 6.4

H(1s) 0.5856 -0.3578 0.1806 6.1

H(16) 0.3834 -0.2776 0.0738 5.3

H(22) 0.4880 -0.0314 0.2177 5.3

H(23) 0.5240 0.r231 0.1258 7.0

H(24) 0.3461 0.2223 -0.0202 6.9

H(25) 0.1359 0.1706 -0.0704 6.8

H(26) 0.0986 0.0186 0.0210 6.1

H(32) o.2695 0.0377 0.4057 6.8

H(33) o.2179 0.0682 0.6391 7.r

H(34) 0.1302 -0.0s89 0.7410 9.8

H(3s) 0.1052 -0.2142 0.6194 12.l

H(36) 0.1475 -0.2429 0.3806 9.7

H(41b) 0.5784 0.4268 0.1507 13.2

H(41c) 0.63s4 0.3229 0.2238 9.2

H(41a) 0.4923 0.3s38 0.2051 13.z

H(42a) 0.63s0 0.3691 0.4699 10.8

H(42b) 0.5740 0.4122 0.3915 10.8

Table 5.2.52 Bond Dístances ¡Å¡ for The [PhjPAu(6-MP)].C2H5OH Complex

Atom Atom Distance Atom Atom Distance

Au s(6) 2.287(t) c(l1) - c(16) 1.3s8(8)

c(13) r.37 s(9)

Au - P(1) 2.237(2) c(12)

s(6) - c(6) r.728(s) c(13) c(14) r.362(9)

P(1) - c(11) 1.804(6) c(41) c(42) 1.40(1)

P(1) c(zr) 1.801(6) c(14) c(1s) 1.3s 1(8)

P(1) - c(31) r.794(6) c(1s) - c(16) 1.368(e)

o(41) - c(42) 1.38(1) c(zr) - c(22) 1.3s2(8)

N(1) - c(2) t.332(7) c(zr) - c(26) 1.366(8)

N(1) - c(6) 1.338(6) c(22) c(23) 1.383(9)

N(3) c(2) 1.31s(7) c(23) - c(24) 1.34(l)

N(3) - c(4) r.329(7) c(24) c(zs) 1.34(1)

N(7) - c(s) r.376(6) c(2s) - c(26) r.363(9)

N(7) - c(8) 1.303(7) c(31) - c(32) 1.373(8)

N(e) - c(4) 1.3s8(6) c(31) - c(36) r.337 (9)

N(e) - c(8) r.3s2(7) c(32) c(33) r.3t r(9)

c(4) c(s) 1.373(7) c(33) c(34) 1.36( 1)

c(s) - c(6) r.379(7) c(34) - c(35) 1.33( l )

c(11) - c(12) t.37e(7) c(3s) - c(36) 1.37(1)

Table 5.2.6: Bond Angles (') For The [PfuPAu(6-MP)] .C2H5OH Complex

Atom Atom Atom Anele Atom Atom Atom Angle

s(6) -Au - P(1) t73.7r(6) P(1) - c(11) - c(16) 118.7(4)

Au s(6) - c(6) 10s.e(2) c(rz) - c(l1) c(16) 11e.8(6)

Au - P(1) - c(11) r11.4(2) c(l1) - c(r2) c(13) 11e.6(6)

Au - P(1) - c(21) rr4.9(2) c(12) - c(13) c(14) 120.0(6)

Au - P(1) - c(31) rr3.3(2> c(13) - c(14) c(15) rt9.9(7)

c(11) - P(1) - c(2r) 10s.7(3) c(14) - c(ls) c(16) 120.e(6)

c(11) - P(1) - c(31) 10s.2(3) c(11) - c(16) c(1s) 11e.8(6)

c(21) - P(1) - c(31) 105.4(3) P(1) - c(zr) c(22) 123.0(s)

c(2) - N(1) - c(6) I 18.7(s) P(1) - c(21) c(26) 1 18.1(5)

c(2) - N(3) - c(4) 111.0(s) c(22) - c(zr) c(26) 118.8(6)

c(s) - N(7) - c(8) 102.8(s) c(21) - c(22) c(23) 120.s(6)

c(4) - N(e) - c(8) 104.0(5) c(22) - c(23) c(24) tr9.7 (1)

N(1) - c(2) - N(3) 128.e(s) c(23) - c(24) c(2s) r20.0(7)

N(3) - c(4) - N(e) 126.s(6) c(24) - c(zs) c(26) 120.8(7)

N(3) - c(4) - c(5) 126.2(s) c(zr) - c(26) c(2s) r20.2(7)

N(e) - c(4) - c(s) 107.3(5) P(1) - c(31) c(32) r22.9(s)

N(7) - c(s) - c(4) 110.1(s) P(1) - c(31) c(36) 118.4(s)

N(7) - c(s) - c(6) r32.2(s) c(32) - c(31) c(36) 118.6(6)

c(4) - c(s) - c(6) r17.1(s) c(31) c(32) c(33) 120.6(7)

s(6) - c(6) - N(1) 116.e(4) c(32) - c(33) c(34) 11e.s(8)

s(6) - c(6) - c(5) tzs.6(4) c(33) - c(34) c(3s) 119.s(8)

N(1) - c(6) - c(5) 117.s(s) c(34) - c(3s) c(36) 121.1(8)

N(7) - c(8) - N(e) 11s.8(s) c(31) - c(36) c(3s) 120.6(8)

P(1) - c(11) - c(rz) 121.5(s) o(41) - c(42) c(4I) i i6.l(9)

Table 5.2.72 Mean Plane Data For The [Phf Au(6-MP)].C2H5OH Complex.

Plane number 1: I-€ast-squales plane through the 6-mercaptopurinate moiety

Atorns Defining Plane oistance (,{) esd (Å.)

s(6) -0.Cn.24 0.0018

N(1) 0.0192 0.0054

N(3) -0.0226 0.0062

N(7) 0.0110 0.0051

N(e) -0.0094 0.0052

c(2) 0.0202 0.0079

c(4) -0.0124 0.00s9

c(s) -0.0003 0.00s4

c(6) 0.0085 0.00s4

c(8) 0.0148 0.0065

Additional Atoms Distance (Å)

Au 0.1465

Mean deviation from plane is 0.0121 Å.

Chi-squared: 56.4.
Table 5.2.7 (continued)

Plane number 2: Least-squares plane through the phenyl ring defined by the atoms C(11) to

c(16).

Atoms Definine Plane Oistance (Å) esd (Å)

c(11) 0.0047 0.0051

c(rz) -0.0023 0.0067

c(13) -0.0050 0.0074

c(14) 0.0060 0.0067

c(1s) -0.0003 0.0068

c(16) -0.0048 0.0057

AdditionalAtom Distance (Å)

P( 1) 0.0342

Mean deviation from plane is 0.0039 (Å).

Chi-squared: 2.8.

Plane number 3: Least-squares plane through the phenyl ring defrned by the atoms C(21) to

c(26).

Atoms Def,rnins Plane Distance (Å) esd (Å)

c(21) 0.0014 0.0051

c(22) -0.0023 0.0062

c(23) 0.0020 0.0073

c(24) -0.0005 0.0068

c(zs) 0.0001 0.0073

c(26) -0.0010 0.0067

Additional Atom Disunce (Å)

P(1) 0.0118

Mean deviation from plane is 0.0012.Ä,.

Chi-squared: 0.3.
Table 5.2.7 (continued)

Plane number 4: Least-squares plane through the phenyl ring defined by the atoms C(31) to

c(36).

Atoms Definine Plane Distance (Å) esd (,{)

c(31) -0.0031 0.0061

c(32) 0.0062 0.0081

c(33) -0.0002 0.0094

c(34) -0.0111 0.0100

c(35) 0.0t77 0.0126

c(36) -0.0024 0.0101

AdditionalAtom Distance (Å)

P(1) 0.0790

Mean deviation from plane is 0.0068 ,&"

Chi-squared: 3.5.
 cz4

c25
c23

czz
c26
czr
C1
c16

CI4 P1 Au S6

cll
c13 c12
c6
c31 N1

c36 N7
C2

c34 c3s N3
C8 C4

N9

Figure 5.2.1: Molecular Structure And, Crystallographic Nrmbering Scheme For

IPhjPAu(6-MP)].
+a

+c

Figure 5.2.2: Unit Cell Diagram Of IPhsPAu(6-MP)].C2H5OH.

 55

ethanol solvent molecules of crystallization in the unit cell such that the ratio of complex to

ethanol molecules is l:1. Hydrogen bonding is observed to occur between O(41) of the ethanol

molecule and H(9) of the 6-mercaptopurinate moiety, at a distance of 1.77 Ã; this is

demonstrated in the extended lattice diagram of Figure 5.2.3. Hydrogen bonding might be

expected to occur between nearby purine moieties; however, the planes of any two purine rings

that are nearest neighbours are only parallel, not co-planar. Figure 5.2.3 also indicates how the

molecules pack in such a way in the lattice such that the phosphine groups form a layer, and the

more polar gold(I), purine and ethanol regions form another layer. There are no significant

Au...Au interactions in the lattice: the closest such interaction is 6.628(1) Å, which is larger

than range of Au...Au contacts of 2.7 5 to 3.25 Å normally considered to indicate a 'significant'

interaction46.

Figure 5.2.1 is an ORTEPa5 diagram of [Ph3PAu(6-MP)] plotted with 30Vo probability

ellipsoids. The gold atom exists in the expected linear geometry defined by the P(1) atom of the

triphenylphosphine ligand and the 5(6) atom derived from the 6-mercaptopurinate moiety, with

a P-Au-S angle of fi3.71(6)". The deviation from ideal geometry may be related to the

presence of the close intramolecular Au...N(7) contact. The intramolecular distance is

2.384(5) .4., less than the sum of the van der Waals radii of Au and N of 3.25 .Å, but not

suggestive of a significant interaction. The length of the P(l)-Au bond is found to be

2.237(l) Ä., which is equivalent within standard deviation to the value of 2.235(3) Å tor

[Ph3PAuCl]a7. Comparison between the Ph3P moieties of [Ph3PAuCl] and [Ph3PAu(6-MP)]

reveals that this region is virtually identical in both complexes; hence, coordination of the 6-MP

ligand to gold has a negligible effect on the electronic factors of the Ph3P ligand.

As expected, the phenyl rings of the phosphine moiety are all planar; the maximum mean

deviation is 0.01(l).Ä. for the ring defined by atoms C(31) to C(36). The maximum deviation of

P(1) out of this ring is 0.079 Å. fne internal bond distances and bond angles are all typical of

electron delocalization in the six-membered aromauc system.

 .R
clA
-ô o

't

Figure 5.2.3: Lattice Diagram Of [PhsPAu(6-MP)].C2H5OH

 56

The Au-S bond distan ce is 2.287 (1) Å, which is a typical value for triorganophosphinegold(I)

thionucleobase complexes; examples of these will be given in Chapter 6. The intramolecular

pammeters of the 6-mercaptopurinate moiety will be discussed in detail in section 5.4.

5.3 Crystal Structure of [(o-Tol) jPAu(6-MP)].CzHsOH

Crystals of the complex [(o-To1)¡PAu(6-MP)].C2H5OH, glown from the slow evaporation of

a concentrated ethanolic solution of the compound, crystallize in the monoclinic space group
P2tln (Crsn, No. lÐ44. Crystal and refinement data are listed in Table 5.3.1 and the derived

parameters are given in Tables 5.3.2 to 5.3.7. Calculated and observed stmcture factors can be
rS
found in the Appendix. The crystallographic numbering scheme.jfshown in the ORTEP

diagram in Figure 5.3.1.

The contents of the unit cell are illustrated in Figure 5.3.2. The ethanol and

f-mercaptopurinate regions are observed to be associated as a layer, as are the phosphine

moieties. Hydrogen bonding occurs between H(9) and N(3) of nearby purine rings, at a

intermolecular distance of 1.93 Å. ttris association is possible as the purine ring systems are

close to co-planar; Figure 5.3.3 shows this interaction in detail. The closest Au...Au contact in

the lattice is at a distance of 7.821(2) Å; as for [Ph3PAu(6-MP)].C2H5OH this distance is not

indicative of a significant interaction.

Figure 5.3.1 shows an ORTEP diagram of the complex with 30Vo thermal ellipsoids. Notable

is the similarity in appearance with [Ph3PAu(6-MP)]. As expected, the P-Au-S chromophore

is nearly linear, with an angle of fi7.03(8)". This is closer to linearity than for
[Ph3PAu(6-MP)]; this may be due to the different hydrogen bonding interactions, or is perhaps

due to the larger cone angle of (o-Tol)3P and the possible consequent steric interactions. The

N(7) atom is directed towards the gold centre at a distance of 2.860(7) Å, again less than the

sum of the van der Waals radii, but not suggestive of any signihcant bonding interaction46.
 57

Table 5.3.1: Crystallographic Parameters for the [(o-Tol)3PAu(6-MP)] 'CzH5OH Complex

Daa [ (o-Tol)rPAu (6-MP)]. C2H5OH

Formula C4H3sAuSPON¿
Formula weight 698.6
Crystal shape hexagonal
Crystal dimensions (mm) 0.07x0.11x0.35
Crystal system monoclinic
Space group P2tln1Cr5n, No. t+¡

a (Å) 10.067(2)
b (Å) 10.518(2)
c (Å) 2s.416(4)

É (') 98.42(2)
v (Å:¡ 2662.1(9)
Z 4
pc¡c. (g
"--3)
u7r I'743
F(000) )aar'ta-76
F (cm-l) 57.16
0limits, cell (") 7.7 to 12.8
0limis, data (') 1.5 to 27.9
hklrange 0 to 12, 0 to 13, -33 to 33
Range of transmission factors 0.939 to 1.070
Scan technique u;20
No. of data measured 6280
No. of unique data 5913
Ramal 0.025
No. of unique data used 4r83
Criterion of ob servability / > 3.0o(1)
No. of parameters 325
R 0.040
Rw 0.041
Residual electron density (e Å-l¡ 3.51
Tabte 5.3.2: Fractional Atomic Coordinates For The [(o-Tol) jPAu(6-MP)] .C2H5OH
Complex.

Atom x v z

Au o.34432(3) 0.s1852(3) 0.r477s(r)

s(6) 0.r72t(2) 0.6422(2) 0.1099(1)

P(1) 0.s073(2) 0.3e18(2) 0.1878(1)

o(41) 0.1220(7) 0.2r3e(6) -0.0267(3)

N(1) 0.rs79(7) 0.8334(6) 0.044s(3)

N(3) 0.331s(8) 0.9469(7) 0.0122(3)

N(7) 0.4869(7) 0.69s0(6) 0.0912(3)

N(e) 0.s481(7) 0.85s2(7) 0.o42s(3)

c(2) 0.2072(t0) 0.9250(9) 0.0176(4)

c(4) 0.4130(e) 0.862s(8) 0.0393(4)

c(s) 0.3778(8) 0.7632(7) 0.0693(3)

c(6) 0.2430(8) 0.7s02(7) 0.0717(3)

c(8) 0.s863(9) 0.7s33(9) 0.0744(4)

c(l1) 0.ss43(7) 0.4320(7) 0.2s73(3)

c(12) 0.ss87(8) 0.3363(8) 0.29sr(4)

c(13) 0.s84s(10) 0.3647(9) 0.3476(4)

c(14) 0.6032(10) 0.4863(11) 0.3635(4)

c(1s) 0.6004(9) 0.s808(8) 0.3272(4)

c(16) 0.s76e(8) 0.ssj4(7) 0.2743(4)

c(17) 0.s82s(8) 0.663e(7) 0.2363(4)

c(21) 0.4648(8) 0.2248(6) 0.1868(3)

c(22) 0.5ss4(8) 0.1387(7) 0.1696(3)

c(23) 0.s2s6(10) 0.0122(8) 0.1666(4)

c(24) 0.404s(10) -0.0294(8) 0.fi92(4)

 Table 5.3.2 (continued)

c(2s) 0.3166(e) 0.0s4s(8) 0.19ss(4)

..:
c(26) 0.344s(8) 0.1820(7) 0.2006(3)
-;.1
I c(27> 0.2468(8) 0.2677(8) o.2212(4)

'-) c(31) 0.6s80(8) 0.4081(7) 0.1s7s(3)

r'.,.ì
'..
:
..af .¡ 0.1869(3)
c(32) 0.7749(8\ o.4418(7)

c(33) 0.88e2(e) 0.4634(e) 0.1673(5)

c(34) 0.8828(11) 0.4s15(e) 0.1135(6)

c(3s) 0.7668(11) 0.4r61(e) 0.0814(4)

c(36) 0.6s26(e) 0.3e35(8) 0.1036(4)

c(37) 0.s280(11) 0.356s(e) 0.0668(4)

c(41) 0.r443(r4) o.2360(12) 0.065s(s)

c(42) 0.r396(t2) 0.300e(12) 0.01s2(5)

Tabte 5.3.3: Anisotropic Thermnl Parameters ForThe [(o-ToI)fAu(6-MP)].CzH5OH

ComPIex.

Atom Uu Un. U¡¡ Un Urc Utz

Au 0.042s(2) 0.044s(2) 0.0442(2) 0.000s(2) 0.0064(2) 0.0099(1)

s(6) 0.040(1) 0.073(2) 0.0ee(2) 0.004(1) 0.011(1) 0.045(2)

P(1) 0.038(1) 0.037(1) 0.034(1) -o.o0o8(9) 0.008(1) 0.0038(e)

o(41) 0.082(s) 0.104(s) 0.042(s) 0.014(4) 0.012(4) -0.00e(4)

N(1) 0.063(s) 0.0s8(4) 0.048(s) 0.005(4) 0.016(4) 0.017(4)

N(3) 0.066(s) 0.067(s) 0.062(6) 0.00s(4) 0.017(s) 0.02s(4)

N(7) 0.042(4) 0.064(s) 0.064(6) 0.002(4) 0.009(4) 0.008(4)

N(e) 0.063(s) 0.066(s) 0.0s0(6) -0.011(4) 0.01s(4) 0.00e(4)

c(2) 0.071(7) 0.064(6) 0.0s8(7) 0.003(s) 0.00e(6) 0.01e(s)

c(4) 0.0s8(6) 0.0se(s) 0.03e(6) -0.006(s) 0.018(s) -0.001(4)

c(s) 0.0s3(5) 0.04e(s) 0.03s(6) -0.004(4) 0.006(4) 0.003(4)

c(6) 0.0s1(s) 0.0s4(s) 0.042(6) 0.000(4) 0.013(s) 0.00e(4)

c(8) 0.0s8(6) 0.071(6) 0.0s0(7) 0.001(s) 0.014(s) 0.010(s)

c(11) 0.036(4) 0.04s(4) 0.028(s) -0.001(3) 0.010(4) -0.001(3)

c(12) 0.0s8(6) 0.0s3(s) 0.042(6\ -0.006(4) 0.008(s) 0.006(4)

c(13) 0.074(1) 0.084(7) 0.031(6) -o.o1s(6) -0.000(s) 0.012(5)

c(14) 0.071(6) 0.108(8) 0.02e(6) -0.01s(6) 0.010(s) -0.01s(6)

c(1s) 0.064(6) 0.067(6) 0.036(6) -0.006(s) 0.012(5) -0.017(s)

c(16) 0.040(s) 0.047(s) 0.043(6) -0.003(4) 0.00e(4) -0.004(4)

c(17) 0.0se(6) 0.043(5) 0.062(7) 0.002(4) 0.007(s) -0.006(4)

c(2r) 0.04e(s) 0.03s(4) 0.034(s) -0.004(3) 0.003(4) 0.001(3)

c(22) 0.0s4(s) 0.046(s) 0.044(6) 0.002(4) 0.012(s) -0.000(4)

c(23) 0.090(7) 0.047(s) 0.0s7(7) 0.0r3(5) 0.02s(6) -0.00s(s)

c(24) 0.088(7) 0.042(s) 0.048(6) -0.011(s) 0.007(6) -0.002(4)

Table 5.3.3 (continued)

c(2s) 0.067(6) 0.054(s) 0.0ss(7) -0.011(s) 0.017(s) 0.011(s)

c(26) 0.0s3(s) 0.044(4) 0.036(6) -0.002(4) 0.013(4) 0.006(4)

c(27) 0.0ss(6) 0.063(s) 0.062(7) -0.008(4) 0.034(5) 0.004(s)

c(31) 0.044(s) 0.042(4) 0.033(5) -0.00s(4) 0.01e(4) 0.004(4)

c(32) 0.048(s) 0.047(4) 0.04s(6) 0.001(4) 0.021(4) -0.0o0(4)

c(33) 0.0s3(6) 0.068(6) 0.086(9) -0.013(s) 0.017(6) -0.00s(6)

c(34) 0.074(8) 0.071(7) 0.10(1) -0.016(6) 0.0s1(7) -0.007(7)

c(3s) 0.0e2(8) 0.07e(7) 0.058(8) -0.013(6) 0.045(7) -0.007(6)

c(36) 0.0s7(6) 0.056(s) 0.os2(7) -0.00e(4) 0.02r(s) -0.001(s)

c(37) o.oe3(8) 0.09s(7) 0.038(7) -0.011(6) 0.017(6) -0.00s(5)

c(41) 0.16(1) 0.13(1) 0.07(1) 0.00(1) 0.02(1) -0.022(8)

c(42) 0.088(e) 0.13(1) 0.0s6(e) -0.014(7) 0.011(7) 0.004(8)

Table 5.3.4: Hydrogen Atom Parameters For The [(o-Tol)SPAU(6-MP)].C2H5OH Complex

Atom x v z B(eq)

H(2) o.r4r9 0.9838 -0.0006 6.1

H(8) 0.679r 0.7269 0.0837 5.6

H(e) 0.6060 0.9110 0.0256 5.6

H(12) 0.5431 0.2487 0.2839 4.8

H(13) 0.589s 0.2972 0.3738 6.0

H(14) 0.6189 0.s063 0.4012 6.6

H(1s) 0.6156 0.6677 o.3394 5.2

H(17a) 0.6714 0.7016 0.2420 5.2

H(17b) 0.5633 0.632r 0.2002 5.2

H(17c) 0.5164 0.7277 0.2420 5.2

H(22) 0.6394 0.1690 0.1s98 4.5

H(23) 0.5892 -0.0480 0.1557 6.0

H(24) 0.3819 -0.1191 0.t764 5.6

H(2s) 0.23t4 0.0234 0.2038 5.5

H(27a) 0.2804 o.3543 o.2222 5.5

H(27b) 0.1613 0.2635 0.198 1 5.5

H(27c) 0.2351 0.24t3 0.2568 5.5

H(32) 0.77& 0.4510 0.2250 4.3

H(33) 0.9718 0.4862 0.1900 6.s

H(34) 0.9626 0.4686 0.0974 7.4

H(3s) 0.76s7 0.4071 0.0434 6.9

H(37a) 0.4551 0.3428 o.o872 1.1

H(37b) 0.5038 0.4240 0.0412 7.1

1l
H(37c) 0.5446 u.¿ t óó 0.0482 I l.t,^

H(41a) 0.0606 0.1908 o.0662 11.0

Table 5.3.4 (continued)

H(41b) 0.2182 0.1758 0.0697 11.0

H(4lc) 0.r574 0.2914 0.0942 11.0

H(42a) 0.2230 0.3468 0.0148 8.6

H(42b) 0.0652 0.3605 0.0110 8.6

Table 5.3.5: Bond Distances (A) For The [(o-Tol)sPAu(6-MP)].CzHsOH Complex.

Atom Atom Distance Atom Atom Distance

Au s(6) 2.266(2) c(14) c(15) 1.36(1)

Au - P(1) 2.239(2) s(6) c(6) 1.71s(8)

c(15) c(16) 1.35(1) P(1) c(11) 1.809(8)

P(1) c(zr) 1.808(7) c(16) c(17) r.49(r)

P(1) c(31) 1.808(8) o(41) c(42) 1.40(1)

N(1) c(2) r.32(1) N(1) c(6) r.343(e)

c(21) c(22) 1.40(1) N(3) c(2) 1.30(1)

c(21) c(26) 1.38(1) N(3) c(4) 1.33(1)

c(22) c(23) 1.36(1) N(7) c(5) 1.36(1)

N(7) c(8) 1.30(1) c(23) c(24) 1.38(1)

N(e) c(4) 1.3s(1) N(e) c(8) r.37 (r)

c(24) - c(2s) 1.36(1) c(2s) c(26) 1.37( 1)

c(4) c(s) 1.37(1) c(5) c(6) r.37 (t)

c(26) c(27) 1.4e(1) c(11) c(12) 1.39(1)

c(l1) - c(16) 1.40(1) c(r2) c(13) 1.36(1)

c(31) - c(32) 1.3s(1) c(31) c(36) 1.37 (r)

c(13) c(14) 1.3s( 1) c(32) c(33) 1.34(1)

c(33) c(34) r.37 (r) c(34) c(3s) 1.37( 1)

c(3s) c(36) 1.37(1) c(36) c(37) 1.s0(1)

c(41) c(42) r.44(2)

Table 5.3.6: Bond Angles (") For The [(o-Tol) jPAu(6-MP)].CzHsOH Complex

Atom Atom Atom Ansle Atom Atom Atom Angle

s(6) - P(1) 177.03(8) c(I1) c(tz) c(13) 120.3(8)

Au - c(6) 10s.3(3) c(r2) - c(13) c(14) r20.2(9)

Au - c(11) rr2.0(2) c(13) c(14) c(1s) 120.3(e)

Au - c(21) 1r4.6(3) c(14) - c(ls) c(16) 121.8(8)

Au - c(31) 110.7(3) c(l1) - c(16) c(1s) 118.s(8)

c(11) - c(2r) r0s.6(4) c(l1) - c(16) c(17) 122.r(8)

c(l1) - c(31) 106.1(4) c(1s) - c(16) c(17) 119.4(8)

c(zt) - c(31) 107.3(4) P(1) c(2\) c(22) 1 18.0(6)

c(2) - c(6) 118.9(8) P(1) c(zt) c(26) r2r.1(6)

c(2) c(4) 110.e(8) c(22) - c(zr) c(26) r20.2(7)

c(s) - c(8) 103.4(7) c(zr) - c(22) c(23) 120.0(8)

c(4) c(8) 10s.8(7) c(22) - c(23) c(24) 11e.5(8)

N(1) - N(3) 128.7(e) c(23) c(24) c(2s) r20.2(8)

N(3) - N(e) r27.4(8) c(24) - c(zs) c(26) r22.r(e)

N(3) - c(s) r27.4(9) c(21) - c(26) c(2s) 117.e(8)

N(e) - c(s) 10s.2(8) c(zr) - c(26) c(27) 122.8(7)

N(7) - c(4) 11 1.7(8) c(2s) - c(26) c(27) 11e.3(8)

N(7) - c(6) 132.3(8) P(1) - c(31) c(32) 120.s(6)

c(4) - c(6) 11s.e(8) P(1) c(31) c(36) t20.2(6)

s(6) - N(1) 115.8(6) c(32) c(31) c(36) 119.2(8)

s(6) c(5) Lzs.e(1) c(31) c(32) c(33) t24.6(9)

N(1) - c(5) 118.2(8) c(32) c(33) c(34) 1 16(1)

N(7) - N(e) 113.8(8) c(33) c(34) c(3s) r22.0(9)

P(1) - c(12) 118.e(6) c(34) - c(3s) c(36) 120(1)

P(1) c(16) r22.r(6) c(31) - c(36) c(35) I 18.s(9)

c(12) c(16) 1 18.9(8) c(31) c(36) c(37) r23.9(8)

c(3s) c(37) 1 18(1) o(41) c(42) c(41) I 10(1)

 Table 5.3.7 (continued)

Plane number 2: Iæast-squares plane through the ortln-tolyl ring defined by the atoms C(11) to

c(16).

Atoms Definine Plane Distance (,Ð esd (.Ä.)

c(11) -0.0041 0.0071

c(12) -0.0017 0.0086

c(13) 0.0106 0.0100

c(14) -0.0089 0.0099

c(1s) -0.0011 0.0091

c(16) 0.0056 0.0076

Additional Atoms Distance (Å)

P(1) -0.1466

C( 17) 0.0901

Mean deviation from plane is 0.0053 (Ä.).

Chi-squared: 2.5.

i
l

'1

i
I

I
Table 5.3.7: Mean Plane Data For The [(o-Tol) jPAu(6-MP)].CzHsOH Complex.

Plane number 1: l,east-squares plane through the 6-mercaptopurine moiety.

Atoms Defrning Plane Distance (Å) esd (Å)

s(6) 0.0134 0.0031

N(1) -0.0479 0.0076

N(3) 0.0324 0.0083

N(7) -0.0363 o.0017

N(e) 0.0282 0.0076

c(2) 0.0058 0.0104

c(4) 0.0196 0.0086

c(s) -0.0223 0.0082

c(6) -0.0s03 0.0086

c(8) 0.0016 0.0097

AdditionalAtom Distance (Å)

Au -0.0444

Mean deviation from plane is 0.0253 (Å).

Chi-squared: 156.3.
Table 5.3.7: (continued)

Plane number 3: Iæast-squares plane through the ortho-tolyl ring def,ured by the atoms C(21) to

c(26).

Atoms Definine Plane oistance (Å) eø (,4)

c(21) -0.0039 0.0078

c(22) -0.0062 0.0084

c(23\ 0.0131 0.0098

c(24) -0.0029 0.0092

c(2s) -0.0105 0.0094

c(26) 0.0111 0.0082

AdditionalAtoms Distance (Å)

c(27) 0.0711

P(1) -0.0856

Mean deviation from plane is 0.0080 (Å).

Chi-squared: 5.3.
Table 5.3.7 (continued)

Plane number 4: Least-squares plane through the ortho-tolyl ring defined by the atoms C(31) to

c(36).

Atoms Definine Plane Pistance (,{) esd (Å)

c(31) -0.0048 0.0070

c(32) 0.0001 0.0074

c(33) 0.0086 0.0093

c(34) -0.0093 0.0100

c(3s) -0.0004 0.0099

c(36) 0.0070 0.0083

AdditionalAtoms Distance (Å)

P(1) -0.1298

Cß7\ 0.0010

Mean deviation from plane is 0.0050 (Å).

Chi-squared: 2.6.
 c2s
c24
czl

cz3 76

c2l
c12 czz
cl3

cl4 cll P1 Au S6

c16 c37
c15
c3r
C6
NI
c36
c32 C5
c17
N7
c35 CZ

c33
c34
C8 N3
C4

N9

Figure 5.3.1: Molecular Structure And Crystallographic Nwnbering Scheme For

[(o-Tol)jPAu(6-MP)].
+a

+c
0

Figure 5.3.2: Unit Cell Diagram Of [(o-ToI) jPAu(6-MP)].CzHsOH

 )

Figure 5.3.3: Diagram lllustrating Intermolecular Hydrogen Bond.ing (indicated by

dnshed lines).
 58

The P(l)-Au distance is2.239(2) Å, which is equivalent within standard deviation to the

value of 2.243(2) Å for [(o-Tol)¡PAuCl155. It is also equivalent to the corresponding value of

2.237(2) Å for [Ph3PAu(6-MP)], suggesting that not only does the coordination of the 6-MP

ligand to the gold centre have little electronic effect on the phosphine moiety but also that the

size of the phosphine cone angle affects the P-Au bond to a negligible extent. This latter

observation is in accordance with the results obtained from the cone angle correlation for

triorganophosphinegold(I) chlorides in Chapter 3. The P-C bond distances also display

equivalent values.

T\e ortho-tolyl rings are all planar; the maximum deviation from planarity is observed for the

ring defined by the atoms C(21) to C(26), of the value 0.008(9) Å. fne phosphorus atom lies

out of the plane to a maximum value of 0.147 Å for the ring defined by the atoms C(11) to

C(16). The methyl groups on all three ring systems only deviate from the plane by less than

0.1 .Å, which is expected as the C(16), C(26) and C(36) atoms are all sp2 trybridized in the

aromatic system, as evidenced by the corresponding angles all being equal to 120' within

standard deviation.

The Au-S bond length ls 2.266(2) A., avalue which is significantly shorter than 2.287 0) L
for [Ph3PAu(6-MP)]. Again, this may be attributable to the relative cone-angles of (o-Tol)3P

and Ph3P, which are I94 and 145' respectivel/9, possibly giving rise to differing steric

interactions. The effect of coordination on the 6-mercaptopurinate moiety is discussed in the

next sectlon.

5.4 Comparison between the í-mercaptopurinate moiery in the free lígand and in the

complexes.

Crystallographic data for the free 6-mercaptopurine ligand has been obtained from the

reference of Sletten, Sletten and Jensen5T on the analysis of 6-mercaptopurine monohydrate.

Tables 5.4.1 and 5.4.2 gre the bond distances and bond angles for 6-mercaptopurine

monohydrate. These values are also given pictorially in Figures 5.4.1 and 5.4.2. Alongside
 59

Table 5.4.1: Bond Distances ¡Å¡ f or í-mercaptopurine MonohydratesT

Atom Atom Distance Atom Atom Distance

N(1) c(2) 1.3s0(2) c(6) - s(6) 1,.676(2)

c(2) - N(3) t.3o7(2) c(s) - N(7) 1.370(2)

N(3) - c(4) r.364(2) N(7) - c(8) r.346(2)

c(4) c(s) r.397(2) c(8) - N(e) r.326(2)

c(s) - c(6) 1.396(2) N(e) - c(4) r.363(2)

c(6) - N(1) r.384(2)

Table 5.4.22 Bond Angles (') For í-mercaptopurine MonohydratesT

Atom Atom Atom Angle Atom Atom Atom Angle

c(6) - c(2) rzs.4(r) c(6) r32.2(r)

10s.9(1)
N(1) - N(3) 12s.1(l) c(4)

c(2) - c(4) l r3.0(1) c(5) 106.1(1)

N(3) - c(s) r24.2(t) N(7) 113.6(1)

c(4) - c(6) r2r.9(r) c(8) 104.s(1)

c(s) - N(1) r 10.4(1) N(e) 109.9(1)

c(s) - s(6) r27.0(r) N(e) rzs.9(r)

N(1) _ s(6) 122.6(r)

 S6

H1

Ht
t22.6 t21 0
I
N
I t0.4 \ 1

t25.4 t 21.9
r 3.ó
I 125.0 124.2
.5
-Hs
H2
\r 13.0
N3
Ne
,/\
Au

6-mercaptopurine S6
ros.q

l16.9 125.6

32 7 1
7
N C5 102 8

il8.7 l17 7 u0I

il5 8

128.9
I 126.2 r07.1
.0
-Hs
H2
\
N3 'r"r'r:;< Nq

105.3
\
He

115.8 r25.9

132.3
[Ph3PAu(6-MP)]
I18.2
I 03.4
NI
I 18.9 115.9 lll.7
l 13.8

I 1?,8.1 121 .4 105-2

105.8
-Hs
ll0
H2 N3
He

[(o-Tol[PAu(6-MP)]

Figure 5.4.2: Schematic Represenration Of The Bond Angles (") InThe Purine Moiery OJ

6-mercaptopurine Monohydrate, IP|EP Au(6-M P )] .C2H 5OH and [(o-Tol)jP Au(6-

MP)l.CzHsOH.
 60

these diagrams are shown the 6-mercaptopurinate regions of the two complexes. The estimated

standard deviations for the values of the complexes have not been given for reasons of clarity

but they can be found in the tables on the previous pages.

Analysis of Figure 5.4.1 indicates how the internal molecular structure of the ring system is

altered upon complexation of the 6-mercaptopurinate ligand to the gold atom via the sulphur

atom. The most significant observation is that concerning the C(6)-S(6) bond. In 6-MPH, the

C(6)-S(6) bond length is 1.676(2) Å, a value indicative of its significant double-bond

character. Upon complexation, the length of this bond increases appreciably, to 1.728(5) ,Â, fo.

[Ph3PAu(6-MP)] and to 1.715(8) Å for [(o-Tol)¡PAu(6-MP)]. Hence, as expected the

C(6FS(6) bond approaches single-bond character as the sulphur atom binds to the gold atom.

The general increase in electron delocalization in the six-membered ring of 6-mercaptopurine

upon complexation leads to the N(l)-C(6) and C(5FC(6) bonds increasing in multiple-bond

character, which in turn lessens the bond order of the C(6)-S(6) interaction. All the bonds in
the six-membered ring system except for C(2FN(3) demonstrate a decrease in length;
N(1)-C(6) undergoes the greatest change. In the five-membered ring, the bonds of C(5)-N(7)

and C(4)-N(9) vary only slightly. An increase in the bond length of C(8)-N(9) and a decrease

in N(7)-C(8) is observed; the bond character in these two bonds has essentially been

exchanged from the free ligand to the complex. The movement in electron density thus suggests

that it is N(9) which is protonated in the complexes, whereas N(7) was protonated in the free

ligand, and justifies the placement of H(9) at this position, with the N-H bond distance fixed at

O.es Å.

The change in the internal angles, as illustrated in Figure 5.4.2, conf,rrms what the previous

paragraph suggested. The internal angles of the six-membered ring all appear to converge to

120", consistent with an increase in aromaticity in the ring. For both complexes the angles

C(4)-C(5)-N(7) and C(5)-C(4)-N(9) increase and decrease in size respectively upon

complexation, which is consistent with the movement of the amino hydrogen fiom N('/) to

N(e).
 61

The arguments above are consistent with the data obtained via the spectral characterization of

the complexes. Contraction of N(1)-C(6) upon complexation, which indicates an increase in

double bond character, was manifested in the infra¡ed spectra by a higher absorption frequency

of the thioamide band I vibrational mode. Similarly, the decrease in double bond character of

C(6)-S(6) is reflected by the decreasing absorption frequency of the thioamide band II

chromophore in the complexes. The observed overall contraction in size of the ring system also

supports the arguments made in Chapter 4 concerning the electronic effects of complexation via

sulphur on the resonance frequencies of the carbon-13 nuclei. Hence, as these interpretations

are now vindicated by the crystallogaphic evidence, then the identity of all the other complexes

prepared can be confirmed by extrapolation.

Even with the inclusion of the sulphur atom as part of the ring system, the purine group in

each of the molecules is planar; the mean deviation from the mean planes for [Ph3PAu(6-MP)]

and [(o-Tol)3PAu(6-MP)] being 0.012 and 0.026 Å respectively. When excluded, calculations

show that the system appea$ to be more planar e.g. in [Ph3PAu(6-MP)] the mean deviation is

0.009 Å. Bittrer way, the mean deviations are small.

All the effects noticed are expected for complexation to gold(I) via the sulphur atom,

consistent with the strucnres of other triorganophosphinegold(I) thiolate complexes. However,

a variety of coordination modes exist for crystal structures involving 6-mercaptopurine-type

thionucleobases in the literature. One example is coordination via N(9) e.g. 6-mercaptopurine

ribosideT3, and another common type is the ligand acting in bidentate fashion, coordinating to

the metal atom via the S(6) and N(7) atoms, e.g. dichloro-(6-mercapto-9-

methylpurine)copper(I!7a, (6-mercaptopurine)diaquodicadmium(IÐ75 and bis(6-mercapto-9-

benzylpurine)palladium(Il)-dimethylacetamideT6. In these cases the internal structure of the

purine moiety is similar to those discussed above given the changes. An example of metal to

sulphur coordination has been reported for dichloro(6-mercaptopurinium)copper(I)13, where

the 6-MP is in a protonated form; the effects here on the internal structure of the
 62

6-mercaptopurinate moiety are many ways the opposite to the effects observed for
deprotonation.

The crystallographic investigations of [Ph3PAu(6-MP)].C2H5OH and

[(o-Tol)3PAu(6-MP)].CzHSOH has revealed a number of observations. As expected, the

P-Au-S chromophore is a nea¡ linear group, consistent with previously observed data for
analogous structures. The bond distances within the 6-mercaptopurinate moiety undergo a

general contraction upon complexation, a result which is expected as the electron density

increases within the ring structure. The ligand coordinates exclusively in the monodentate
mode; the N(7) atom is oriented towa¡ds the gold centre in the solid state, although not at a

intramolecular distance indicative of a significant interaction. The specftoscopic data concerning

these complexes is consistent with the observed intramolecular parameters.

 63

CHAFT|ER 6

Crystallographic Investigations of Triorganophosphinegold(I) Thiolates

6.L Introduction

There are now several examples of crystal structures of triorganophosphinegold(I) thiolates

with the general formula [R¡PAu(SR')] in the literature. Common to all these complexes is the

SR' moiety coordinating in a monodentate mode, as a thiolate ligand, i.e. with an Au-S-R'

linkage, and an invariably linear P-Au-S chromophore. Such structural characteristics were

also observed in Chapter 5 for the [Ph3PAu(6-MP)] and [(o-Tol)¡PAu(6-MP)] complexes.

Thus, in a similar fashion to the triorganophosphinegold(I) chlorides analyzed in Chapter 3, a

study may be performed on these complexes to determine whether any simple relationship

exists between the steric effects of the phosphine and thiolate groups, and the intramolecular

parameters of P-Au, Au-S, P-Au-S and possibly the Au...N interaction observed in most of

the complexes; such a study is performed in this chapter. In order to gain additional information

on complexes possessing the Cycl3P phosphine group, the crystal structure determination of

the complex 6-n-propyl-2-thiouracilato(tricyclohexylphosphine)gold(I), [Cycl3PAu(6p2-TU)],

was performed.

6.2 Crystal structure of the [CycljPAu(6p2-fu)] complex

The complex [Cycl3PAu(6p2-TU)] was prepared by the literature methodl9; crystals of the

complex were obtained from the slow evaporation of a saturated ethanolic solution of the

compound, and the complex crystallizes in the monoclinic space group PLtlc (C25n, ltto- lÐ44.
 64

Table 6.2.12 Crystallographic Parameters For The [CycþPAu(6p2-fU)] Complex

Data lCyclgPAu(6p2-TU)l
Formula C25Ha2AuSPONz
Formula weight 646.6
Crystal shape rectangular prism
Crystal dimensions (mm) 0.16x0.16x0.29
Crystal system monoclinic
Space group P2tlc 1Ç, No. t+¡
4 (Å) e.s3e(2)
b (Å) 16.4s2(4)
c (Å) 16.880(2)
p (") es.37(2)
v (År¡ 2637.4(8)
Z 4
pc¿c. (g c--3) r.628
F(000) )z{ 216
u (cm-l) 57.56
0 limits, cell (') 13.1 to 15.4
0 limits, data (") 1.5 to 27.9
hklrange 0 to 12, 0 to 21, -20 to 20
Range of transmission factors 0.985 to 1.012
Scan technique a;20
No. of data measured 6899
No. of unique data 6524
Ramal 0.060
No. of unique data used 369s
Criterion of observability 1> 3.0o(Ð
No. of parameters 280
R 0.043
Rw 0.039
Residual electron density (e Å-l¡ -1.28 to 0.90
 65

Crystat and refinement data are listed in Table 6.2.1, and the derived results are given in Tables

6.2.2 to 6.2.7. The observed and calculated structure factors can be found in the Appendix.

The crystallographic numbering scheme is shown in the ORTEP45 diagram in Figure 6.2.1,

plotted with 30 Vo thermal ellipsoids.

The unit cell contents of [Cycl3PAu(6p2-TU)] are displayed in Figure 6.2.2 and are clearly

demonsrrative of the P21lc space group. As observed in other triorganophosphinegold(I)

derivatives containing the thiouracilate anion9,19,6l, centrosyrnmetrically related molecules are

associated via hydrogen bonding contacts in the lattice. They involve the N(3)-H(3) and O(4')

aroms such that the H(3)...O(4') separation is 1.90 Å and the N(3)-H(3)...O(4') angle is 161'
(symmetry operation for O(4') is -x, l-y, -z)" The closest gold to gold interaction is

3.460(1) ,4,, which is too large to be considered as a'significant' interaction46.

The molecular structure of [Cycl3PAu(6p2-TU)] is shown in Figure 6.2.2. As expected, the

P-Au-S chromophore is linear, the angle being 171 .6(1)" . The P(lFAu and Au-S(2) bond

lengrhs are 2.248(3) and 2.302(3) Å respectively. These values are equivalent to those

observed for the related complex [Cycl3PAu(6m2-TU)177 the implications of this will be

discussed in the next section. The three P-C bond lengths are all equivalent to within standard

deviation, suggesting the electronic environment about these bonds is identical. The cyclohexyl

g¡oups exist in the'chair' conformation; relatively large thermal motion is associated with these

atoms.

The 6-n-propyl-2-thiouracilate moiety is coordinated as expected to the gold centre via the

sulphur atom, as a thiolate rather than a thione. The two bond distances of N(1)-C(2) and

N(3FC(2) are 1.28(1) and 1.37(l) Å respectively, indicating the former has greater double
bond character. Hence deprotonation of the free ligand occurs at N(1), consistent with results

observed for other triorganophosphinegold(I) thiouracilates9,19,62,18. The distance between

N(1) and Au is 3.061(9) ,Ä,, less than the sum of the van der V/aal radii, but, like with the two

$-mercaptopurinate complexes in Chapter 5 and other analogous complexes, not indicative of a

Table 6.2.2: Fractional Atomic Coordinates For The [CycllPAu(6p2-TU)] Complex

Atom x v z

Au 0.40117(4) 0.7rs2s(3) 0.226s2(3)

s(2) 0.26s3(3) 0.6070(2) o.1792(2)

P(1) 0.5417(3) 0.8183(2) 0.21r4(2)

o(4) -0.01s1(e) o.s63s(s) -0.0732(s)

N(1) 0.2t4s(e) 0.7192(6) 0.0689(6)

N(3) 0.1137(8) 0.se37(s) 0.0415(s)

c(2) 0.1es7(9) 0.64s8(7) 0.08e6(6)

c(4) 0.0s25(13) 0.6143(8) -0.0323(8)

c(s) 0.0743(1s) 0.6972(9) -0.0507(8)

c(6) 0.rs23(r4) 0.746r(e) -0.000e(e)

c(l1) 0.7079(10) 0.8113(6) o.227e(6)

c(12) 0.8076(11) 0.8823(7) 0.242s(7)

c(13) 09317(r2) 0.8727(8) 0.1e28(8)

c(14) 1.0081(12) 0.79s0(10) 0.2090(8)

c(15) 0.9106(13) 0.t232(8) o.2002(t)

c(16) 0.7821(11) 0.7306(7) 0.24s0(6)

c(21) 0.5778(14) 0.8208(8) 0.31e4(7)

c(22) 0.6t44(r4) 0.e027(8) 0.4149(8)

c(23) 0.6442(26) 0.8949(1 1) 0.s0s6(10)

c(24) 0.6002(24) 0.8381(1s) 0.5457(10)

c(25) 0.s671(18) 0.761s(10) 0.s 100(9)

c(26) 0.s342(2s) 0.7634(rr) 0.4218(e)

c(31) 0.4687(10) 0.9161(6) 0.23es(6)

c(32) 0.3266(12) 0.929t(7) 0.2614(8)

c(33) o.2670(12) 1.0126(8) 0.2380(11)

 Table 6.2.2 (c o ntinued)

c(34) 0.2619(17) 1.0240(e) 0.1s33(10)

c(35) 0.4042(Ls) 1.0090(e) 0.1268(8)

c(36) 0.4s80(12) 0.e267(7) 0.1sOs(7)

c(61) 0.t764(2r\ 0.8342(10) -0.0176(11)

c(62) 0.1260(26\ 0.8678(12) -0.o779(16)

c(63) o.1669(22) 0.950e(11) -0.0911(14)

..,
Tabte 6.2.32 Anisotropic Thermal Parameters For The [CyclsPAu(6p2-fu)] Complex

Atom Urr Uzz U¡¡ Un Ur¡ Uzz

Au 0.0382(2) 0.0390(2) 0.0s47(2) -0.0046(3) -0.0015(2) -0.0068(3)

s(2) 0.0s2(2) 0.042(2) 0.06s(2) -0.007(1) -0.013(2) 0.000(1)

P(1) 0.042(2) 0.038(2) 0.046(2) -0.00s(1) 0.003(1) -0.006(1)

o(4) 0.108(7) 0.074(7) 0.091(7) -0.033(6) -0.047(6) 0.013(6)

N(1) 0.060(6) 0.046(6) 0.07s(7) -0.013(6) -0.011(s) 0.008(6)

N(3) 0.043(6) 0.041(6) 0.066(7) -0.00s(4) -0.013(s) 0.00s(s)

c(2) 0.024(6) 0.044(7) 0.067(8) -0.000(5) -0.003(s) -0.012(6)

c(4) 0.060(e) 0.07(1) 0.07(1) -0.01s(7) -0.023(7) -0.002(8)

c(5) 0.11(1) 0.07(1) 0.10(1) -0.02(1) -0.04(1) 0.04(1)

c(6) 0.0e(1) 0.07(1) 0.10(1) -0.017(8) -0.032(e) 0.011(9)

c(11) 0.037(6) 0.048(7) 0.04e(7) -0.001(s) 0.00s(5) 0.00s(s)

c(12) 0.036(7) 0.064(e) 0.0e(1) -0.007(6) 0.008(6) -0.010(7)

c(13) 0.048(e) 0.07(1) 0.1 3(1 ) -0.009(7) 0.02e(8) -0.00(1)

c(14) 0.0s2(8) 0.10(1) 0.13(1) -0.012(e) 0.034(8) -0.04(1)

c(15) 0.068(e) 0.08(1) 0.0e(1) 0.017(e) 0.024(8) -0.01s(e)

c(16) 0.0s2(8) 0.06(1) 0.068(8) 0.013(6) 0.017(6) -0.007(7)

c(21) 0.13(1) 0.062(e) 0.04e(8) -0.044(8) 0.021(8) -0.016(7)

c(22) 0.12(1) 0.08(1) 0.06(1) -0.013(e) 0.004(8) -0.009(8)

c(23) 0.41(3) 0.10(2) 0.06(1) -0.06(2) 0.00(2) -0.04(1)

c(24) 0.23(2) 0.23(3) 0.06(1) -0.0e(2) 0.01(1) 0.06(2)

c(25) 0.t6(2) 0.10(1) 0.08(1) -0.06(1) -0.00(1) 0.01(1)

c(26) 0.43(3) 0.16(2) 0.04(1) -0.16(2) 0.01(1) 0.02(1)

c(31) 0.043(7) 0.046(7) 0.0s 1(7) -0.005(6) 0.007(6) -0.013(6)

c(32) 0.0s0(8) 0.061(9) 0.1 1(1) 0.004(7) 0.001(8) -0.023(8)

c(33) 0.043(e) 0.047(9) 0.22(2) 0.017(7) -0.01(1) -0.04(1)

 Table 6.2.3 (continued)

c(34) 0.12(1) 0.07(1) 0.12(1) 0.02(1) -0.06(1) 0.01(1)

c(3s) 0.10(1) 0.08(1) 0.10(1) 0.02(1) -0.02(1) 0.024(9)

c(36) 0.070(9) 0.066(e) 0.066(e) 0.02t(7) -0.00e(7) 0.007(7)

c(61) 0.2s(2) 0.07(1) 0.ls(2) -0.08(1) -0.r2(2) 0.07(1)

c(62) 0.30(3) 0.11(2) 0.30(3) -0.07(2) -0.12(2) 0.13(2)

c(63) 0.28(3) 0.0e(2) 0.29(3) -0.04(2) -0.03(2) 0.11(2)

I
Table 6.2.4: Hydrogen Atom Parameters For The [CycljPAu(6p2-TU)] Complex.

Atom X v z B(eq)

H(3) 0.0983 0.5403 0.0606 5.2

H(s) 0.0309 0.7r87 -0.1007 9.r

H(11) 0.6835 0.8113 0.17 10 4.5

H(12a) 0.7592 0.9325 0.2277 6.1

H(12b) 0.8429 0.8843 0.2984 6.1

H(13a) 0.8977 0.8745 0.1369 7.8

H(13b) 0.9975 0.9r73 0.2047 1.8

H(14a) r.0794 0.7895 0.r719 8.2

H(14b) 1.0532 0.7962 o.2629 8.2

H(15a) 0.8807 0.7166 0.144r 1.4

H(1sb) 0.9637 0.6755 0.2193 7.4

H(16a) 0.8115 0.7267 0.3016 5.7

H(l6b) 0.7r87 0.6867 0.229r 19.8

H(21) 0.6743 0.8015 0.380s 1.2

H(22a) 0.6973 0.9239 0.3922 7.7

H(22b) 0.536s 0.9396 0.4033 1.1

H(23a) 0.7488 0.8927 0.5152 t6.4

H(23b) 0.6130 0.9448 0.5218 4.2

H(24a) 0.5164 0.8585 0.5663 14.9

H(24b) 0.6726 0.828s 0.s896 14.9

H(25a) 0.4859 0.7404 0.5333 10.0

H(2sb) 0.647r 0.7256 0.5225 10.0

H(26a) 0.4335 0.1627 o.4r2l 18.0

H(26b) 0.5735 0.7t36 0.4020 18.0

H(31) 0.5304 0.9582 o.2629 4.5

Table 6.2.4 (co ntínued)

H(32b) 0.2628 0.8864 0.2463 7.2

H(32a) 0.3329 0.9276 0.325L 7.2

H(33a) 0.17t9 1.0180 0.2545 8.7

H(33b) 0.3260 1.0548 0.263s 8.7

H(34a) 0.1927 0.9860 0.t275 9.4

H(34b) 0.2300 t.0791, 0.1405 9.4

H(35a) 0.3970 1.0137 0.0694 8.7

H(3sb) 0.467r 1.0498 0.1506 8.7

H(36a) 0.5502 0.9201 0.r32r 6.5

H(36b) 0.3943 0.88s9 0.1260 7.2

H(61a) 0.1410 0.8639 0.0265 15.1

H(61b) 0.2761 0.8412 -0.0167 15.1

H(62a) o.1496 0.8361 -0.t226 19.8

H(62b) 0.0226 0.8671 -0.0765 19.8

H(63a) 0.2661 0.9548 -0.0876 17.8

H(63b) 0.1255 0.9678 -0.1439 17.8

H(63c) 0.1281 0.9857 -0.0515 20.8

Table 6.2.52 Bond Distances (Å) por The [CycIjPAu(6p2-TU)] Complex

Atom Atom Distance Atom Atom Distance

Au s(2) 2.302(3) c(13) c(14) 1.48(2)

Au - P(1) 2.248(3) c(14) c(15) 1.50(2)

s(2) c(2) 1.72(r) c(32) c(33) 1.5s(2)

P(1) - c(11) 1.81(1) c(33) - c(34) 1.44(2)

P(1) c(2r) 1.82(1) c(34) c(35) r.49(2)

P(1) c(31) 1.82(1) c(35) c(36) r.4e(2)

o(4) c(4) r.23(1) c(61) c(62) r.22(2)

N(1) - c(2) 1.28(1) c(62) c(63) r.44(2)

N(1) c(6) 1.34(r) c(1s) c(16) 1.s0(1)

N(3) - c(2) 1.37(1) c(2r) c(22) 1.s0(2)

N(3) c(4) 1.37(r) c(2t) c(26) r.28(2)

c(4) c(s) r.42(2) c(22) c(23) 1.s4(2)

c(.5) c(6) r.34(2) c(23) c(24) r.2s(2)

c(6) c(61) 1.s0(2) c(24) c(zs) r.42(2)

c(l1) c(rz) 1.s 1(1) c(2s) c(26) t.4e(2)

c(11) c(16) 1.52(1) c(31) c(32) 1.49(r)

c(t2) c(13) 1.s2(l) c(31) c(36) 1.s1(1)

Table 6.2.6: Bond Angles ( ") For The [Cycl jPAu(6p2-TU)] Complex

Atom Atom Atom Angle A¡om Atom Atom Anele

s(2) - P(1) n7.6(r) c(l1) - c(rz) c(13) 1 10(1)

Au - c(2) 100.2(4) c(12) - c(13) c(14) rr2(r)

Au - c(l1) 109.4(3) c(13) - c(14) c(1s) tr2(1)

Au - c(zt) rr3.e(4) c(14) - c(1s) c(16) 1 14(1)

Au - c(31) 11 1.6(3) c(11) - c(16) - c(ls) 11 1(1)

c(11) - c(2r) 108.4(s) P(1) - c(zr) c(22) 11s.7(9)

c(11) - c(31) 10s.2(5) P(1) - c(zr) c(26) 120(1)

c(21) - c(31) 107.e(s) c(22) - c(zr) c(26) Lzr(r)

c(2) - c(6) 1 19(1) c(zr) - c(22) c(23) 1 10(1)

c(2) - c(4) r24(r) c(22) - c(23) c(24) r24(2)

s(2) - N(1) 122.7(8) c(23) - c(24) c(zs) r20(2)

s(2) - N(3) 116.1(8) c(24) - c(zs) c(26) 1 1s(1)

N(1) - N(3) r2r(1) c(2t) - c(26) c(zs) 122(2)

o(4) - N(3) 120(1) P(1) - c(31) c(32) 11 1.6(8)

o(4) c(s) 128(1) P(1) - c(31) c(36) rr2.1(7)

N(3) - c(s) 112(1) c(32) - c(31) c(36) 108.7(9)

c(4) - c(6) 122(1) c(31) - c(32) c(33) 1 10(1)

N(1) - c(s) r22(r) c(32) c(33) c(34) 114(1)

N(1) - c(61) 1 1s(1) c(33) - c(34) c(3s) 10e(1)

c(s) - c(61) t23(r) c(34) - c(3s) c(36) rr2(r)

P(1) - c(12) 116.s(8) c(31) - c(36) c(35) 111(1)

P(1) - c(16) 112.8(7) c(6) - c(61) c(62) r23(2)

c(rz) - c(16) I 1 1.7(8) c(61) - c(62) c(63) 118(2)

I

Table 6.2.7: Mean Plane Data ForThe [CycljPAu(6p2-TU)] Complex.

Least squares plane through the Gn-propyl-2-thiouracilate moiety.

Atoms Definine Plane Pistance (Å) esd (.Ä')

i
i
I
N(1) 0.0075 0.0092
I
¡
!

N(3) -0.0156 0.0085

Ì

CQ) 0.0059 0.0095

c(4) 0.0294 0.0130

c(s) -0.0075 0.01s5

c(6) -0.0203 0.0149

AdditionalAtoms Distance (Ä.)

Au 0.1910

s(2) -0.0235

P(1) 0.4893

o(4) 0.0s83

c(61) -0.0760

c(62) -0.1189

c(63) -0.0444

Mean deviation from plane is 0.0144 (Å).

1
Chi-squared: 9.9.
i

ì
 c63

c62

c6l C5
c34

o4
C4
c36
N1
c33
c N3
c3l C2
c12
c3z
cl1
PI Au S2
c14
cl5
cl6

c22 czt

c26

cz3
c25
c24

Figure 6.2.L: Molecular Structure And Crystallographic Nwnbering Scheme For

[Cycl jPAu(6p2-ru)] .
 +c
0

Figure 6.2.22 Unit Cell Diagrarn Of [CyclsPAu(6p2-TU)]

 66

bonding interaction. High thermal motion is noted for the carbon atoms of the propyl chain; this

was also observed in the [Et3PAu(6p2-fU¡0t complex.

The crystal structure of 6-n-propyl-2-thiouracil has been reported in the literatureTS; however,

the relatively high errors associated wittr the light atom positions in the complex and those in the

structure of the thionucleobase itself preclude a meaningful discussion conceming the derived

parameters. The structure of this complex is closely related to [Cycl3PAu(6m2-TU)]77 (1),

lEt3PAu(6p2-TUl61 (2), Bt3PAu(2-TU¡e (3) and [Ph¡PAu(2-TU)]le (4). Comparisons can

hence be made between these complexes for the thiolate group. Table 6.2.8 shows the
intramolecula¡ bond distances involved.

Table 6.2.8: Bond Distances ¡Å¡ f or The Thíouracilate Moiety

lCyclqPAu(6p2-Tu)l 1 2 3 4

s(2)-c(2) r.72(L) 1.73(1) t.1r(2), r.74(2) r.7z(r) r.722(8), r.765(7)

N(1)-c(2) 1.28(1) r.29(t) 1.33(2), 1.30(2) 1.31(1) 1.33(1), r.29(r)

N(1)-c(6) 1.34(1) 1.37(1) r.37(2), 1.38(2) r.37 (r) r.37(t), 1.39(l)

N(3)-c(2) t.37(t) 1.3s(1) r.37(2), 1.36(2) l.3s(1) r.36(1), 1.34(l)

N(3)-C(4) 1.37(1) 1.40(1) r.43(2), r.36(2) 1.38(1) r.37(l), 1.40(l)

c(4)-c(s) 1.42(2) 1.3e(1) 1.43(2), r.3e(2) 1.40(1) 1.41(1), 1.41(5)

c(4)-o(4) r.23(r) 1.23(t) t.zs(z), r.23(2) r.24(r) 1.25(1), 1.24(r)

c(s)-c(6) r.34(2) r.34(2) r.33(2), r.3s(2) r.3s(2) 1.35(1), 1.34(1)

It is evident from Table 6.2.8 that most of the constituent distances are equivalent within

standard deviation between the three complexes (both [Et¡PAu(6p2-TU)] and [Ph3PAu(2-TU)]

contained two molecules each in their asymmetric crystallographic units). The electron density

around the ring is also identical, with C(4)-O(4) and C(5)-C(6) possessing the expected double

bond character in all the structures. This suggests that the internal structure of ligands based on

2-thiouracilate is independent of the nature of the phosphine group and of the alkyl groups
 67

external to the aromatic system. Mean plane calculations show that the six atoms of the

thionucleobase in [Cycl3PAu(6p2-TU)] form a planar system, with a mean deviation of

0.01(1) Å. fne O(4), C(61) and S(2) aroms lie out of the plane by 0.0583, 0.0760 and

0.0235 Å, respectively.

6.3 C o ne - an g Ie co rr el atio n for tior g arnp ho sp hi ne g o I d( I ) t hi o la t e s

As discussed in Chapter 3, the cone-angte is a parameter that quantifies the steric effect of

bulky phosphine groups. Triorganophosphinegold(I) thiolates of the general formula

[R¡PAu(SR')], where the SR' group is a thionucleobase derivative, contain two bulky ligands,
as the thiolate moiety can have significant size. The cone-angle correlation study for

triorganophosphinegold(I) chlorides indicated that the P-Au bond distance in these complexes

is invariant when the individual molecules crystallize as discrete molecules, i.e. with no

significant intermolecular interactions such as close Au...Au contacts. However, the presence

of another bulky ligand bound to the gold centre may cause a variation in the P-Au values in a

series of complexes, or result in noticeable trends in the Au-S or P-Au-S chromophores.

Table 6.3.1 shows the important intramolecular parameters for a representative selection of

triorganophosphinegold(I) thiolates reported in the literature. No significant Au...Au

interactions were reported for any of these complexes. The cone-angles for Et3P, Ph3P, Cycl3P

and (o-Tol)3P are 732, L45,170 and 194 ' respectivel/9, and the complexes are listed in Table

6.3.1 in order of increasing cone angle. The P-Au bond distance ranges in length from

2.248(2) to 2.255(5).Ä. for the Et3P complexes ,2.237(2) to 2.260(3) Ä for Ph3P, 2.244(3) to

2.292(3)Å for Cycl3P and,2.239(2) Å for [(o-Tol)¡PAu(6-MP)]. Not considering the value for

[Ph3PAu(6-MP)], the values for the other Ph3P complexes are all equivalent within standard
deviation, and this is also the case for the two Et3P complexes. The P-Au range for the Cycl3P

complexes appears large; however, [Cycl3PAu(2mba)] displays intermolecular hydrogen

bonding, and 1-methyl-2-mercaptoimidazole is not a true thionucleobase derivative. Notable is

that these two complexes possess no close Au...N interactions. Also notable is that the Au...N

contacts for [Ph3PAu(6-MP)] and [(o-Tol)3PAu(6-MP)], which display the shortest P-Au
 68

Table 6.3.1: Intramolecular Parameters Of The P-Au-S Chromophore

Complex Au-p (Å) Au-s (Ä.) P-Au-S (") Au...N (Å) Ref

IEt3PAu(2-TU)] 2.248(2) 2.310(2) t7 6.9(r) 3.113(2) tel

[Et3PAu(6p2-TU)] 2.24e(s) 2.328(4) 17s.0(2) 3.r2(r) t6ll

2.2ss(s) 2.314(s) 176.9(2) 3.11(1)

IPh3PAu(2-TU)] 2.248(2) 2.296(2) 17s.4(2) 3.23(r) tlel

2.248(2) 2.300(2) r77.0(2) 3.13(1)

[Ph3PAu(2-pyms)] 2.2s3(2) 2.310(3) tt 4.7 (L) 2.951(8) Í62)

[Ph3PAuLl] 2.2s6(2) 2.308(2) 178.6(2) 3.312(4) Í7el

[Ph3PAu(2-pys)] 2.2s8(r) 2.297(2) r77.9(t) 3.1 18(4) t62l

lPh3PAuL2l 2.2s8(2) 2.299(2) r7 6.43(8) 3.414(4) t80l

lPh¡PAu(S-CoHs)l 2.2s9(2) 2.296(2) 179.12(t) t81l

2.2s8(2) 2.302(2) 17 s.7e(6)

[Ph3PAu (S -2,4,6- C1HzMe ¡ ) ] 2.2ss(2) 2.284(2) 17s.24(7) t81l

[Ph¡PAu(S -2,4,6-CdH2Et3)] 2.260(3) 2.288(4) 176.2(r) t81l

[Ph3 PAu (S -2,4,6- C6Hz iPr¡ ) ] 2.2ss(2) 2.284(2) 176.3s(s) t81l

This
[Ph3PAu(6-MP)] 2.237(2) 2.287(r) r73.7 r(6) 2.884(s)
work

[Cycl3PAu(2mba)] 2.27r(r) 2.3r3(r) 176.8(l) Í62)

ICycl3PAuL3] 2.292(3) 2.330(3) 172.O(r) 3.64r(s) Í821

[Cycl3PAu(6m2-TU)] 2.244(3) 2.zee(3) 176.1 (r) 3.0e5(8) u7t

This
[Cycl3PAu(6p2-TU)] 2.248(3) 2.302(3) r77.6(r) 3.061(9)
work
This
[(o-Tol)3PAu(6-MP)] 2.23e(2) 2.266(2) 177.03(8) 2.860(7)
work
Note: LlH = 8-mercaptotheophylline,L2lH = 2-mercaptobenzoxazole and L3H = l-methyl-2-
mercaptoimidazole.
 69

distances, are signif,rcanty shorter than in the other complexes. Hence, the P-Au bond distance

appears to be independent of the cone-angle for those complexes containing six-membered

aromatic thionucleobase derivatives.

The Au-S bond distance shows a greater variation between the complexes, with a range

extending fuom2.266(2) to 2.330(3) Å. Howeuer, the variation is not related to the size of the

phosphine cone-angle, nor does it appear to depend on the size of the thiolate e.g. in the series

represented by the complexes of the general formula [Ph¡PAu(S -2,4,6-C6HzR¡)]81 where

R = H, Me, Et or iPr, the2,4,6-C6Íl2iPry ligand would intuitively have the larger steric effects,

but the COHs ligand gives rise to the longest Au-S bond in the resultant complexes. The

P-Au-S bond angle displays the range of values 172.0(l) to 179.12(7)". These values also
appeil to be independent of the bulkiness of the two ligands bound to the gold. The Au...N
intramolecular contact varies largely in size, but maintains a relatively narrow range of 3.061(9)

to 3.23(1) Å when the thiolate is a derivative of 2-thiouracil.

The conclusions from the analysis of monodentate triorganophosphinegold(I) thiolates based

on thionucleobase related moieties are as follows: the linearity of the P-Au-S moiety is largely

unaffected by the nature of the phosphine or thiolate bound to the gold centre; the P-Au and

Au-S bond distances are independent of the cone-angle of the phosphine, but can be affected

by the nature of the coordinated thiolate; and the Au...N interaction is of a secondary nature.

The intramolecular parameters of the P-Au-S are thus not determined by steric factors but are

more likely determined by the electronic effects of the coordinating thiolate.

 70

CHAPTER 7

Assessment of Anti-Arthritic Activity

The effectiveness of the complexes described in this thesis against rheumatoid arthritis was

determined via in viyo biological testing. The assessment was performed by Dr. M.W.

Whitehouse and co-workers at the Departrnent of Pathology, The University of Adelaide.

The complexes were tested on both male and female Dark Agouti rats. The choice of these

rodents is based on the knowledge that Dark Agouti rats possess an immune response to

rheumatoid arthritis which resembles closely that of humans, and this particular breed has been

found to be sensitive to gold-based drugs. Hence, any positive results obtained may be

extrapolated to give justification for later testing on humans.

Tests are continuing at the time of writing, but some interesting results have already been

obtained for a selection of complexes. The protocol of testing involves injection of an

arrhdtogen into the hind leg to induce swelling in the tail base and hind quarter joints. [n a

preliminary trial, the complex [Ph3PAu(6-MP)], as 100 mg in saline solution, was co-
administered with the arthritogen as a single dose to a female specimen" 6-mercaptopurine

(6MPH), Auranofin and [Au(CN)2]- were similarly injected and assayed against an untreated

specimen. The results a¡e summa¡ized in Table 7.1.

The untreated specimen, injected only with arthritogen, suffered weight loss and a significant

increase in swelling in the hind quarters, an obviously adverse reaction. By comparison, the

other complexes produced greater than 50Vo less swelling, indicating the complexes were
 7l

Table 7.Iz Biological Data For Femnle Dark Agouti Rats Afier Anti-arthritic Treatment.

Complex milligram dose Aweight (g) Apaw swelling (mm)

[Ph3PAu(6-MP)] 100 +09 0.37

6MPH 25 +09 0.51

Auranofin 100 +03 0.71

lAu(CN)zl- 20 +14 0.10

Untreated -11 1.83

negating the effects of the arttritogen to a large extent. [Au(CN)z]- was most successful, being

the species mentioned in Chapter 1 as being perhaps the main active species in the inflammation

reduction process. [Ph3PAu(6-MP)] leads to only half the swelling than for Auranofin in these

trials, and to an increase in weight, so that the rat is generally healthier. Auranofin has also been

observed to be toxic to specimens when given as multiple doses8. Therefore [Ph¡PAu(6-MP)],

on the basis of these results, appears to be more successful than Auranofin in treating
rheumatoid arthritis, at least in this model. Gmercaptopurine itself also appears to be beneficial.

Three other complexes have been tested via eight regular doses after initial arthritogen

injection. The results are given in Table 7.2.

Table 7.22 Biological Data For Female Dark Agouti Rats After Anti-arthritic Treatment

Complex milligram Aweight (g) Apaw swelling incidence of Rating

dose (mm) disease

lEr3PAu(6-MP)l 10 -09 0.45 013 +

ICycl3PAu(6-MP)] 10 -05 0.08 013 +

[(n-Tol)¡PAu(6-MP)] 10 -n 1.07 213 +3

Untreated -19 1.69 +4

 72

Incidence of disease indicates how many specimens of the three rats tested for each complex

acquired the symptoms of arth¡itis. Thus it is evident from qualitative analysis of Table 7 .2 that

both [EI3PAu(6-MP)] and [Cycl3PAu(6-MP)] are very efficient at combatting the disease.

However, the associated weight loss indicates that some side effects are present which are

clearly detrimental to the health of the rats. The effectiveness of each complex was determined

via a qualitative rating systemS, indicating severity of disease, compared simultaneously with

the results obtained from the standard, aurothiomalate. A number of factors were assessed,

including weight, overall health of the rat and the effect on the swelling. From the same testing

protocol, Auranofin receives a rating of +, so [Et3PAu(6-MP)] and [Cycl3PAu(6-MP)] are

comparable with this complex. [(rn-Tol):PAu(GMP)] evidently has little effect on swelling and

produces a significant weight loss, hence a rating of +3, only slightly more effective than no

treatment at all. On the same scale, [Ph¡PAu(6-MP)] would receive a rating of + or even 0.

Some interesting observations can hence be made in terms of a tentative structure/activity

relationship. 6-mercaptopurine and its complexes appear to have a significant effect on a¡thritic

swelling; possibly the solubility characteristics of this ligand provide for a comparatively large

quantity of gold to be transferred to the site of actionS. Comparisons with

triorganophosphinegold(I) thiouracilates with the same phosphine show an improvement in

acriviry with the change in thiolate e.g. [Ph3PAu(2-TU)] and [EI3PAu(2-TU)] have ratings of

+2 and +3 respectivelyS'9. The triphenylphosphine ligand also appears to be the best phosphine

in terms of both activity and toxicity (roughly associated with weight loss); the addition of a
methyl group, as in [(m-Tol)3PAu(6-MP)], gives a significant decrease in the efficiency of

treatment. This difference might be related to the comparative solubilities of the phosphine

ligandsS. Generally, the effectiveness of the complexes is in the order of Ph3P > Cycl3P > Et3P

> (rn-Tol)3P, in accordance with ea¡lier ¡s5ul¡s9,10.

The combination of Ph3P and 6-MPH thus appears to possess suitable characteristics for an

effective gold(I) complex which could be utilized in the treatment of rheumatoid arthritis. This

is at variance with the structure of the Et3P-containing drug Auranofin, but the effectiveness of
 t3

[PhjPAu(6-MP)] is promising. Further work is continuing on the other complexes, to possibly

result in an improved understanding of any structure/activity relationship that exists for

triorganophosphinegold(I) tltiolates.
 74

CHAPTER 8

Conclusion

The aim of the work presented in this thesis was to synthesize a range of novel

triorganophosphinegold(I) complexes containing the 6-mercaptopurinate ligand and a variety of

phosphines, with possible applications in the treatment of rheumatoid arthritis. Complexes of

the type [R3PAu(6-MP)] (where R3P = Et3P, Cycl3P, PhMe2P, Ph3P, (o-Tol)3P, (nt-Tol)3P

or (p-Tol)3P), t(PhzP(CHz)nPPhzXAuCl)(Au(6-MP))l (where n = 2 ot 3), and

t@h2P(CHz)nPPhz)(Au(6-MP))zl (where n = 1, 2 or 3) were prepared from the corresponding

triorganophosphinegold(I) chloride precursors via the metathetical reaction with base and

6-mercaptopurine in the appropriate molar quantities, as described in Chapter 2. The

composition and purity of the samples was determined from microanalytical and spectroscopic

evidence.

The triorganophosphinegold(I) chloride and triorganophosphinegold(I) 6-mercaptopurinate

complexes were characterized using the techniques of infrared and multinuclear nuclear

magnetic resonance (nmr) spectroscopy (lH and 13C, and 3lP for the 6-MP complexes), and

for the 6-mercaptopurinate complexes by Fast Atom Bombardment - mass spectroscopy (FAB-

MS). Infrared data obtained for these complexes indicated complex formation via the
appearance of both 6-mercaptopurine and phosphine absorption peaks in the spectra, and by

alteration of the frequencies of the thioamide chromophore. Absorptions of the phosphine

moieties were found to be independent of the presence of the purine moiety.

 75

The resonances and integration found in the lH nmr spectra of the complexes are consistent

with the proposed stoichiometries. The chemical shifts of the H2 and H8 proton resonances

showed little variation with complexation. The 13C nmr spectra revealed that the C5 and C8

nuclei were the most sensitive to, and thus the most indicative of, complexation. 31P nmr

spectra showed single signals in all the spectra, which suggested that, for the complexes with

the general formula [(PhzP(CHz)nPPhzXAuCl)(Au(6-MP))1 (where n = 2 or 3), the two

independent phosphorus atoms possess the same resonance frequency. Low temperature nmr

studies on one of these complexes revealed two signals, thus suggesting the ligands are

fluctional at ambient temperature.

The FAB-MS studies of the complexes revealed the occurrence of high nuclearity phosphorus-

gold(I)-sulphur clusters in most of the complexes, consistent with the observations for other

triorganophosphinegold(I) thiolates. The molecular ion was more coÍìmonly observed for the

complexes of the type [R3PAu(6-MP)], but the aggregate containing two gold atoms to one

6-mercaptopurinate fragment was observed in high abundance for the complexes based on the

dpp-, dppe and dppp phosphines also. No otherwise significant trends were observed for the

latter series. The combined spectroscopic evidence suggested product formation in all cases,

with no significant differences between the complexes.

Single crystal X-ray structure determinations were performed on the complexes

lPhMezPAuCll, [Ph¡PAu(6-MP)].CzHsOH, [(o-Tol)¡PAu(6-MP)].CzHsOH and

[Cycl3PAu(6p2-TU)]. The studies all revealed the near linear P-Au-Cl or S chromophore
expected from analogous examples found in the literature. The results from the analysis of

[PhMe2PAuCl] were used in a study to comp¿ìre the phosphine cone angle (0) and a new
quantiry found in the literature, the ligand repulsive energy @p), with the P-Au and Au-Cl

bond lengths for a variety of structurally characterized triorganophosphinegold(I) chloride

complexes. The study revealed that the P-Au bond distance was independent of 0 for
complexes containing no signif,rcant gold to gold interactions in the lattice- As expe.cterl, the

Au-Cl bond length was found to be unrelated to 0 and probably dependent on electronic
factors. The Ep quantity appeared to be no better than 0 in determining any steric effects of the
 16

phosphine on the rest of the molecule, despite its more sophisticated calculation. The crystal

structure determinations on [Ph3PAu(6-MP)].CzH5OH and [(o-Tol)¡PAu(6-MP)].CzHsOH

confirm the spectroscopic observations and reveal that the deprotonated 6-mercaptopurine

molecule is coordinated in a monodentate mode to the gold(I) atom via the sulphur atom

exclusively. The Gmercaptopurine moiety is planar, and is oriented with the N(7) atom di¡ected

to rhe gold(I) atom; similar observations have been made for other triorganophosphinegold(I)

thiolates. The six-membered ring system displays a general shortening of all the constituent

bonds upon complexation when compared to the free ligand, an effect that is expected due to

the changes in aromaticity. The observed alterations in intramolecular parameters are consistent

with the spectroscopic data. The complex [Cycl3PAu(6p2-TU)] possessed intramolecular

characteristics consistent with analogous complexes- The phosphine and thiolate groups in

triorganophosphinegold(I) thiolates have no discernable steric effects on the P-Au-S

chromophore, the variations in the intramolecular parameters likely being due to electronic or

packing factors.

The complexes that were assessed for their anti-arthritic activity were found to be generally

effective, with activity ratings rivalling that of the clinically available drug Auranofin. The

complex [Ph3PAu(6-MP)] showed improved activity and less toxicity over Auranofin on a

rating scheme based on the severity of rheumatoid arthritis experienced by Dark Agouti rats.

The trend of Ph3P being more active than Cycl3P which was more active than Et3P or
(m-Tol)¡P for the same thiolate utilized was observed, consistent with earlier results. The

$-mercaptopurine ligand was found to be effective as the thiolate ligand, which is possibly

related to its solubility in the bodily fluids.

This project also has further scope in the study of the anti-arthritic activity of these complexes.

For instance, specially modified phosphines or 6-mercaptopurinates could be utilized, and the

resultant gold(I) complexes investigated to determine what effects sructural alterations have on

the activity of these types of complexes, and possibly lead to a better understanding of the

structure / activity relationships.

 REFERENCES

1 E.R.T. Tiekink and M.W. V/hitehouse, Chem. Aust.,57,346-348 (1990)

2 C.K. Mirabelli, R.K.Johnson, L.F. Faucette, C-M. Sung, K. Muirhead and S-T
Crooke, Can. Res., 45, 32-39 (1985).

3 S.J. Berners-Price, C.K. Mirabelli, R.K.Johnson, M.R. Mattern, F.L. McCabe,

L.F. Faucette, C-M. Sung, S-M. Mong, P.J. Sadler and S.T. Crooke, Can. Res.,
46,5486-5493 (1986).

4 R.V. Parish, Interdisc. Sci. Rev., L7 , 221-228 (L992).

5 G.J. Higby, Gold Bull.. 15, 130-140 (1982).

6 J. Reedijk, A-M.J. Fichtinger-Schepman, A.T.van Oosteron and P. van de Putte,

Struct. Bond.,67, 53-87 (1987).

7 E.M. Kinsch and D.w. Stephan, Inorg. chim. Acta,9I,263-267 (1984).

8 M.V/. Whitehouse, personal communication.

g C.S.W. Harker, E.R.T. Tiekink and M.W. Whitehouse, Inorg. Chim. Acta,l8l,
23-30 (1991).

10 P.D. Cookson, Honours Report,The University of Adelaide, 1991.

11 K.C. Agrawal, K.B. Bears, D. Marcus and H.B. Jonassen, Proc. Am. Soc. Cancer
Res., L9,23 (1978).

12 S.M. Skinner, J.M. Swatzell and R.W. Lewis, Res. Comm. Chem. Path. Pharm',
19, 165-168 (1978).

13 E. Dubler and E. Gyr,Inorg. Chem.,z7, 1466-7473 (1988).

14 C- Périgaud, G, Gosselin anrl J.L. Imbach, Nucleos.ides and Nucleotides, 11, 903-
e4s (1992).
15 G.L. Floersheim, K. Brune and K. Seiler, Agents and Actions,3,24-27 (1973).

16 M.P. Arizti, A. Garcia-Orad, F. Sommer, L. Silvestro, P. Massiot, P. Chevallier,

J.M. Gutiénez-7-ornlla, E. Colacio, M. M. de Pancorbo and H. Tapiero, Anticancer
R¿s., 11, 625-628 (1991).

t7 M.P. Arizti, A. Garcia-Orad, J.M. Gutiénez-Znrrilla, E. Colacio and M. M. de

Pancorbo, Metal lons in Biology and Medicine,385-389, P. Collery, L.A. Poirier,
M. Manfait and J.C. Etienne (Eds.), John Libbey Eurotext, Paris, 1990.

18 H. Schmidbaur and K.C. Dash, Adv. Inorg. Chem. Radiochem.,25, 239-266

(1e82).

L9 B.F. Hoskins, L. Zhenrong and E.R.T. Tiekink, Inorg. Chím. Acta,158, 7-8
(1e8e).

20 A.K. Al-Sa'ady, c.A. McAuliffe, R.v. Parish and J.A. Sandbank, Inorg. Synth.,
23, t9t-t95 (1985).

2T S.J. Berners-Price and P.J. sadler, Inorg. chem.,25,3822-3821 (1986).

22 B.P. Block, Inorg. Synth., 4, 14-16 (1953).

23 Aldric h C atalo g H andb ook of F i ne C hemic al s, p.1224, 1992-1993.

24 L. Malatesta, L. Naldini, G. Simonetta and F. Cariati, Coord. Chem. Rev.,1,255'

262 (1966).

25 C.S.V/. Harker and E.R.T. Tiekink, Acta Cryst.,C46,1546-1541 (1990)'

26 H. Schmidbaur, A. V/ohlleben, F. Vy'agner, O. Orama and G. Huttner, Chem- Ber.,

110, 1748-1754 (1977).

27 D.S. Eggleston, D.F. Chodosh, G.R. Girard and D.T. IJrlll, Inorg. Chim. Acta,
108,22t-226 (1985).

28 C.K. Mirabelli, D.T. Hill, L.F. Faucette, F.L. McCabe, G.R. Girard, D.B. Bryan,
B.M. Sutton, J.O. Bartus, S.T. Crooke and R.K. Johnson, ,/. Med. Chem.,30,
2181-2190 (1987).

29 G.M. Sheldrick, SHELXSS6: Program for the Automatic Solution of Crystal

Structures, Göttingen, Germany (l 986).
30 teXsan, Crystal Structure Analysis Package of the Molecular Structure Corporation,
Texas, U.S.A. (1992).

3r N. Walker and D. Stuart, Acta Cryst, 439, 158-166 (1983).

32 S. Attar, V/.H. Bearden, N.W. Alcock, E.C. Alyea and J.H. Nelson, Inorg. Chem.,
29,425-433 (1990).

33 C.A. McAuliffe, R.V. Parish and P.D. Randall, "f. Chem. Soc., Dalton Trans',
r730-t735 Q979).

34 D.H. Williams and I. Fleming, Spectroscopic Methods in Organic Chemistry,

McGraw-Hill Book Co.,4tlt Ed., 1989.

35 A.D. Cross, Introduction to Practícal Infrared Spectroscopy, Butterworths

Publications Ltd., 1960.

36 C.J. Pouch ert,The Aldrich Library of Infrared Spectra, Aldrich Chemical Co', 2nd
Ed., 1975.

37 R. Cini, A. Cinquantini, M. Sabat and L.G. Marzilli, Inorg. Chem.,24,3903-3908

(198s).

38 C.J. Pouchert and J.R. Campbell,The Aldrích Library of

In NMR Specta, Aldrich
Chemical Co.,1974.

39 M. Akhtar, P.D. Ellis, A.G. MacDiarmid and J.D. Odom,lnorg. Chem.,ll'2917-

2921 (1972).

40 L.F. Johnson and W.C. Jankowski, Carbon-L3 NMR Spectra: A Collection of

As s íg ne d, C o ded and I ndexed Sp ectr a, Wiley-Interscience, 1 972'

4t E. Cariati, L. Ganadu, L. Naldini and S. Seneci, Gazz. Chim. Ital.,109, 181-185,

(1e7e).

42 B.E. Mann, J. Chem. Soc., Perkin t(,30-34 (1912).

43 J. Schrami, M. Capka and V. Blechta, Mag. Res. Chem.,30,544-547 (1992)-

M T. Hahn (Ed.), InternationalTables For Crystallography,D' Reidel Pub. Co., 1983'

45 C.K. Johnson, ORTEP II, Report 5316, Oak Ridge National Laboratory,
Tennessee, U.S.A. (197 6).
46 H. Schmidbaut, Gold BuII',23,ll-21(1990)'

47 N.C. Baenziger, w.E. Bennett and D.M. Soboroff, Acta Cryst-,5_32,962-963

(re76).

48 E.R.T. Tiekink, Acta Cryst, C45, 1233-1234 (1989)'

49 C.A. Tolman, Chem. Rev.,77,313-348 (1977)'

Pergamon
50 G. Wilkinson (Ed.), Comprehensive Coordínation Chemistry, Ch'14,
Press, 1st Ed. (1987).

51 T.L. Brown,Inorg. Chem-,31, 1286-1294 (1992)'

Acta cryst',
52 J.A. Muir, M.M. Muir, L.B. Pulgar, P.G. Jones and G.M. Sheldrick,
c41, 1174-1176 (1985).
(1991)'
53 M.M. Muir, S.I. Cuadrado and J.A. Muir, Acta cryst., c47 , 1072-107 4
(1977)'
54 P.B. Hitchcock and P.L. Pye, J. Chem. Soc., DaltonTrans',1457-1460

(1990)'
55 C.S.W. Harker and E.R.T. Tiekink, Acta cryst., c46, 1546-1547

(1991)'
56 C.S.V/. Harker and E.R.T. Tiekink, Acta Cryst., C47 ,878-879

(1969)'
57 E. Sletten, J. Sletten and L.H. Jensen, Acta cryst.,[.25,1330-1338

58 G.M. Brown, Acta Cryst.,825, 1338-1353 (1969)'

(1912)'
59 D. Lichtenberg, F. Bergmann and,Z. Neiman, Isr. J. Chem',10, 805-8ll

(1992)'
60 P.D. Cookson and E.R.T. Tiekink, J. coord. chem.,26,313-320

61 p.D. Cookson and E.R.T. Tiekink, J. Cryst. Spectro. Res.,23,231-234 (1993)'

(1993)'
62 P.D. Cookson and E.R.T. Tiekink, J. Chem. Soc., DaltonTrans',259-263

(1974)'
63 B. Singh and K.P. Thakur, J.lnorg. Nucl. chem.,36, 1135-1737

64 J. Brigando, D. Colaitis and M. Morel, Bull. soc. chim. Fr., L0, 3440-3445
(1e6e).

37-41
65 R. Barbieri, E. Riva¡ola, F. Di Bianca and F. Huber, Inorg' Chim' Acta,57 '
(1982).
66C.N.R.RaoandR.Venkatarughavan,Spectrochim.Acta,lS,54l-547(1962).

67L-M.Twanmoh,H-B.Wood,Jr.andJ.S.Driscoll,J.HeterocyclicChem.,|0,
187-190 (1973).

Chim' Acta'34' 137-144 (1979)'

68 N. Kottmair and W' Beck' Inorg'

69 C.N.Banwel^|,Fund.amentalsofMolecularSpectroscopy'McGraw-HillBookCo.,
3rd Ed., 1983.

30' 394l-3943 (1974)'

70 E. Breitmaier andW' Voetter 'Tetrahedron'
(1967)'
zlet' Inorg' Chem''6' 823-830
7l G.S. Reddy and R' Schmut

7Z V.Parthasarathi,P'T'BeurskensandH'J'B'Slot'^Acr¿Cryst''439'860-864
(1983).

57 ll57-1162 (1968)'
73 E. Shefter, J. Pharmaceutícal Sciences' '
(1975)'
Cryst'' 831' 2019-2022
74 E. Sletten and A' Apeland' Acta

75 E.A.H.GriffithandE'L'Amma'J'Chern'Soc''Chem'Comm''1013-1014
(1e7e).

and S.J' Lippard' Inorg' Chem.,l3, 815-822 (191 4)'

76 H.I. Heitner

in press
77 P.D. Cookson and E'R'T' Tiekink'

78 N.Okabe,T.Fujiwara,Y'YamagahandK'Tomita'Bull'Chem'Soc'Jpn"56'
1s43 (1983).

79 E.Colacio,A.Romerosa'J'Ruiz'P'Román'J'M'Gutiénez-Zotnlla'A'Vegasand
30' 37 43 (199 1)'
M. Martinez-Ripoll, I nor g' C hern''
1420' (1989)'
Muir' ActaCryst'' C45'
80 M.M. Muir, S.I. Cuadrado and J'A'

81 M.Nakamoto,W.HillerandH.Schmibaur'Chem.Ber.,|26'605-610(1993).

82 F.Bonati,A.Burini,B'R'Pietroni'E'GiorginiandB'Bovio'J'Organomet
Chem., 344, 119-135 (1988)'
 APPE,NDIX

Structure Factor Tables

Table A1: Observed And Calculated Structure Factors For The IPhMezPAuCl] Complex.

l0lFlo vs 10lFIc
h k I Fo FcaigF h k I Fo EcslgF hk I Eo FcslgF h k I Fo Fc51gE h k I Eo Fc51gF

00 II9O 1186 9 06 309 353 36 0 14 6 a45 24

804 141 t214 1239 14 1 10 Ì909 1958 19
00 35?1 3498 22 07 864 835 17 0 15 I L283 1211 2L 142 l 0l ?03 16 r t0 525 543 2l
00 536 454 18 07 s62 566 15 0 15 4 622 620 11 143 911 99 19 1 10 412 461 18
oI r824 1802 10 0? r690 1-t1? 16 0 15 5 1063 1096 r9 141 r918 196 15 I l0 1442 1434 30
01 1600 1531 10 07 0 15 1 441 414 42 145 1191 114 15 I 10 637 605 24
01 3't't 2 3643 2t 07 1608 t636 23 0 16 0 243 334 23 146 342 36 tl 1 10 609 683 18
01 564 502 t2 07 1302 1346 25 0 16 1 !224 t242 30 141 939 96 I 10 615 682
01 !328 7234 t4 01 115 0 tL42 2t 0 16 956 946 23 149 040 91 24 t 11 1083 105r
01 16 97 1518 21 0l 562 61s 19 0 16 3 408 453 31 151 925 91 22 1 11 1411 1395
01 1907 1996 24 0f 866 884 24 0 16 5 663 693 18 152 120{ 118 20 1 11 642 629
OI 930 900 22 0? 491 521 30 0 16 1 3 68 335 35 153 549 55 t4 t lt 516 642
01 83 9 196 20 08 1790 t't't 1 16 0 17 4 910 918 19 151 823 199 16 I 1I 528 526
02 2059 2085 13 00 1079 1099 23 0 18 0 500 561 14 155 t3{l 1349 16 r 1t r4 66 153 6
02 1465 7406 J-2 08 28a1 2985 24 0 10 I I05 ?10 15 156 I 959 2071 18 1 11 s99 605
02 665 658 10 08 1896 1886 22 0 18 2 699 ?09 2L 151 52L 550 23 I lt 413 490
02 3659 3550 20 08 429 456 I5 0 18 3 414 452 32 158 344 306 I lt 609 614
02 195 2 1A'12 14 08 652 693 l4 0 10 513 556 31 159 122 80 4 26 tt2 453 439
02 1009 956 1l 08 11-t 6 Lt1 2 20 0 19 L '152 750 16 I 5 10 911 996 21 I Ì2 631 621
02 1346 1350 19 08 ?98 641 19 0 20 't 96 804 20 160 610 626 13 I12 2058 2025
02 1234 1235 26 08 159 525 40 10 I \942 2226 l1 161 2200 2TE5 2l 7\2 184 810
03 119 758 t5 09 1408 t3't 6 t7 l0 2 15?8 1588 t0 162 2t31 2L9r 2T tt2 519 533
03 -t
41 756 14 09 899 931 10 3 2A52 2818 16 t6l I 919 191I 2T r12 484 4 98
03 113 6 1135 14 09 12 81 13 2l 25 10 4 134 .I
JE 14 15{ 953 966 17 1 1.2 l68 141
03 262 249 13 09 682 661 17 10 6 295 301 2t 165 859 056 1 13 304 261
0l 351 342 13 09 r642 t61 6 19 10 1 t624 1545 l9 )-61 1r 10 112 s 22 1 t3 1076 t04r
03 23 16 2366 11 09 1390 1339 29 10 I 850 188 20 166 125 682 l8 1 t3 269 241
03 3 9'l 450 29 09 399 386 25 10 9 113 6 1091 29 L69 11L 498 2't 1 13 41{ 405
03 1310 L422 29 09 581 623 2t 11 I 221 A 2L56 16 t70 601 555 t4 I 13 100I t034 24
04 3751 3809 21 09 ?33 118 28 11 23 4! 22 40 13 171 23'tl 2338 18 I 13 750 l{3 18
04 1?90 1?'r2 13 09 515 600 {l t1 3 1600 153? 72 tr2 961 1000 24 r 13 369 332 29
01 1113 )-420 12 0 10 1400 L392 23 tl 4 't 16 691 t4 t't3 1828 185? 23 1 13 98I 7021 22
01 155 9 1561 12 0 10 1{55 t422 24 1t 5 851 791 16 114 1{66 118? 23 I 14 15 91 150? 20
04 1016 1873 18 0 10 1504 1S99 21 11 6 2321 220,1 18 175 L22I 1224 t9 1 t4 251 204 30
04 355 3?9 18 0 10 1197 t264 26 11 7 1181 110 2 20 1?6 1645 t639 19 1 14 593 5St t6
04 700 689 15 0 t0 ?96 820 19 11. 10 1396 t341 30 1-t1 601 565 23 1 14 1063 109
04 I040 to32 20 0 10 10't 9 1101 22 t2 0 4364 431 Ll8 l0l6 1054 l9 1 14 53 0 45 22
04 s42 522 r8 0 10 1032 r042 24 t2 1 2151 215 14 1 l 10 693 ?40 35 I 14 35 9 36 36
05 2143 21?8 15 0 1r 603 568 15 12 L423 131 14 180 2062 2097 t1 1 ls 591 58 15
05 258 256 14 0 Ll 68? 683 18 L2 3 r279 120 11 181 2530 2465 23 1 15 825 83 18
05 2366 2459 79 0 11 131 4 13r6 29 t2 4 2451 230 16 182 a92 926 L9 1 Ls 392 36 22
05 1561 1563 14 0 11 113 6 tl't 2 25 l2 1009 91 183 1189 tr96 25 I 15 t032 101 25
05 4!6 391 t2 012 538 556 t9 I2 6 819 19 r84 t-909 1857 18 I 15 683 ?1 t8
05 850 859 t8 012 118 2 11 6l 21 I2 1 816 131 19 185 1608 1584 26 1 15 312 30 35
05 L27L 1244 L9 072 92r 914 22 t2 I 650 561 t6 186 156 162 t6 1 16 145 68 19
05 140 a20 11 012 992 1025 25 I2 9 4L4 399 40 190 556 580 1l I 16 r641 163 0 21
05 5{4 s?5 21 o12 358 349 21 13 0 423 319 9 192 142 ?43 16 1 16 605 593 t6
05 476 4?0 35 0 i-2 623 635 20 t3 I L926 969 l7 193 1406 1451 25 1 16 469 24
05 4251 4290 24 ot2 382 428 5? 13 1995 941 17 194 I t6 s31 54
06 1165 Ll60 t5 013 114 5 115 2 2l 13 3 21 42 2At2 16 195 1 2'l 102 l6 I 17 624 62 t5
06 866 8{6 15 0 13 939 952 24 I3 4 831 801 14 Ì96 33'l 34 39 1 17 966 94 24
06 342 381 14 0 13 1111 1160 24 t3 6 364 3E9 17 191 1025 102 19 I lf 392 40 26
06 257't 2592 t1 0 t3 525 560 36 13 'l 1586 1631 19 198 1220 t29 28 1 1l 891 88 2l
06 92 I 954 1-' 0 13 495 s28 30 13 8 a24 856 19 199 62t 64 25 I 18 331 30 24
06 393 375 tl 0 14 2345 23 05 l3 9 595 636 30 r 10 0 916 96 19 1 18 951 891 L1
06 925 946 22 0 14 414 4't g 14 0 2436 2119 r 5 I 10 r 519 58 13 r 18 334 306
1 18 236 20t 39 511 141 |t 2 l0 0 121 { t233 L1 2 18 3 465 43 20 34 9â2 962 24
1 18 343 309 29 24 ?48 129 16 270 1 L21 L 1264 18 2r8 4 292 34 33 35 2088 2054 14
I t9 1't2 454 2t 24 112 0 114 3 24 210 2 1689 163l 19 2I85 {70 4'l 23 35 1536 1508 t4
I 20 614 621 15 24 9 382 333 33 210 3 770 ?84 18 2190 521 51 1? 95 943 925 17
t20 3s6 428 23 25 0 613 599 16 2to 4 162 150 19 2t9 1 591 56? I6 35 202 t't 3 30
20 5003 49-r? 25 25 1 2308 2336 16 2lo 5 960 975 24 2t93 328 319 21 35 t239 tzr 6 19
20 1935 1861 t1 25 2 2L33 2tr5 11 2t0 6 914 928 2L 301 6t2 80 4 9 35 r631 I5t 3 19
20 1159 1290 10 25 3 23rt 228'l 18 2ro 't 516 {82 24 302 141 146 15 35 10?5 1013 22
20 323 302 9 25 4 496 502 13 2 lt 1 949 930 20 303 1480 't L6 13 526 485 t9
20 2529 2649 16 25 5 361 336 11 2tr 2 429 442 I8 304 2109 3021 t7 35 362 368
31
20 2t20 2IA8 16 25 6 1151 113 9 20 2tr 3 L2S't I2't 4 2t 105 339 329 2T 35 2t
126 126
20 359 359 19 25 ? 1013 1000 23 2r1 4 999 98? 24 301 462 899 tl 35 10 564 630
26
20 113{ 1068 21 25 8 696 100 t? 2r]^ 5 255 232 35 303 1798 1861 22 36 0
I
t4
1019 1061
20 550 503 19 26 0 3026 3044 19 2 11 1 569 553 23 309 525 531 25 36 1255 12 51
15
20 7?0 ?38 19 26 I 1611 16 4 5 16 2rl I 969 956 2l 3 0 10 469 lf3 33 36 2 t31 4 14 03
1?
20 457 414 4I 26 2 1006 966 1? 2tt 9 4r1 115 1t 310 959 959 I 36 3 19
1951 19 01
2\ 933 931 l 26 3 32t 210 18 2t2 0 586 592 1{ 311 21 6t 2029 l5 36 4 1812 1-t35
19
2t 159't 1569 11 26 4 2033 t982 18 2t2 I 1042 981 2T 3t2 2513 255 5 t5 36 6 8t 4 835
20
2t 3643 3ø'11 21 26 r324 t32l 18 212 815 800 I8 313 1740 1?68 ls 35 1 904 087 20
2I 2405 2443 t5 26 6 903 869 22 212 all 931 2t 311 519 621 t3 76 I 1406 r4).3 26
2t 252 25't t6 26 'l 905 902 18 212 6 866 816 18 315 2t6ø 2240 L1 36 9 425 410 34
2l 992 900 16 26 9 198 802 I9 2t2 1 650 651 2T 316 1352 r281 1E 31 0 115 8 t'l41 15
27 1361 1342 18 26 10 412 387 36 2L2 9 425 411 {0 311 551 52I t? 31 1 3042 3081 20
27 7626 7562 20 21 1531 15 6? 15 2t3 0 15{6 1492 t9 319 444 {15 l0 3l 2 1f 0l 1?ll L1

2L 643 565 21 2'l I 546 544 t3 213 1 851 825 17 3 I r0 669 65'1 26 31 3 2062 2043 t9
2L 506 522 J2 1l? I 1?33 1l 2L3 3 522 509 17 3 1 1Ì 5s6 530 35 3f 4 142 129 Ì8
2L 4't0 505 10 21 3 1{78 1404 18 2t3 4 1038 t066 23 320 15?9 155{ 1.0 31 5 103 9 1088 24
22 1594 1581 10 21 4 L362 t3l1 l9 2t3 1015 rt25 20 321 2569 2661 15 31 6 840 815 20
.I 31
22 1597 1612 12 2'l 5 1302 1264 20 2t3 30? 365 33 322 509 494 t2 1 366 360 28
22 95t 946 15 21 6 t129 1t 17 22 213 I 586 5r0 21 323 L222 ttSl 1l 3) I 9l 419 26
4

22 2222 2230 rs 2'l 1 9?0 953 19 2 t4 1 421 399 t9 324 145s 1529 15 31 10 161 353 49
22 1998 1977 15 I 593 555 2t 214 2 1?28 1700 21 214r 2168 ll 38 0 r524 15 41 ì5
22 806 785 1? 21 9 845 84 { 19 2 14 3 103 8 1055 24 326 9t2 899 2r 38 I 1954 1989 l?
22 431 440 16 21 10 621 555 28 214 5 321 35t 31 321 128 614 16 38 2 I203 1211 l9
22 t72r t096 22 0 414 429 14 2t4 6 594 593 2\ 328 t012 991 20 38 3 4't 3 416 tl
22 1217 t19ø 23 28 1 110 5 10 61 1l 2 14 1 650 645 24 329 693 682 21 38 t211 r200 2l
4

22 7021 992 2t 2a 2 2556 2454 20 2 15 0 1{11 13Ef 20 3 2 10 460 195 34 l8 5 121 9 t290
22 146 468 42 28 3 1 658 164
19 0 275 1085 10-19 21 330 222 234 t2 38 6 r 5l2 1417 23
23 156 125 16 28 4 rt?3 1I I3 20 215 319 380 23 331 11 87 1t9l t2 38 8 625 564 23
23 1689 166? 13 28 5 633 631 15 215 442 463 2l 332 l15 3245 20
E l8 9 468 4 60 35
23 1252 t234 15 28 6 180 110 20 2t5 1086 1055 25 333 Il46 t55E 1l 38 t0 885 93 0 24
23 r01? 973 l4 2ø 1 t222 1184 2t5 823 a21 18 334 226 248 24 39 0 12t0 t252 ìl
23 t346 !242 t4 2a 8 802 189 l8 2 16 910 9Ì 4 10 335 621 581 ì6 39 I 80t 821 20
23 1292 t285 t6 2A 9 675 665 24 216 116 143 t9 336 1185 1151 Ì9 39 2 1135 114 0 l9
23 1900 1809 18 29 0 1851 1896 1f 216 466 448 20 331 1 023 999 24 39 3 tlt5 t102 20
23 510 530 17 29 I 2ll1 2t29 18 276 434 430 23 338 4r3 351 26 l9 9f I 985 23
4

23 451 439 28 29 2 613 653 1l 2 16 688 645 l8 J40 6 99 884 Il 39 5 30r 301 31
23 983 1019 22 29 3 119 5 1198 20 2t6 8t4 8t4 2t J41 lJJU !2 l4 !i t9 6 501 {41
23 501 582 38 29 4 1367 1306 20 2r1 ?5 4 73I 19 342 523 508 tl 39 1 902 9t0 t9
24 2588 26r't 16 29 5 t23 I t251 211 266 209 30 341 648 616 16 39 I 119 ll3 20
1265 1261 t4 29 6 94'I 926 19 2tf 6t2 606 17 344 1261 1201 t9 f9 9 603 581 29
24 15r7 148{ 15 29 1 321 313 33 211 809 126 20 345 ll6l l158 l6 I to 0 238 249 25
24 18fl 1896 16 29 I 526 513 26 2 t8 319 292 26 146 851 815 t6 3 10 l 401 402 ll
24 1542 1538 16 29 9 5l1 520 2A 2 tE 641 618 t5 341 I08 7?5 l9 3 l0 2 10 01 10 0l 2l
24 996 1014 1? 29 10 396 406 41 2I8 484 416 t8 348 all 845 2t 3 t0 3 948 912 ìl
3 t0 3-t5 382 24 40 0 623 581 11 46 I4l3 Ì478 t5 4125 342 369 21 52 6 5C6 606 ll
3 10 820 817 1l 40 1 2522 2452 15 46 696 124 t5 4126 1tt0 1208 28 I 948 921 22
3 10 103 700 18 40 2 1348 132f 11 46 224 208 30 4t2 1 133 150 2I 52 9 538 562 t0
3 10 1 1226 1203 29 40 3 889 820 t2 46 324 248 24 4 t3 0 I 691 ll09 I9 5l 0 t9l 408 ì0
3 10 I 480 413 30 404 515 613 12 465 1'720 1f 13 { 13 623 630 14 531 9r2 811 12
3 10 9 688 695 28 405 294r 3335 20 466 1181 tt?3 25 4 13 384 399 2l 532 104 0 3041 19
3 11 0 222L 2289 19 401 L024 LL20 24 461 r81 133 19 4 13 513 516 1l 533 101 685 15
3 11 1 965 922 20 409 1221 1203 29 468 430 391 29 { 13 rt53 Ì tll 25 534 459 431 20
3 11 3 492 {88 18 410 r553 1545 11 469 960 926 4 13 159 409 29 535 463 443 21
3 lt 4 t1?l 1201 23 411 r878 1811 t2 4 6 10 523 513 36 4 13 441 413 31 536 11f1 It52 23
3 tl 5 8'16 885 20 412 3 629 3142 20 410 2413 2458 1l 4 13 4 08 321 38 531 111 116 16
3 11 6 150 3'to 32 413 656 651 15 411 341 310 I5 4 14 585 584 ls 540 229 159 14
3t20 60I 6rl 15 414 41? 104 14 412 2100 2136 Ì0 { 1{ 354 352 24 541 t 1l6 117 2 13
3 t2 I 948 938 21 415 trs? 1199 1E 413 441 452 18 4 14 1 610 1591 22 542 915 921 t 5
3!22 910 906 17 416 1498 1540 20 414 1489 110 9 2T 4 14 2 85 238 35 544 t2s2 t215 22
3L23 r225 1252 22 411 196 1A8 20 415 188 113 ll 4 l{ 980 95t 20 545 I41 1444 23
6
3124 4 85 419 20 418 371 280 3r 4't6 163 169 19 { 15 l80l t8r2 20 546 783775 18
3126 600 605 21 {19 3r5 204 43 411 't 48 129 18 1 ls s 41 sSf 1f 541 592606 20
3 t2 'l 780 't 53 20 420 551 552 11 419 860 420 1 15 416 483 18 548 918 966 22
3 13 0 984 1019 21 421. 311 3 05 9 480 311 314 1l 1 15 833 828 20 549 ?30 689 23
3 13 1 l0 01 995 22 422 154 68 6 13 481 741 12ø 14 1 15 1111 l1l7 25 422 356 42
3 13 2 361 355 22 423 410 {48 15 182 118 3'l r 15 4 16 632 641 16 550 15 90 1609 l{
3133 13 21 L325 22 121 2103 2670 2r 483 1119 L152 20 4 16 { 85 {60 20 551 163? 1583 15
3 13 a 921 925 19 125 1349 1327 r8 484 11¡2 1228 23 1 16 10?8 1059 22 552 944 90{ 1l
3 13 5 341 3{8 30 426 284 270 26 485 850 801 20 4 1? 1M55 Ì9 553 430 422 L1
3 13 1 {19 410 32 421 624 626 7'l 481 1322 t264 28 { 1? {00 319 554 114 5 Ltol 23
3 13 I 433 432 3'l 428 1569 1580 25 488 1r 1l l0f8 23 I 1? 95r 993 l9 555 1586 1580 24
3 11 1 502 593 t5 429 681 686 23 189 ?08 655 26 a 18 315 314 23 1t6 ?01 19
311 2 610 650 ls 430 r202 !202 1l 490 3006 3 017 20 1 18 301 320 30 559 71t 690 24
3 la 1 304 321 31 431 2381 2391 rs 491 1744 1E13 18 1 18 649 643 t6 560 390 365 t2
3 r4 5 528 498 2r 432 73 9 120 16 492 216 258 24 { 19 145 149 1? 561 1f56 1706 t6
3 11 6 L221 1221 28 433 453 4 66 15 493 l0l8 10{8 2l 1 t9 3t9 3ll 23 562 525 513 12
3 11 1 {09 380 32 434 r150 1165 21 494 1519 15{9 22 50 6?0 539 I2 s63 160 5 166? 19
3 15 0 1094 1055 21 435 1825 1821 19 495 516 55? 19 50 161 144 l9 564 r68? 1663 22
3 15 1 103 0 I02l 22 436 318 326 25 491 {04 36r 30 50 Ì258 1101 13 565 244 223 40
3 15 2 234 176 34 43'l 753 196 t1 t98 509 q't 9 30 50 2340 2484 18 556 644 615 19
3 15 3 110 0 1055 23 {39 502 452 29 4 t0 0 3 4'l 36? 18 50 479 58? t6 56'l 73I 754 19
3 15 4 856 832 20 410 328 314 10 4 10 I 1502 1593 18 50 250 229 32 568 1460 1434 30
3 15 5 158 408 21 441 201L 2023 11 4 10 2 !012 1050 20 50 1809 1918 24 510 18 41 1835 16
3 15 1 553 556 26 442 10 0? 991 15 4 t0 3 1090 1,0 81 23 51 ta3 2t2 14 5f1 221 I 2219 rA
3 16 I 388 449 22 443 1640 1651 t 8 4 10 4 659 683 16 51 240L 2445 14 512 I 893 1934 18
3 16 2 701 690 16 444 1489 L43'l 20 4 10 5 50t- 488 51 2239 2193 14 5'1 3 r369 1381 20
3 16 3 tog2 1016 25 445 1369 1363 2t 4 10 6 1065 1102 20 51 896 881 15 514 10 91 1011 23
3 16 5 319 355 32 446 ?36 733 t6 4 10 1 415 4't 9 J2 51 115 128 19 515 s8 { 96t 20
3166 618 6t2 2l 448 1285 t31{ 26 4 10 I t93 482 33 51 1963 2091 19 5?6 815897 19
3 1? 0 t263 L27L 2\ 449 431 321 33 4 11 0 526 536 l{ 51 501 553 18 5?1 389301 33
3 1? 1 4 68 422 r8 150 11.35 1129 13 4 11 1 668 '705 14 51 500 54{ 5?8 4'12 535 32
3 t? 3 234 254 38 451 173 0 1703 14 1 11 2 I5L 864 l't 51 113 415 2'l s80 416 429 t4
3 11 4 961 941 19 452 2't 63 2819 19 4 11 3 1439 )-315 2l 51 461 {69 33 581 1 905 1911 1f

3 1l 5 57t 516 20 453 933 946 2l 4 11 4 342 3t2 28 52 569 612 t2 582 909 934 20
3 18 2 129 436 2r {51 360 32A 23 4 11 1 ?61 ígz zo 52 2514 2519 15 503 917 955 1?
3 18 3 549 52Ì t8 455 {53 428 20 4 11 9 534 568 36 52 1200 t110 13 584 5?1 566 18
3 19 0 125 409 20 156 312 t2a3 23 4L22 {63 450 18 1 1 51 1181 t6 505 118 6 1233 21
3 19 2 3S9 4tl 23 451 465 461 23 4t23 2't 2 221 31, 52 912 961 t8 586 1426 1445 2f
3 19 3 43'' 161 2l 460 91 890 14 4124 338 211 26 52 203E 9¿ 2I 588 5tt 45? 31
590 926 9L6 19 602 50 1446 13 662 1020 L022 t6 612 889 89 25 133 I552 1513 23
591 133 788 16 603 '12 691 16 663 621 612 15 6 13 l46l 41 28 134 619 lt6 19
592 1615 1648 l9 604 00 9?0 16 664 1115 1158 23 6 13 310 31 2A 135 533 538 30
593 1524 t524 20 01 2016 25 665 133 6 r32L 21 6 13 193 41 21 136 501 515 41
594 539 502 l9 601 48 saf 24 666 980 945 23 6 13 912 99 22 13f 952 915 26
595 551 5't0 20 609 6ø 158 2s 661 575 562 2s 6 13 56E 68 26 138 411 463 54
596 320 292 36 611 03 1005 12 668 425 426 34 6 13 5r5 45 38 139 630 6't0 41
591 to26 1041 24 612 2950 3069 18 669 63 9 535 29 6 t4 181 81 19 140 1394 1409 18
599 55I 553 33 613 968 943 l4 6'1 0 131 4 ¡.314 16 6 14 5E3 20 141 1049 1018 20

5 10 0 't 6t 158 I5 614 597 569 13 611 '1 42 130 r4 6 14 8ll 861 21 't42 869 808 18
5 10 1 30? 2't 4 22 615 1018 968 2l 612 r161 1160 r0 6 14 1111 110 9 24 't43 810 190 t1
5 10 2 at2 821 t6 616 1040 1170 23 613 1025 1062 22 6 t5 13 71 l.410 30 144 t421 )-44r 29
5 10 3 9s5 1006 24 611 1091 1152 20 6't4 849 821 19 6 15 4 81 190 28 145 655 615 26
5 10 4 578 533 18 619 591 670 30 6't5 i-28 6 1211 26 6 15 {93 541 30 146 621 631 3 4
5 10 5 52s 199 21 620 {80 492 11 6't6 495 184 25 6 15 ô57 88? 2l 141 43'l {81 40
5 10 6 818 856 1t 621 t2r2 \226 12 61'l 999 962 25 6 15 419 4¡3 33 148 526 603 44
5 t0 1 969 l01r 2 5 622 169 166 14 619 801 010 26 6 16 710 116 2t 149 545 37t 4!
5 10 8 460 4?5 35 623 1374 1343 15 680 924 939 18 6 16 513 516 2'I 150 148 116 76
5 10 9 {35 4?9 45 624 1El9 lf43 l9 681 880 9t9 2t 6 16 124 4l9 32 751 816 804 1?
5 11 0 2140 2162 t9 625 ?30 755 18 682 1312 1334 19 6 16 320 251 4f ?52 545 495 1?
5 11 1 1352 l4t0 2{ 626 1,4 1 415 31 683 L441 1414 20 611 433 160 32 153 573 5? 4 18
5 tl 5 s32 509 21 621 465 {68 24 684 6 t7 515 24
613 155 Il1 6 t195
5 11 1 526 503 21 628 1205 128S 22 686 486 511 26 6 1l 4 45 451 34 756 101 4 r063 23
5t20 {00 390 19 629 503 533 33 641 933 954 22 6 18 563 560 26 l5f 14L 826
5),21 ll?0 1236 2t 630 801 810 13 688 l9{ 806 2{ 6 lE 244 265 44 159 615 662 45
631 689 385 383 48 -l 2lr8 2030 l9 160 210 231 26
5122 392 40r 2t t562 1520 t3 0
5723 t249 1260 23 612 ?5E ?06 16 690 20a4 2012 lA 70 2 202 lE2 30 161 | 626 l5?5 2t
5 12 1 522 522 20 633 423 383 I4 691 10?4 10r4 19 l0 3 2t92 2139 2l 162 t229 119 4 24
5t25 383 383 20 634 869 s62 1? 692 649 650 l.s l0 4 Ì164 1141 23 163 1503 r514
5t26 509 169 24 635 115 3 1164 2â 693 3s2 386 24 't0 5 5A2 696 t6 164 924 921 2T
5 12 1 1t6 't 67 22 636 9?3 1002 22 694 1588 Ì604 23 l0 l 462 162 24 165 695 611 25
5 13 0 910 928 22 631 795 aL2 19 695 139 129 L1 70 1204 10).3 26 161 I58 110 32
5 13 1 919 916 t1 638 588 595 24 696 614 683 20 l0 9 681 506 35 168 1t6 699 36
5 13 2 35 9 386 23 639 516 5 69 29 691 554 539 25 ?1 0 Ì t-14 1).56 r? 110 925 9t5 23
5 13 J 1135 24 6 3 t0 546 5 87 36 698 11r 461 36 1\ 1 113l tl29 11 1't1 801 164 20
s 13 4 161 748 18 640 115 ?03 14 6 10 1 1205 L261 20 lL 2 | 411 14 {? 18 112 1311 1294 25
5 13 1 16'l 16-1 30 641 115 3 1125 14 6 10 2 551 575 15 l1 3 954 2r
98? 1-t3 926 85? 23
5 1{ I 601 659 1s 642 303 245 16 6 10 3 r068 1096 23 f1 4 828 19
814 1f4 1330 14 01 32
643 6 10 4 393 J2L 24 -tl 811 20 f15 669 562 26
5 14 2 't 99 829 19 r466 L49'l 18 5 890
5 14 3 353 3 4'l 25 644 940 903 6 10 5 914 885 22 lt 6 1168 1500 30 116 r239 1231
5 14 5 300 263 35 645 110l 1r3 20 6 10 5 125 146 20 ll 1 836 aol 23 118 832 840 32
5 14 6 1288 L239 28 64'l 434 44 29 6 10 1 424 46'1 34 l1 I 518 34
633 180 1I5 2 115 4 24
5 15 0 t022 7032 23 648 926 95 22 6 tl 0 303 263 27 lt 9 585 38
124 181 I8I ] 1814 24
s 15 I 862 061 18 550 1085 108 14 6 11 1 s58 563 1s l1 10 849 831 39 f82 481 4f0 23
5 15 3 t012 L066 25 651 611 60 13 6 11 2 589 616 15 0 2588 2612 79 ?83 r204 t209 30
5 15 4 809 183 ll 652 23t8 223 18 6 lt 3 856 930 18 12 L 1973 2084 l8 184 922 939 23
5 t6 0 499 515 r8 651 1016 98 I9 6 11 4 611 102 t1 12 2 466 416 l4 185 1t 5I 118 0 21
5 16 1 561 559 17 654 905 83 1E 6 tl 1 586 640 3l 12 J t237 t230 22 186 t29 112 2A
5 16 2 313 J55 24 655 305 188 35 6 lt I 563 63t 43 12 4 7210 1240 26 191 426 334 23
5 16 3 1085 \os2 25 656 l24E t264 29 6t20 569 521 2r 12 806 191 2r 192 682 613 18
5 1l 0 L341 t33t 22 651 40? 456 32 612 1 451 501 26 12 1 429 419 {l 193 1264 l2t6 30
5 lt 4 949 909 r 9 658 541 5 90 28 6122 604 593 2I 12 I 522 503 40 194 199 825 21
5 18 3 458 464 22 659 498 445 34 6t23 561 524 24 73 0 r26). t212 11 t95 818 851
600 21 65 267r t1 660 1445 1423 t5 6t24 401 332 35 13 1 142 l3 9 t5 191 94f 941 2l
60t 2401 23't5 76 661 r492 1440 15 6725 491 462 33 ll 2 1ll0 1111 20 198 518 661 44
I 10 0 1044 1018 2 0 816 965 923 22 890 590 564 r9 92 4 1496 r469 26 912 1 696 618 22
7 10 1 361 334 29 811 105 5 1051 28 891 809 ?49 20 93 0 ?91 tl
181 9122 1ì42 tr22
7 I0 2 1424 t382 2ê 819 834 713 35 892 a26 841 2L 93 I 940 2r
918 9123 396 3 9l 31
r 10 3 573 632 24 a20 tJ62 1380 18 893 415 485 29 93 3 141.0 1404 25 9125 441 441 36
? 10 { 625 648 25 821 1008 1016 19 894 819 805 2l 93 4 161 190 t9 9 12 6 3 98 388 45
? t0 5 560 626 3D 822 149 ?50 17 895 901 932 22 9l 94E 901 l0 9 lJ 1 555 525 21
f 10 5 114 10e 21 823 14 01 1359 2l 896 063 837 25 93 9 452 433 61 9 13 2 4t2 423 31
-, 10 1 311 359 58 824 881 902 I 10 0 381 42a 29 94 0 1639 1683 20 9 Ì3 4 531 560 30
7 11 0 1332 t364 21 a26 152 't't 2A I 10 I 1086 1081 22 94 I 219 250 28 9 13 5 45 9 496 38
l tt I 5rf 509 23 a21 5l4 50 44 8 t0 2 946 A1A 20 94 2 453 394 20 9 t4 1 841 846 2t
f tL 2 5f0 s61 23 a29 141 14 31 I 10 3 956 929 2r 94 3 85? 840 18 9 14 4 509 429 30
I 11 3 549 4't4 24 830 152 11 15 I 10 4 303 2f1 46 94 982 953 24 9 ts 1 510 515 29
? 1t 4 I05 041 2L 811 384 38 18 I 10 5 699 155 26 94 5 564 5â6 2l 9 t5 2 364 244 36
7 tr 5 854 905 24 832 615 63 16 I t0 6 6lt 644 33 94 1 641 658 38 9 16 I 4r8 416 38
7 11 1 545 584 40 833 555 5l 18 8 11 0 412 459 25 95 1 3 44 358 25 9 t6 2 95t 942 23
1t2 I 802 808 19 834 398 368 28 8 11 3 318 330 l4 95 2 6 83 913 2l Ì0 0 0 2542 23A5 23
1t22 881 950 22 835 584 584 2l I lt 4 a22 A31 2r 95 l 440 420 21 10 0 l 185 ?69 ì9
 1t23 993 \026 24 836 1461 1444 30 8 lt 1 3f4 308 54 9 5 4 429 4013r l0 04 5?3 t 4l6
1t25 489 465 33 831 602 558 42 8t20365 317 33 9 5 s 6s9 frl21 10 05 595 54s
'tt26 513 510 3l 840 r348 1350 t9 8t21913 883 20 9 5 6 1066 rr21 26 10 0l 190 059
7 13 0 626 518 22 841 15?l 1541 20 8722581 652 2s 9 s l 548 583 4s 10 10 98 1053
? 13 1 510 515 25 842 843 786 t9 a124t31 330 44 9 6 0 306 33928 10 1l l1 I03
I 13 2 53I 513 2s 843 r0?8 1120 2l â125640 642 28 9 6 I 732r 1328 24 10 t2 95 961
7 13 3 451 479 30 8{4 819 El2 18 E 13 I 63't 6L\ 23 9 6 2 1216 1.153 2f 10 13 42 1453
I 13 1 102 593 23 845 608 608 26 8132399 317 33 9 6 3 1321 1331 28 10 14 64 704
I 13 6 436 311 40 841 498 582 49 8 13 4 588 6L6 28 9 6 4 49r 42120 l0 15 2A 321
? Ì4 I 1003 1067 21 050 704 138 Ls I 13 5 810 811 24 9 6 5 127 41118 10 16 ?8 116
'I 14 3 568 519 2s 85r 994 921 23 8 14 0 302 285 13 9 6 6 160 10A 2A 1.0 17 194 804
? 14 5 613 630 28 852 946 942 t9 814r528 542 29 9 6 1 595 684)6 10 20 166 80?
1 74 6 582 551 31 853 1191 1158 26 8 14 2 L496 r49S 32 9 1 0 432 44924 10 2I 383 404 23
? 15 0 109 122 22 854 1r48 1r43 23 8 14 { 317 265 16 9 ? \ 1336 t2AA 26 10 22 660 6{6 t5
I 15 I 394 402 J4 856 639 656 32 t150123 399 34 9 1 2 160 14818 10 23 1013 10{l
.t88 20
l 15 3 4 98 494 30 851 710 738 34 I 15 I 609 619 25 9 1 3 992 9'14 24 l0 24 '160 18
? ls 4 '120 151 24 858 540 624 49 8Ìs2464 4't2 3r 9 1 4 A02 84822 10 5?3 514 25
? 15 5 508 455 3r 860 2052 2042 22 I 15 4 {09 425 3A 9 1 5 a43 A4521 r0 519 s78 30
? L6 r 163 111 2l 861 994 969 24 8 16 7 149 196 23 9 1 I 501 62654 r0 21 582 663 42
7 16 2 1015 988 21 062 ?80 768 18 81625t2 56{ 3l 9 8 0 r34l 1325 26 r0 3l 90I 936 l8
1163 541 569 29 863 621 592 20 I 16 3 4?1 413 3l 9 8 r 1323 1295 21 10 32 645 631 11
I ll 0 g2t 841 21 954 1131 1388 30 9 0 I 1?30 1633 2t 9 E 2 315 34331 l0 33 918 885 21
1I1 I 52r 485 28 865 196 180 23 902ø3'l ??9 19 9 I 3 1015 991 24 10 5t8 56L 29
1t'l 2 2âr 228 45 ô68 418 349 60 9 0 r 1811 1800 21 9 I 4 t0{3 1039 22 10 36 1030 r01L 26
? 18 1 366 330 36 87r 32A 335 29 906611 592 21 9 I 5 140 s08 21 10 40 1r60 1186 23
600 4131 )98't 26 8?2 469 426 27 9 0 7 960 L069 23 9 9 0 72f ?5016 10 41 4r9 415 2r
801 1253 116{ 20 8't3 928 939 20 9 0 9 560 184 s2 9 9 3 631 61123 10 42 863 ø16 2t
802 588 598 15 8?4 62L 58'l 24 9 1 0 1009 t00't 22 9 9 1 918 90821 10 43 911 818 22
801 756 102 19 815 L211 L292 26 9r1693 ?08 15 9 9 5 565 58832 10 44 852 820 22
804 Tø26 1110 23 8f6 641 123 32 9 I 2 763 ?86 19 9 9 l 651 59236 10 46 132 668 21
005 536 502 2L 811 895 885 30 9 1 3 1096 tL01 21 9 10 0 551 5f1 23 10 41 3 97 381 58
80'l 540 518 34 880 t0{4 1061 19 9 1 { 450 12A 22 9 r0 2 LL56 Ll41 24 10 50 4 85 490 19
810 932 913 2t 881 715 l?3 19 9 1 61366 t352 24 9 10 1 310 286 41 10 51 1216 1241 24
011 832 818 21 882 [t23 7119 2'l 9r'l 623 613 3 9 9 10 5 148 El6 25 10 435 381 24
812 lrlI 1138 20 E83 1055 1036 2{ 9 2 02011 2Lt1 20 9 11 r 939 902 20 10 53 123I T2JL 29
813 t66'l t101 2l 884 568 { 95 26 9 2 1 1035 1083 21 9 11 2 631 601 23 10 54 120 692 22
814 64 6 625 16 885 4r9 124 38 922139 435 19 9 11 5 803 8?? 25 10 57 646 636 38
815 886 855 19 886 164 't69 29 9 2 31138 1139 24 9 11 6 452 443 41 10 60 t62A 112t 24
10 6 1 401 323 2s 11 1 5 165 19t 20 rt 12 0 535 4A6 29 12 10 4 408 439 44 14 52 159 s29 22
10 6 2 329 2'tt 34 lt 1 6 143 14'l 25 11 12 1 36? 302 41 12 1l I 469 504 36 14 53 3?0 338 41

10 6 1 562 s62 24 11 2 0 876 931 19 11 12 2 646 612 28 12 t1 2 364 298 45 14 5t 428 405 31
10 6 4 861 82A 2L 11 2 | 4A2 410 19 11 12 4 315 34s 50 12 11 3 601 605 30 14 62 515 623 2A

10 6 5 504 466 34 1r 2 2 700 ?10 1l 11 13 0 359 291 40 13 0 l. 434 446 30 14 10 415 418 29
10 I 0 901 935 22 11 2 3 580 615 2l 11 13 1 s51 612 32 13 0 4 920 953 21 14 12 53S 522 30
10 ? 1 254 262 4t 11 2 4 980 966 23 11 13 3 609 640 29 13 0 5 413 416 41 14 80 525 568 28
10 1 2 938 916 23 629 662 26 1200713 648 IE 13 r I 951 947 23 15 01 631 612 26
t0 1 3 546 st4 26 11 2 6 516 519 35 t201618 589 20 13 1 2 664 64A 2\ 15 l0 416 466 35
10 'l 4 788 1't't 23 11 21 414 469 45 !20211r 188 t9 13 1 3 511 459 27 15 1I 3 93 336 76
10 'l 5 504 543 36 tt 3 0 6L3 6't1 16 !2 0 4 879 117 20 13 | 5 691 135 26 15 20 360 4I2 J1
10 1 6 536 5t-0 39 1t 3 1 139 803 l8 L2 0 5 1007 966 27 13 2 1 155 ?68 1,8 ls 2T 6?l 69-t 24

10 1 1 525 545 {5 11 J2 16't 143 18 t20?536 536 l1 13 2 2 ø54 A81 2l 15 30 351 352 38
10 a 2 1343 1312 30 11 3 3 985 10s6 22 7210906 889 2t 13 2 4 320 429 4f
10 I 3 831 198 20 11 3 4 523 531 26 t211818 8S0 13 2 5 633 661 21
t0 E 4 309 316 49 11 3 1 482 500 48 12 I 2 rr32 115 0 29 Ì3 3 1 5E3 558 21
10 I 5 541 516 33 11 4 0 725 ?86 18 12 I 3 62'l 598 21 13 3 2 956 95I 23
10 I 6 640 620 3i 11 4 3 49A 491 26 1214568 598 25 t3 4 I 213 30r 42
10 a 1 544 564 42 11 4 4 433 4sE 34 t215380 451 40 13 4 2 s1A 54L 25
10 9 0 333 351 3s 11 4 5 147 149 25 t216575 5 90 30 13 4 5 5A9 621 32
10 9 I 131 0 1280 30 11 4 'l 600 50? 10 L2 2 0 383 381 26 13 5 0 594 653 22
10 9 2 620 6L2 24 11 5 0 834 850 21 t224110 ø21 20 13 s L 491 493 26
t0 9 3 699 614 24 11 5 1 529 553 2r 1225156 13'l 23 13 5 2 391 355 34
10 9 4 318 319 49 11 5 2 ?55 717 I I 1-2 3 0 4?8 509 22 13 5 3 33? 356 43
10 9 5 133 142 21 tr 5 3 394 416 33 1-2 3 I 951 1003 21 13 5 5 {52 543 43
10 9 6 5 65 549 35 11 s 4 512 s14 28 L233512 554 22 13 6 0 490 586 25
10 10 0 't19 145 19 t1 5 5 462 491 38 t235622 641 28 l3 6 r 509 502 26
r0 10 1 629 6)-6 24 11 5 6 ?08 690 31 t240636 6't 2 18 13 6 3 482 441 33
10 10 2 10 41 70L2 26 11 6 0 861 894 21 t241419 502 23 t3 6 4 119 1r9 28
r0 10 4 s 0-t 461 32 11 6 2 730 70ó 20 L242613 692 20 13 I 0 3?9 366 33
10 10 5 380 389 45 11 6 3 802 119 2r t2 4 4 849 442 2T 13 1 | 899 e52 2r
10 10 5 416 550 4 9 11 6 4 694 698 25 t2 1 5 414 358 40 13 1 2 419 542 34
l0 lt 0 408 343 32 11 6 6 576 597 38 1216412 451 {3 13 1 3 694 143 26
10 11 1 519 548 28 11 7 1 1510 1568 28 125195s 9{{ 13 7 4 436 388 40
10 tt 3 596 584 29 11 1 2 2¿9 238 42 1-2 5 2 831 866 2t t3 0 I 51{ 525 28
10 11 4 558 614 33 tI 1 3 1060 1040 22 12 5 3 -r59 145 2l 13 A 2 5ø1 551 21
t0 12 1 {65 468 33 lt 'l 5 569 563 34 !255406 394 15 L3 I 3 353 356 4l
10 12 2 413 3t3 36 11 8 0 931 969 23 1256392 126 s3 13 9 0 JAO 424 31
t0125 51. 6 544 34 L1 81 500 482 21 1260611 600 20 13 9 1 17r 489 32
10 13 0 113 495 33 11 82 615 634 25 t2624lO 446 32 13 9 2 5J6 5'15 33
r0 13 I 5't 6 632 29 11 I 1 't75 106 27 t263355 365 12 13 I 3 4E? 511 3l
t0 1{ 2 982 964 24 11 8 5 5?4 5?9 33 L265r45 695 28 13 10 0 {30 425 36
10 15 0 461 439 34 11 I 6 624 6Ll 34 t2 l 0 1094 !088 22 14 0 1 110 ?56 23
l0 15 1 550 556 30 ll 9 0 13t 144 20 L2 'l 2 92'l 976 22 14 0 2 94L 941 23
11 0 I 339 240 70 11 91 468 499 30 t214624 690 32 14 1 1 199 450 2l
11 0 2 514 562 20 11 92 695 682 24 7280403 448 31 14 1 2 906 961 23
11 0 3 859 't 62 20 11 9 3 541 585 32 t282382 33{ 38 14 1 4 388 341 40
lt 0 4 1006 985 2\ 11 9 4 625 635 29 t283688 62L 26 14 2 r 5lr 543 26
11 0 6 612 5't2 25 11 10 1 358 333 38 t285411 452 46 1{ 2 Z 412 343 31
tl 0 l ?41 151 2'' 11 10 2 404 459 39 t2 9 0 881 905 r 9 1( 2 4 451 481 35
11 1 0 359 424 2f 11 10 3 460 420 35 129L9l2 93r 23 14 3 I 450 484 29
11 1 1 1211 1302 25 11 10 5 563 s92 35 L2 9 3 52J. 512 28 14 3 4 39s 416 4l
11 I 2 740 140 1l 11 11 0 '169 140 22 L2 9 4 5{1 540 35 t4 4 1 634 641 22
11 1 3 944 928 2r 11 11 Ì 590 655 24 12 10 2 644 618 21 14 4 3 441 426 37
11 I 4 3 9l 38? 30 11 rr 4 401 435 44 12 10 I 411 2A1 40 t4 5 I 325 335 40
Table A2 Obsemed And Cølculated Slructure Factors For The IPhsPAu(6-MP)l CzHsOH Complex.

l0lPlo vs 10lFlc
h k I Fo FcslgF h k I Fo Fc slgF hklFo Ec stqF h k I Fo Fc algE h k I Fo Ec slgF

0 0 1 1554 16Ì4 I 0 3529s 300 l 0 6 r 830 839 l 0944404409 0 16 -1 191 153 l4

0 0 212021182 1 0 3 6 140 r42 t4 062969 98? I 0 9 5 121 420t0 0 16 0 131 108 20
0 0 3 162 19a 'l O 31L66 145 14 0 6 3 89{ 853 9 0 9 6 459 188 1l 0 17 -2 t3E 155 20
0 0 413421331 9 0 3 I 155 101 1? 0 6 4 398 406 8 0 9 ? 300 302 lÌ 0 17 2 20't 202 15
0 0 5 1310 1313 10 0 39146 lr9 2l 065264 266 I 0 9 0 262 25013 0 17 3 144 144 20
0 0 6 621 63610 0 4 -10 167 191 20 066641 680 11 0 9 9 160 L8222 1 -17 -3 168 1f I 18
0 0 l 503 511 12 0 4 -9 239 20? 13 0 6 't 319 3?6 10 0 10 -1 158 113 14 1 -1-t -2 t64 r60 18
00839640690 4 -0 25s 256 t7 066322 324 t0 0 10 -2 135 138 13 1 -11 -1 t45 115 19
0 0 9 382 39310 0 4 -'t 494 4f9 13 0 7 -9 155 148 20 0 10 -1 t94 202 9 1 -17 I t42 t65 22
0 0 t0 212 262 13 0 4 -6 595 611 11 0 ? -8 304 285 10 01001911849 1 -rl 3 186 r51 20
0t-625222180 4 -5 61'l 610 9 o1-1320 293 9 01072552638 1 -15 -5 164 184 19
0 1 -5 98 10515 0 4 -{ 840 83 9 I 01-621a 222 L0 0 10 2 L53 t44 L2 1 -15 -4 285 294 ).2
0l-411610290 4 -3 6t2 626 1 01-5231 218 I 0 10 4 221 232 lO 1 -15 -3 263 214 12
01-3193r8950 4 -2 14D9 t429 9 0 -t7 -4 555 559 10 0 10 5 219 254 \t 1 -15 -2 715 t53 1s
01-262663250 4 -1 1097 1082 't 0 -3 887 161 9 0 10 6 r88 166 15 I -15 o 223 229 12
0 1 -1 316 319 4 0 4 0 7023 10 21 't 01-2124 122 I 0 11 -l 165 r?0 18 1 -Ì5 1 309 290 10
0 I I 329 310 4 0 41559 683 6 0r-1601 601 I 0 1l -5 306 31? 10 I -r5 19t 15
01257457350 4 2 t029 1018 7 0 ? 0 456 {5'} E 0 11 -5 449 441 ll I -r5 4 140 ro4 23
01319120250 { 3 1104 t0s4 I 0 I I 693 696 I 0 11 -4 494 492 10 I -15 5 150 r24 22
01424I22660 4 4 ?08 710 I 07261â 613 I 0 1r -3 436 420 9 I -15 6 138 1t9 22
01620519290 4 s 411 4t2 ø 0 7 3 515 579 9 0 tr -2 366 35'Ì 9 I -14 -2 t30 117 l8
0 1 1 189 20012 0 46356 363 I 0f4520 521 tO 0 t1 -1 638 631 10 I -14 1 198 182 13
0 2 -10 302 323 12 0 47459 452 10 075166 350 I 0 11 0 579 512 10 I -14 2 t41 t44 20
0 2 -9 214 2ø212 0 4 8 448 4 60 11 0 7 6 606 598 12 0 11 1 568 5?0 11 I -14 3 139 81 23
0 2 -8 256 26611 0 49266 304 13 0 7 f 348 356 9 0112481{8E9 I _I3 -1 I12 r60 18
0 2 -1 {49 450 9 0 5 -8 247 254 12 0 7 I 23t 262 14 0 ).1 3 393 397 I 1 -13 -6 220 20L t4
0 2 -6 752 ll3 1.0 0 5 -1 492 499 10 0 -t 9 110 L69 20 0 11 4 1?0 456 1.0 1 -13 -5 228 241- t4
o2-583583990 5 -6 335 340 I 08-7173 205 16 0 11 5 109 426 10 1 -13 -4 313 324 10
02-412012580 s -5 195 187 9 08-6326 335 I 0 11 6 3?0 368 10 I -13 -3 2'10 268 rO
02-3199ø0210 s -4 J27 311 I 08-5204 205 10 0 11 1 t92 205 11 1 -13 -2 212 223 tl
0 2 -2 9551000 ? 0 5 -3 644 646 ø 0 I -4 339 346 A 0 rt I 20a 224 11 1 -13 -1 281 29t 9
0 2 -r 1399 1364 I 0 5 -2 169 't53 'l 08-3341 141 9 0 13 -6 20I L92 16 1 -r3 0 361 370 9
o2099291r60 5 -1 594 591 ? 08-2498 498 t0 0 t3 -5 254 24s 12 1 -13 1 365 363 9
o2L11211350 5 0 689 644 6 0 I -1 503 494 9 0 13 -4 250 265 12 1 -13 2 18r 173 15
o 2 211{91t40 ? 0 5 I 438 432 1 0 I 0 {80 4 60 9 0 13 -3 220 2L3 r5 1 -13 3 233 187 13
0 2 3It991224 I 0 5 2 t122 1104 I 08160't 621 9 o 13 -2 361 3?0 9 I -r3 4 256 229 12
0 2 4 14?8 1494 10 0 5 3 566 5 64 I 0824I8 401 t 0 0 13 -1 468 469 10 I -13 5 253 2t1 13
o2581981190 5 4 560 550 9 083233 234 I 0 13 0 169 469 9 I -t3 6 146 !31 20
0 2 6 608 60310 0 5 339 336 1 0 I 4 148 134 t3 013r2982949 | -72 6 162 187 19
o 2 7 498 51312 0 55446 434 9 0 I 5 394 389 10 01323L63034 I -12 -5 303 285 r0
o 2 I 5{0 536 10 0 51429 446 1t 0 I 6 383 369 10 01134254399 r -72 -4 211
0 2 9 366 39310 0 58221 22't 14 081209 224 74 0 t3 4 421 432 10 r -t2 -3 ztt 19? t1
0 2 l0 215 215t3 0 5 9 161 155 20 0 9 -9 t89 210 18 0 13 5 295 306 1Ì I -12 -2 L91 203 11
0 3 -? 244 226L0 0 5 10 155 L6t 23 09-6266 266 13 0 t3 6 186 169 1l IT2 -t 291 3r2 I
0 3 -6 186 392 9 0 6 -r0 766 153 r9 0 9 -? 181 1?? 15 0 13 1 199 201 ll r -t2 0 241 23A 9
03-534934280 6 -9 193 162 t6 09-6201 202 72 0 t5 -5 155 106 19 L12 I 2r2 2t2 lr
0 3 -4 542 514 I 0 6 -ø 268 280 lt 0 9 -5 465 413 9 0 t5 -3 228 222 12 | -t2 3 16l 16-t 16
0 3 -3 403 399 l 0 6 -1 260 263 l0 0 9 -4 602 594 t1 0 15 -2 281 292 l0 | -12 4 2I9 2r't 13
03-296196L10 6 -6 229 233 \0 09-3496 481 11 0 15 -1 191 206 14 T .I2 5 2r4 206 t3
03-136536950 6 -5 351 357 7 09-2304 218 9 0 15 0 126 146 20 r -72 6 1?0 142 11
03052662250 6 -4 44L 435 10 0 9 -r {{1 133 10 0 15 1 165 162 16 1 -11 -8 142 136 23
0 3 1 541 550 5 0 6 -3 183 182 I 0 9 0 831 826 9 0 15 2 26L 255 1l r -11 -7 180 206 r8
0321211L060 6 -2 632 521 ã 0 9 1 833 810 9 0 ts 3 2'lI 280 12 I -11 -6 269 295 12
0 3 3 t81 163 I 0 6 -1 582 561 7 092121 735 9 0 15 4 211 220 L4 1 -11 -5 205 298 10
03414244590 60283 3r1 6 093421 415 I 0 L6 -2 171 156 16 1 -rt -4 228 22't LO
1 -11 -3 222 231 l0 I -l -5 336 337 I I -3 -9 114 142 20 1 -1 9 lfl 161 18 T2 -1 1156 1140 l
L -tL -2 359 3-t5 I I -'t -4 t17 126 tt 1 -3 -8 r58 126 t6 1 -r 10 113 As 22 L2 0 16r 160 4
1 -11 -r 493 4S7 11 1 -? -3 115 121 13 I -3 -5 258 259 1 I 0 -11 190 168 18 T2 L ).266 1231 8
1 -11 0 431 434 9 t -l -2 135 13 0 9 1 -3 -4 539 529 ø 1 0 -r0 115 201 20 2 rt66 1156 8
1-11 I 304 287 I I -1 -I 2'11 210 6 1 -3 -3 545 53 9 ? 1 0 -9 321 33L rO L2 3 831 a22 1
r -11 2 259 242 \1 1 -1 0 2'14 2'12 6 L -3 -2 425 420 6 1 0 -8 341 358 9 t2 4 584 601 8
1 -11 3 259 248 LO 1 -1 1 140 145 11 1 -3 -1 1013 985 7 r 0 -l 50? 496 12 T2 5 399 3 95 I
t-11 4 33? 313 I I -'t 2 521 518 10 1-30500 1?5 5 I 0 -6 635 639 10 r2 6 356 353 I
1 -11 5 233 239 L2 r -1 3 139 134 12 1-31118 681 6 10-51801628 I2 1 449 421 tO
1 -11 6 181 181 ls I -1 6 188 11't 12 1-32149 166 6 1 0 -{ 166 1A3 1 I2 I 400 410 r0
I -11 I 155 t16 19 1 -1 1 241 238 tt 1-33226 223 5 10-39089131 t2 9 256 253 13
I -1.0 -9 r{t t32 22 r -6 -9 2ø4 3tÌ 12 1 -3 4 360 349 l I O -2 1625 1599 9 t2 10 159 105 2r
1 -10 -l 256 255 12 1 -6 -A 491 511 Ì1 r -3 6 205 205 10 1 0 -Ì t'121 1151 9 13 -t1 18s 200 18
1 -10 -6 38s 38? 10 I -5 -? 506 533 9 1-3?181 186 t3 1 0 0 1r?0 1260 l 13 -ro r12 153 19
1 -10 -5 42r 418 10 1 -6 -6 385 391 10 I -2 -11 15{ 160 2I 1019299256 13 -9 155 I92 T9
1 -10 -4 350 359 9 Ì -6 -5 387 388 8 | -2 -10 243 221 \4 I 0 2 336 340 6 I] -8 440 441 11
1 -10 -3 24r 251 9 L -6 -4 9'17 961 9 L -2 -9 32'l 33r 10 1 0 3 ll53 rr71 8 l3 -'t 5? 9 5A6 t2
1 -10 -2 391 402 9 1 -6 -3 t322 t3t0 9 ! -2 -A 423 435 11 I 0 4 1004 9r2 I l3 -6 103 694 10
r -10 -1 543 545 10 1 -6 -2 942 93 6 I )- -2 -1 496 499 12 1050568389 13 -5 641 645 9
r -r0 0 555 553 10 1 -6 -1 765 't 5't 'l I -2 -6 613 601 10 1 0 6 394 385 9 13 -4 133 ?30 8
I -10 1 394 384 9 Ì -6 0 803 805 8 r -2 -5 1045 1034 9 10121928t9 13 3 861 863 1
1-10 2 269 281 9 7 -6 1- rt94 1187 10 | -2 -4 191 191 A 1083663139 13 -2 1090 1100 ?
r -10 3 447 440 9 1 -6 2 994 991 9 7 -2 -3 116 788 f r 0 9 290 30912 t3 -1 2249 2256 13
1-10 4 281 280 9 7 -6 3 843 851 9 r -2 -2 t11 169 4 I 0 t0 193 r-t3 1l t3 0 f21 131 6
I -10 5 169 185 14 I -6 4 559 549 9 | -2 -t 1211 )-238 A r 1 -r1 r95 218 18 13 1 841 858 6
I -10 7 199 185 14 I -6 5 512 4 83 11 \ -2 0 1553 1517 9 1 1 -10 23t 251 15 13 2 IO18 1016 I
I -9 -5 251 263 t0 1 -6 6 416 4? I 9 I -2 L 1225 1192 I Ì r -9 171 Ì86 lf Ìl 3 133I t323 9
r -9 -4 289 301 I 1 -6 f 508 509 10 | -2 2 1009 1012 l r 1 -8 145 128 17 13 4 910 894 9
r-9-331131281 -6 I 333 346 10 7-23690 6A6 1 1r-13593f79 13 5 442 452 11
7-9-221221411 -6 9 201 209 t5 t-24666 692 ø 1 I -6 552 510 l0 13 6 32r 313 8
I 9 -1 480 41510 1 -5 -6 195 225 rr l-25842 83t 9 11-59589519 t3 1 484 496 10
1-9026226211 -5 -2 r92 101 6 1-266tr 621 r1 rt-42432446 t3 a 316 364 9
1 -9 I r51 13712 1 -5 1 119 109 11 I-21298 304 9 1t-39139491 13 9 210 289 13
1-923r43t2a1 -5 3 105 111 12 t-2831s 3r4 9 17-29219246 13 t0 194 193 18
r-9343942891 -4 -r0 22ø 242 t5 t-29335 349 1l 11-199r9666 l4 -9 199 208 L6
r -9 4 340 323 I 1 4 -9 4t2 431 9 r -2 lo 244 I 1 0 744 ?40 5 t4 -8 189 2t6 t4
r 9 5 161 171 14 1 -4 I 443 480 t1 I -1 11 r58 It9 21 t1r3252935 t4 1 i26 84 l7
1 -8 -8 262 2tf t2 1 -4 -1 5f3 591 \2 1 -1 -10 216 2r4 t5 1 1 2 854 419 6 14 -6 29r 219 t
1 -8 -l 54s 551 10 1 -4 -6 216 210 I 1 1 -9 196 205 t5 1138848181 t4 -5 33 9 341 I
1 -8 -6 516 591 13 I -4 -5 1'lø 786 9 I -1 -l 201 212 11 I I 4 rl0 116 I t4 4 438 445 9
I -8 -5 416 458 12 1 -4 -4 1090 1092 9 1 -1 -6 417 466 10 1 I 5 531 523r0 Ì4 -3 469 456 1
I -8 -4 455 487 lt 1 -4 -3 t244 I2tf 9 1 -1 -5 513 52t 9 t1642'l4Jl9 14 -2 522 516 7
1-8-390188591 -4 -2 t314 1319 9 I -t -4 462 461 1 1113363368 t4 -t 926 902 I
I -8 -2 914 961 9 1 -4 -1 -t41 f40 5 7 -L -7 2r2 203 5 1 r I 307 31rr0 14 o82 64 9
1 -8 -1 â09 808 I 1 -4 0 11.23 t-r27 I 1 -1 -2 -ls9
160 151 4 1 1 9 263 25213 14 1 425 433 6
.141 1 1 10 203 1-19 1l 14 2 317 3?9 8
1-8068366181 -4 | t239 1229 9 1 -1 r 5
r -ß 1 57q 561 t0 I 4 ? 1162 1153 0 1 -l 0 1181 1199 1 t 2 -10 192 119 11 14 3 698 100 I
1 -8 2 904 90110 1 -4 3 822 821 I I -1 1 048 836 6 | 2 -9 205 193 14 t4 4 288 2ø3 1
I -8 3 910 90310 I -4 4 613 668 I 1Ì2339 341 5 I 2 -8 118 t60 14 I4 l I83 |t6 14
1 -8 4 563 541 11 1 -4 5 831 823 tO 113624 636 1 I 2 7 345 334 I l4 I 251 253 12
1-8534836791 -4 6 570 684 11 Ì -1 4 4f3 412 I r 2 -6 529 531 11 t5 -9 239 212 t4
I -8 6 333 325 I 1 -4 1 369 312 9 1-15423 421 I 12-55125599 I5 -8 410 419 11
I -0 ? 400 40110 1 4 I r81 167 l5 r-16289 289 ø 12-44394428 l5 -l 685 616 1r
1 -8 A 225 24314 I -4 9 230 24r t4 t11299 296 9 12-3168114f l5 -6 434 436 9
1 I -6 I99 2t3t2 I -4 10 2s3 244 t4 t -1 I t88 192 t5 | 2 2 109S 1092 l 15 -5 494 509 10
I 5 -4 150 ?45 I 1 9 -4 590 588 t0 I Ì3 -4 141 154 18 2 -t2 -5 391 388 10 2 -1 I 323 322 I
I 5 -3 t355 1334 9 I 9 3 435 431 9 1 tl -3 206 201 t4 2 -t2 -4 131 323 E 2 -1 2 460 453 l0
1 5 -2 1505 1486 10 1 9 -2 500 489 1t 1 13 -2 320 321 9 2 12 3 202 220 12 2 -l l 230 233 I
1 5 -l 1223 1200 9 I 9 -1 591 611 9 I t3 -r 212 213 to 2 -r2 -2 184 391 I 4 225 ?31 9
I 5 0 965 916 1 90905 890 9 1130282 296 9 -t2 -t 412 4A6 lO 2-1 5 t29 123 t6
r 5 1 1230 1255 I 9 I 838 831 9 t13t203 209 lt -I2 0 412 419 lO 2-1 6 153 r70 Ì6
1 5 2t382 1361 9 92541 s3 9 10 1132265 251 10 -72 | 2A3 2A6 lO 2 6 -9 300 323 r1
I 5 3 980 942 9 9 3 360 350 9 1 t3 3 3?9 38t 9 -t2 2 264 265 tl 2 -6 -8 35 4 359 9
r 5 4 565 584 9 9 4 591 s7r 11 1 13 4 210 201 L2 -L2 3 33r 326 9 2 -6 -'t 291 285 9
1 5 5 684 683 t0 95131 144 t2 I t3 5 141 178 21 -12 4 334 334 10 2 -6 -6 283 284 I
156823 819 11 96391 411 9 1 14 -7 1s6 153 20 -72 s 236 220 13 2 -6 -5 520 530 11
r 5 ? 568 592 t4 91255 26't t3 1 14 -6 179 165 15 -7L -2 t30 t21 16 2 -6 -4 112 691 9
1 5 I 341 3rt 10 9 8 214 206 t6 I 1{ -5 158 t 21 l5 -11 1 141 166 ll 2-6-3 820 83 0 8
159211 24t 16 10 -6 126 98 19 1 11 -3 205 220 14 -10 -a 216 244 t2 2-6-2 816 809 I
I 6 -6 Ì98 225 tI ro -5 22t 201 I0 r t4 -2 310 318 9 -10 -l 362 365 r0 2 -6 -I 611 616 I
I6-2200 211 E t0 -4 205 187 10 1 14 -1 201 204 L2 -10 -6 385 39{ 10 2 -6 0 854 830 I
1 6 -l l?9 169 6 l0 -3 138 113 15 1 11 | 213 211 tt -10 -5 3?{ 384 9 2 -6 1 1083 1005 9
I 6 0 l2l :.26 I 10 -2 151 112 t2 1 t4 2 296 298 10 -10 -4 35? 335 I 2 -6 2 819 E?l 9
16t221 221 6 10 -1 329 315 I 1 1{ 3 239 251 L3 -to -J 462 454 t2 2 -6 3 434 431 10
1 6 2 368 361 9 t0 0 183 193 r0 1 14 4 112 179 1l -10 -2 591 593 10 2-64 559 538 10
163246 239 6 10 I 200 204 9 I 15 -4 r6t t 08 20 -10 -l 591 581 10 2 -6 5 555 561 l2
I 6 5 14{ 115 14 10 2 713 167 11 1 15 -3 190 179 14 -10 0 430 {25 9 2 -6 6 542 53f 13
I 6 -t
6 234 236 \l 10 3 242 235 9 r L5 -2 L11 130 18 -10 1 338 341 8 2 -6 1 246 278 t0
I 6 191 150 14 10 5 170 150 15 t152L59 159 r6 -10 2 {83 484 l0 2 -6 8 111 r58 1l
I 7 -10 162 )-49 20 10 6 116 184 1l 1157L32 118 2I -10 3 a65 {82 10 2-5-9 291 323 1L
t1-9240 234 14 10 ? 159 139 19 I 16 -3 22! 205 14 -10 4 351 350 I 2 -5 -8 425 426 t\
1l-8363 313 9 11 -7 189 2t3 t6 I t5 -2 215 1E? 14 -10 5 213 221 ll 2 -5 -'l 269 210 9
r1-12A8 286 9 LL -6 294 295 LO 1 15 -1 215 179 13 -10 6 260 260 12 2-5-6 263 265 A
1 7 -6 358 363 I 11 -5 368 318 9 1 t6 0 204 180 t 1 -10 ? 19t 195 16 2-5-5 425 413 1L
t1-5626 614 10 lt -4 306 304 I I t6 I 242 232 t2 -9 -7 181 149 t5 2 -5 -4 692 667 I
!1-1142 't43 9 11 -3 352 336 9 116221L 225 t3 -9 -3 195 191 10 2-5-a 4A'l 4 83 8
1?-3984 914 9 tl -2 161 462 I 1 16 3 180 191 1? -9 -2 261 219 1 2-5-2 488 1't6 1
r1-2525 506 11 11 -1 607 604 11 1 l8 0 1{5 t 53 20 -a -9 203 275 16 2-5-l 508 506 7
1?-1714 ?0{ I 11 0 566 554 11 1 18 1 117 186 17 -8 -8 311 350 10 2-50 446 {?0 ô
1 ? 0 1011 1033 I 11 1 452 165 9 2 -L6 -4 L95 189 16 -8 -l 1{8 t31 11 2-sI 526 522 6
1 7 1 l33t 1335 10 11 2 359 366 I 2 -l-6 0 168 208 19 -8 -6 56{ 576 13 2-52 609 60I I
1 I 2 113 128 ø 11 3 435 147 10 2 -15 -3 l{a t31 20 -8 -S 316 3't2 tO 2-53 324 323 1
113632 631 9 lt 4 486 {65 10 2 -15 -1 182 168 r5 -8 -4 566 656 l0 2-54 282 2A4 1
I l 4 603 590 10 11 5 36{ 362 9 2 -t5 0 191 186 t5 -8 -3 112 16t 9 2-5s 32r 315 7
115192 800 l1 11 6 209 210 1s 2 -L5 2 r53 109 21 -8 -2 856 847 9 2 -5 6 361 312 9
116592 5't9 t2 11 't 202 190 17 2 -r4 -5 2t0 234 15 -0 -1 628 614 9 2 -5 1 228 2L4 t2
I 7 ? 345 339 9 11 A 226 240 16 2 -t4 -4 238 226 12 -8 0 499 511 l0 2 4-10 218 2:.9 t5
1 I 8 261 21D t-3 \2 -6 220 202 73 2 -14 -3 151 196 t7 -8 1 787 ?80 lt 2 4 -9 249 11
1192L2 234 t1 12 -5 189 155 13 2 -r4 -2 226 221 t2 -E 2 801 802 10 2 -4 -8 309 318 9
18-5275 261 I 12 -4 155 t58 15 2 -r4 -l 2â6 286 L0 -8 3 568 578 11 2-4-1 363 368 8
Ia-4262 245 'l 12 -2 302 292 I 2 -74 339 9 -8 4 259 246 9 2 -4 -6 610 682 10
1 8 0 153 163 8 12 -t 399 398 l0 2 -r4 7 223 2t3 13 -E 5 26A 260 9 2 -4 -5 101 681 9
I 8 1 {r3 405 I0 72 0 2t3 224 7r 2 -r4 2 136 t14 23 -8 6 344 i4A 9 2 4 -4 941 926 8
1E2215 261 1 t2 1 2r0 20r 11 2 -L4 3 196 15? 16 -8 1 320 J2l IO 2 -4 -3 6I1 622 1
18320'l 191 9 12 2 t65 103 13 2 -L4 4 205 2tt 16 -1 -8 23J 230 t3 2 -4 -2 941 933 7
I 9 -9 218 238 t5 12 3 289 309 10 2 -L4 6 144 | 4't 23 -1 -4 330 328 1 2 -4 -1 613 61-6 1
I 9 -8 ll9 L92 11 t2 4 2't8 286 10 2 -13 -1. 130 146 19 -1 -3 419 466 9 2 -4 0 326 322 6
r9-1254 240 7L 12 5 240 252 13 2 -t3 3 163 t35 r8 -1 -2 t25 8? 10 2 -4 I 1069 1035 I
1 9 -6 401 398 10 13 -l 133 t29 22 2 -t2 -'t 225 221 14 -t -1 350 3{4 ? 2 -4 2 643 641 1
r 9 -5 561 570 11 13 -5 tl2 156 14 2 -t2 -6 334 342 10 -1 0 158 144 9 2 -4 3 516 513 I
2 -4 1 388 3?6 I -1 I 418 410 6 2 3 -4 811 810 8 6t6L16334 294 361 314 9
2-45592 585 11 -1 2 Lt26 1150 S 2 3 -3 1360 1359 9 624294209 29s 30r 305 10
2 -4 6 {11 41? 10 -1 3 1064 1049 I 2 3 -2 \5't8 1607 10 6 3 399 389 I 296 181 216 )-6
2-4?r55 136 16 -1 4 923 92t 9 23-t1A3 1'19 1 6 4 445 4L2 tr 210-1 2ts 2 01 1.3
2 -4 9 113 200 19 -1. 5 809 801 10 230967 966 'l 6528E215ø 2to-6 334 331 I
2 -3 -10 265 286 13 -1 6 461 4?1 9 2 3 11298 131.3 8 6631a32I9 2 10 -5 316 3ft 8
2 -3 -9 32A 321 t0 -1 1 452 460 10 2 3 21901 1868 11 6 -t 114 155 20 2L0-4 344 330 9
2 -7 -8 312 330 9 -1 I 443 454 10 2 3 31105 1096 9 6 S 22r 224 15 2ro-3 386 3 50 I
2 -3 -1 299 301 I -1 9 263 201 13 2 3 4 123 't09 9 1 -9 249 246 t3 2to-2 415 471 9
2 -3 -6 546 544 10 0 -8 148 t-2 9 15 2 3 5 536 551 11 l -8 261 251 10 2 r0 -1 821 832 10
2 -3 -5 t286 1288 10 0 -6 235 219 ¿ 2 3 6 616 669 lt 1 -1 233 254 77 2 10 0 694 685 10
2 -3 -4 ).280 t269 9 0 -4 13r 135 I 2 3 7 605 633 11 1 -6 330 321 1 2t0 1 388 399 9
2 -3 -3 598 611 l o -2 451 434 6 2 3 I 396 398 9 7 -s 510 528 10 2102 442 426 I
2 -3 -2 415 421 6 0 -t 212 245 1 24-¿t56 152 16 1 -4 6t2 625 tO 2to3 491 502 l3
2 -3 -1 1199 1102 9 00191 16s 5 24-1215 248 9 ? -3 592 580 10 2t04 108 't 21 L2

2 -3 0 2188 2193 12 01492 505 6 24-6ti6 146 13 ? -2 513 570 10 2 10 5 324 318 9
2 -3 I 1381 1354 9 0 3 200 2A2 5 24-4263 211 6 1 -t 149 12ê I 2 t0 6 249 256 lJ
2-321r3 699 1 04422 403 10 2 4 -3 101 r13 11 7 0 1060 1068 9 2 70 1 231 244 A5
2-13662 660 I 06124 92 l-l 24-2940 9t3 I 1Le428319 2 l0 I 212 261 Ll
2 -3 4 898 8-r5 9 07215 2T6 T2 24-t346 351 E 125365349 2 11 -s 141 152 16
2-35606 597 10 0 I tl5 |t 2 r'l 2 4 0 37t 313 1 1 3 439 442 lt 2rt-4 241 259 11
2-)6432 434 I 1 -11 236 258 15 2 4 1 r82 19? 6 l 4 640 645 11 2TI.3 186 t62 15
2 -J 't 286 294 t0 I -10 232 25r 15 2 4 2 311 29A 6 l 5 504 509 13 2TL-2 238 231 9
2-78214 295 t2 L -9 293 294 l0 213L23 139 11 163684059 2 lt -1 290 2A5 A
2-3 92t5 206 ls I -8 348 356 I 2 4 1 250 251 1 1 1 237 232 lJ 2lI 0 293 291 A
2 -2 -9 201 211 t4 1 -7 ?03 696 11 245294 216 6 I I 208 230 17 2tl 1 166 L68 12
2 -2 -8 242 250 11 | -6 924 901 9 2 5 -11 1s9 150 19 6 -9 2t8 203 14 2712 232 246 lO
2 -2 -1 253 264 9 1 -5 884 8't3 I 2 5 -r0 203 196 16 I -8 203 211 14 2tL3 310 J61 9
2 -2 -6 276 266 1 I -4 1017 1001 I 25-921L 252 t3 a -7 ztL 20-t t2 2r1 4 226 222 L2
2 -2 -5 58L 560 9 1 -3 1081 1102 I 2 5 -8 {04 111 9 8 -6 1?9 480 9 2t2-1 290 294 tt
2 -2 -4 145 449 I | -2 2160 2t44 t2 25-1494 182 t2 I -5 531 538 11 212-6 314 319 10
2 -2 -3 430 435 'l I -1 835 s52 6 2 5 -6 56'l 5?1 1t I -4 523 509 t0 2L2-5 208 202 12
2 -2 -2 554 650 6 1 0 1008 9't9 1 25-5419 19? 10 6 -3 467 441 12 2t2-4 253 235 rl
2 -2 -t 1t34 rt22 1 I I 1036 1064 7 2 5 -4 1004 1012 9 I -2 609 511 1l 2t2-3 450 428 10
2 -2 0 2416 2356 t3 r 2 t541 1538 9 2 5 -3 t282 !259 9 I -l 680 6't3 9 2t2-2 510 516 13
2-27236 218 5 t 3 I2{3 1230 9 2 5 -2 1110 1095 9 8 0 178 ??0 9 2t2-1 400 3q8 10
2-22366 356 ? 14856 85r 9 25-L621 630 8 815725899 2120 265 214 9
2-23295 293 1 15510 493 10 250912 999 6 6 2 43f 448 tl 2t2 1 286 2E0 I
2-24691 682 9 1 6 368 366 I 2 5 1 1186 t225 9 8 3 358 342 9 2122 4 05 398 10
2 -2 5 558 536 ll |I 52t 509 13 252641 849 I 8 4 4r4 400 9 2123 539 511 13
2-26179 1?? 13 I 8 46{ 46A t2 253616 620 9 854014009 2124 {11 424 t0
2 -2 l 161 166 15 r 9 219 304 13 2 5 4 569 518 10 I 6 210 211 lt 212s 198 225 15
2-2S158 L15 T9 2 -1 tr8 103 17 255132 7r0 11 3 7 193 193 16 2126 200 t97 16
2-29792 192 71 2 -5 t54 t48 9 2 5 5 788 763 11 I I 181 209 19 2 14 -5 189 183 16
2 -1 -10 3s? 364 1t 2 -4 236 226 5 25'l 394 414 10 9 -l 260 261 10 2 14 -4 212 250 14
2 -t -9 321 333 10 2 -3 t16 169 5 254249 23t 13 9 6 356 310 9 2L4-3 381 383 9
2 -t -8 328 331 8 2 -1 119 928 26-923I 22t 14 9 -5 295 315 I 2 t4 2 384 391 10
2 t -1 114 454 l2 2 0 184 l.63 s 26-8t31 155 19 9 -4 366 310 8 2t4-l 3t8 309 9
2 -t -6 891 894 10 2Jt09 t1 10 26-6r39 r20 13 9 -3 117 3t3 8 2 14 0 349 351 9
2 -1. -5 8s9 856 9 3 -10 218 218 r5 2 6 -5 {05 489 10 9 -2 399 393 9 2 14 I 369 312 9
2 -t -4 451 4 89 I 3 -9 300 335 11 2 5 -4 414 {83 t0 9 -t 542 535 10 2 14 2 417 402 ro
2 -I -3 LL29 1125 8 3 -8 588 s81 13 26-3259 265 6 9 0 363 370 I 2143 2a1 291 lr
2 -r -2 1629 1631 9 3 -1 704 697 1t 26-2r24 91 t2 9 I 449 45s 11 2 ),4 4 2L6 224 14
2 t -t 1391 t358 I 3 -6 4A2 462 r0 26-tr93 195 7 923463121 2 14 5 2L3 2t9 \s
2 -r 0 1{98 t483 9 3 -S 42A 43t 9 2 6 0 430 145 I 934033019 2t6-3 16s r81 1?
2 t6 -2 l6a 152 15 -9 6 214 t 94 t-2 3-64342 328 ø -2 -2 r51 t4r 6 310 433 449 1
2 16 -1 t94 185 15 -9 -5 191 213 12 3 6 5 255 228 rO -2 -t 95 103 11 311 993 1028 l
2L6025L 249 12 -9 -4 441 431 9 3 -6 6 156 142 l6 -2 0 {83 456 ? 312 907 930 8
216I263 259 12 -9 -3 631 625 10 3 5 -1r l.-19 169 1l -z 1 206 ì90 5 313 108{ 1099 9
2t62241 252 L3 -9 -2 498 480 11 3 5 -10 286 290 12 -2 2 t21 t34 9 314 6t? 601 t0
2 t8 0 151 162 r9 -9 -1 l/l J62 9 I -5 -9 JtJ J26 LO -2 4 1U4 84 15 115 281 28J n
3 -r4 -6 230 229 t5 -9 0 291 307 I 3 -5 -0 281 281 tO -2 5 119 84 1l lr6 361 382 9
I -14 -5 230 240 l4 -9 1 4f3 418 9 3 -5 I 365 384 9 -2 1 121 16 20 311 411 46t 11
3 -14 -4 117 162 t6 -9 2 391 42L ø 3-56511 506 1l -t -ll 252 212 14 3t8 310 312 rr
3 t4 -3 2t1 194 13 -9 3 399 405 r0 35-595E 952 10 -t -10 311 323 t] 319 t16 r?0 19
3 -t4 -2 240 252 12 94235 263 11 35-4832 825 9 -I -9 292 290 rO 3 2 -9 t7? 2t4 16
3 -r4 -1 311 291 r0 -9 5 264 2-t 5 11 3-53102 109 E -r -8 258 229 9 3 2 -A f8? 4 05 9
3 -14 0 165 t52 t6 -8 -8 199 190 15 f,-52651 653 I -t -l 690 109 11 32-1 602 621 \t
3 14 I 21r 187 14 -8 7 194 191 t4 3-5lAf2 900 I 1 -6 183 181 9 3 2 -6 258 256 1
3 -14 3 213 792 t6 -a -6 241 236 10 3 -5 0 1092 1114 9 -1 -5 991 992 9 3 2 -5 219 21I f
3 -I4 4 2t6 194 1.5 -8 -5 175 180 12 3 -5 I 983 994 9 -1 4 484 502 I 324 531 548 8
3 13 5 t44 151 20 -8 4 430 431 9 3-52465 4E6 9 -1 3 1460 14?8 9 3 2 -3 1103 t10s 8
3 -t2 -6 264 244 12 3 -8 -3 468 462 11 3-5 3 523 510 l0 -1 -2 t344 1375 9 3 2 -2 f6a ta2 f
3 -12 5 266 233 10 3 -8 -2 340 348 I 3 -5 4 60r 602 10 -l -r 836 83I l 7 2 -t 45t 452 1
3 -12 -4 252 244 10 3 -8 -1 335 320 I 3 -5 5 618 629 12 -1 0 1000 1021 I 120 502 5r9 l
3 -12 -3 28\ 293 10 3 -8 0 363 369 9 3 -5 6 312 3?5 9 -t 1 838 8a2 1 321 9S9 966 A
3 -r2 -2 162 456 10 3 -8 1 439 1s0 9 3 -5 1 254 252 t2 -1 2 1305 L320 9 919 933 8
3 -r2 -r 432 448 10 3 -8 2 293 292 g 3 -5 8 195 210 1l I 3 1115 1108 9 323 159 463 9
3 -12 0 26s 281 10 3 -8 3 ta2 t91 L2 3 -5 9 220 226 rs -r { 834 835 9 324 569 531 10
3 -L2 I 240 2s9 L2 3-8 4 201 188 11 3 -4 -8 20s t96 t2 -1 5 501 515 l2 125 451 433 I
3 -L2 2 256 248 \2 3-8 5 186 1r3 13 3 -4 -1 2t8 208 r0 -l 6 451 454 10 f26 510 s13 10
3 -12 3 3tt 310 t0 3-8 6 228 t96 12 J -4 -1 I21 108 10 -1 I 464 466 11 f21 391 391 l0
3 -t2 | 230 208 t3 3-8 ? 196 210 16 3 -4 -3 328 318 6 -1 I {t9 414 11 328 160 155 t9
J -Lr -1 236 229 t3 7-1 -9 318 349 10 3 -4 -1 294 291 1 -1 9 233 272 75 3 3 -t0 200 t98 I6
3 -lt -6 243 241 t2 3-1 -8 392 {09 10 3 -4 0 154 130 8 0 -9 1{3 164 19 3 3 -9 250 240 t1
3 -11 -5 168 164 15 3-7 -7 308 331 9 3 -4 1 160 137 I o -8 212 214:.1 3 3 -8 325 310 8
3 -11 -3 269 258 9 3-f -6 402 {03 10 3 -1 1 108 86 16 0 -? 310 303 0 33-f 481 410 t2
3 -11 -2 330 343 I 3 -'l -5 {?4 161 11 3-3 -10 212 309 13 0 -6 355 362 9 3 3 -6 35I 3 65 9
3 -11 -1 353 360 S 3-1 -1 696 695 LO 3-3 -9 313 353 9 0 -5 373 345 9 3 3 -5 595 5 91 9
3 -11 0 2L3 215 11 3 -'l -t 692 699 9 3-3 -8 2't s 295 10 0 -t 335 338 g 3 3 -4 169 113 I
3 -11 1 225 206 11 3-1 -2 62t 606 9 3-3 -1 662 619 11. 0 -3 419 484 1 3 3 -3 961 981 I
3 -lL 2 232 219 12 3-1 -1 534 s26 9 3-3 -6 a41 810 10 0 -2 701 695 f 3 I -2 s21 830 8
3 -11 3 200 t 99 13 3-1 0 685 683 10 3-3 82L ø24 9 0 -1 711 144 1 3 3 -1 1169 1160 9
3 -10 -8 t69 1.8 6 19 3 -'l 1 786 777 L0 3-3 -4 601 633 I 0 0 838 804 l 330 169 't't 4 1
3 -10 -1 211 2AA 72 3-? 2 557 5r8 10 3 -3 -3 194 s11 7 01131 130 7 331 rt39 1146 8
3 -10 -6 331 339 9 3-1 3 356 373 I 3 -3 t20'l L2L6 8 02513 56 1 132 90 8 92 0 8
3 -L0 -5 301 303 9 3 -'l 4 310 362 I 3 -3 -l 1579 1573 10 0 3 549 55 I 333 666 646 8
3 -r0 -{ 30s 317 I 3-1 5 515 509 13 3 -3 0 1861 18ft 11 04329 32 1 334 364 365 0
3 -10 -3 469 465 9 3 -'l 6 269 285 rl 3 -3 1 8{2 858 0 5 206 20 t0 335 459 458 9
3 -LO -2 424 410 9 3 -'l I 209 198 t{ 3-3 2 510 14 0 ? 171 t5 15 336 f22 130 12
3 -10 -1 323 331 1 3-6 -g t21 13 20 3-3 3 812 33 r -10 226 23 1{ 331 361 3l1 9
3 -10 0 255 267 9 3-6 -'t 23 4 201 t0 3 -3 4 901 g2 r -9 330 33 10 3 4-10 231 22I T3
3 -10 I 100 407 9 3-6 -5 298 288 'l 3-3 5 70? l6 1 -8 161 1'l t0 3 4 -9 344 340 9
3 -10 2 54'l 554 12 3-6 -4 159 168 11 3-3 6 329 2l I -l 569 5l tl, 3 4 -8 383 401 9
3 -10 3 311 395 9 3-6 -3 33? 316 I 3-3 1 136 43 r -6 12â 12 9 3 4 -l 348 329 I
3 -10 4 202 199 13 3-6 -2 3!1 3Lt 'l 3-3 8 323 21 l1 1 -5 ?10 ?00 8 3 4 -6 232 244 I
3 -t0 6 r99 18{ 15 3-6 0 346 344 I 3-3 9 218 61 14 1 -{ 10{2 1048 I 3 4 -5 6s5 661 9
3 -10 1 225 208 14 3-6 I 166 152 L0 3-2 -6 219 36 I 1 -3 E98 932 1 3 4 -4 10l f 1082 9
3 -9 -8 293 201 tl. 3-6 2 2't4 268 1 3-2 -4 t't 1 63 'l 1 -2 rl54 1163 8 34-3 r265 t2s9 9
3 -9 -'t 259 243 t7 3-6 3 170 16{ 10 3-2 -3 t29 00 I 1 -t t{96 15 41 9 34-2 43 0 43s 9
34-1612 618 I 31 5 290 2ã2 I 312 5 210 223 LS -11 3 24r 253 4 -s -9 241 212 L2
3 4 0 1,091 r090 I 38 -9 203 209 \1 3t2 5 21I 280 t3 -11 4 156 114 18 4 -5 -8 345 t58 9
3 4 rL092 1110 8 38 -a 249 244 tL 3 13 -1 L13 l6? 19 -10 -7 159 134 18 4 -5 -7 412 480 9
31216ø 496 I 30 -? 366 369 9 3 L3 -2 2?8 22L 10 -10 -6 155 1{s t6 {-5-6 555 562 r1
3 4 3 355 365 I 38 -6 520 535 t2 3 13 -1 230 225 lO -10 -4 169 141 l3 4-5-5 894 888 10
3 1 4 546 520 10 38 -5 655 668 11 3 13 0 221 233 11 -1 0 -Ì 130 135 16 4 -5 -4 140 125 9
345512 540 11 30 -4 565 565 11 3 13 I 231 224 l7 -10 0 188 208 t3 4 -5 -3 494 4 9t 9
3 4 6 457 428 10 38 -3 635 613 11 3 13 131 r41 20 -10 1 196 111 t3 4 -5 2 ?04 594 8
3 1 ? 314 323 r0 38 -2 690 661 t0 3 13 3 206 220 t4 -10 2 130 r26 19 4 -5 -1 7269 1294 t0
3 4 8 238 235 14 38 -1 I0 65 1055 10 3 13 141 19 19 -9 -9 212 21r 13 4 -5 0 t289 1260 10
3 1 9 171 t1I 20 30 0 134 760 9 3 14 -5 229 2r8 15 -9 -8 296 282 tt 451 121 f25 9
3 5 -11 140 30 1 612 614 9 3 14 -4 222 244 11 -9 -1 245 11 4 -5 2 464 483 10
35-0214 280 10 38 5?3 56{ 10 3 t4 -3 23L 230 13 -9 -6 260 249 10 453 66r 634 10
3 5 -? 1l{ 159 12 38 3 758 7{1 11 3 1{ 256 266 tO -9 -5 309 305 I 4 -5 4 650 641 I1
3 5 -6 31s 314 ? 38 4 634 635 t2 3 1{ -t 252 258 10 -9 -4 608 599 11 4 -5 s 359 163 I
3 5 -5 190 196 9 38 5 458 471 r1 3 14 0 2A'l 285 10 -9 -3 581 599 11 4 -5 6 212 292 rl
35-4292 291 'l 38 6 369 351 9 3 14 1 330 321 9 -9 -2 408 419 9 4 -5 f 190 181 16
35-3508 498 9 38 1 300 331 12 3 14 2A1 303 1l -9 -t 35E 369 8 4 -4 -t0 2t9 222 15
35-2t28 125 10 38 I 321 344 12 3 14 3 213 230 14 -9 0 498 52ø L3 4 -4 1 325 344 I
3s-1792 192 8 3 10 -0 200 201 L4 3 15 -4 251 2t3 15 -9 1 598 631 13 4 -4 -6 55 9 543 10
3 5 0 546 543 0 3 10 -'l 298 298 9 3 15 -3 2LO 196 14 -9 2 419 495 t0 4 -4 -5 3f8 368 I
3 5 I 611 621 I 3 10 -6 351 35? 9 3 15 0 151 158 18 -9 3 295 304 9 4 -4 -4 245 252 6
352129 135 10 3 l0 -5 315 37r 9 3 15 1 234 215 13 -9 4 299 308 9 4-4-3 339 328 'l
3 5 3 500 4?7 r0 3 10 -4 420 435 9 3 16 -1 t14 r38 15 -9 5 215 293 1l 4 -4 -2 583 5 95 I
3 5 1 398 312 9 3 10 -3 s31 s3? 10 3 15 0 186 187 15 -9 6 230 269 14 4-4-l 53s 540 9
3 5 5 {56 458 L0 3 t0 116 754 1r 3 1l -l 168 111 1l -1 -to 243 26I L4 4 -4 0 507 410 9
3 5 6 304 301 10 3 10 -t 119 ?76 10 3 1l 0 198 191 15 -l -9 358 357 10 4 -4 I 4 01 42t r0
3 6 -10 255 253 13 3 10 0 419 487 Il 3 17 1 179 158 16 -? -8 346 342 9 4 -4 2 33 8 329 I
3 6 -9 331 J27 10 3 10 1 401 4L2 9 4 -15 0 140 L22 2t -l -7 388 3-19 9 4 -4 3 408 420 I
3 6 -8 311 310 9 3 10 620 603 11 4 -11 -5 131 96 2L -1 -6 149 44ç l0 4 -4 4 445 425 9
36-1251 261 9 3 10 3 802 8t2 t2 4 -r4 166 159 r7 -1 -5 631 625 r\ 4 -4 5 2t0 192 rl
36-6521 539 1t 3 t0 4 506 5L9 10 4 -13 -6 202 2tt t6 -1 -4 115 ?49 10 4 -4 6 198 185 13
36-5871 88? 10 3 10 5 333 350 10 4 -13 -1 162 14s t6 -7 -3 600 602 10 4 -4 1 193 150 15
3 6 -4 114 11A 9 3 10 5 231 243 t4 4 -r3 -2 255 2{5 tt -1 -2 'tto 581 9 4 -3 -11 198 111 16
36-371s 713 9 3 10 1 325 339 12 { -13 -t 200 190 13 -1 -r s22 539 10 4 -3 -10 225 220 14
36-2221 250 1 31r -1 165 160 16 { -13 0 194 2L5 14 -1 0 662 659 l0 4 -3 -9 213 263 10
35-1931 962 9 3 lt -6 163 132 15 4 -13 1 201 213 15 -'t I 611 601 10 4 -3 -0 351 350 I
3 6 0 1293 1304 9 3 11 -3 234 232 a2 4 -13 2 2L2 205 1s -1 2 503 504 11 4-3-1 356 345 I
3 6 It249 t231 9 3 11 180 160 I2 { -13 3 186 180 1l -1 3 344 364 I 4 3 -6 553 532 10
362116 ? 08 9 3 11 -1 t64 168 L2 4 -t2 1.3 0 t12 20 -'7 4 {18 41r 10 4 -3 -5 31'l 396 I
363621 -tto 597 10 3 lL I r45 153 14 4 -t2 -4 150 15I 1't -1 5 3?4 378 10 4-)-4 4A1 496 9
3 6 4 699 10 3 11 r26 115 17 4 -12 -3 L24 165 20 -'t 6 J23 329 t0 4-3-3 698 710 I
3 6 5 611 610 t2 311 3 163 151 15 4 -t2 0 14{ 115 17 -6 -6 114 96 18 4-3-Z 685 f04 I
3 6 6 455 475 t1 712 233 25't !3 4 -72 2 149 157 19 -6 -5 33E 323 I 4 -3 -1 87I 883 I
361291 269 LT 312 -6 200 202 13 4 -11 -9 147 t15 22 -6 -4 265 29t 1 4-30 52r I
368245 25s 1s 312 -5 2l'l 217 t3 4 -11 -'l 299 300 1l -6 -3 19? 198 I 4 -3 1 213 282 6
3 7 -6 169 158 12 3L2 -4 285 216 t2 4 -11 -5 224 233 13 -6 -r 428 430 r0 4-i2 611 63'l 9
3 1 -5 224 218 9 312 -3 169 {48 11 4 -11 222 20t 72 -6 0 632 602 10 4-3 1 163 ?00 l0
3 7 -4 308 306 I J12 415 {91 10 4 -11 -4 318 131 9 -6 1 135 156 l3 4-34 561 551 11
31-2t14 104 13 3t2 -1 252 231 9 4 -tt -3 457 193 10 -6 2 103 1Ì 9 t? 4 -3 5 343 )f6 9
3 I -1 251 243 1 3 t2 0 265 260 9 { -11 -2 {43 468 10 -6 4 26J 280 9 4 -3 6 263 215 1l
3 1 0 366 316 1 3t2 1 401 100 9 { -r1 -1 191 168 12 -6 -t 6 146 99 18 4-f'l 'l \1 329 11
31t265 255 6 3t2 2 517 513 l0 4 -11 0 269 261 10 -6 138 I2T 2I 4 -3 I 213 281 t3
312L93 r t0 9 3t2 385 381 10 4 -11 I 209 282 10 -5 -11 16? L30 18 4 -2 -tO 194 112
314255 262 9 3t2 4 t16 163 l6 4 -1L 2 314 362 9 -5 -r0 228 228 Ls 4 2 -8 254 245 Ì0
1 -2 -1 603 602 11 4I -10 160 t66 19 44 0 1214 1L9r 9 I -3 444 452 9 412-2 246 252 l0
4 -2 -6 540 546 10 41 -9 t46 14? l8 44 1 9¿4 995 9 g -2 815 81? t0 412-7 t42 160 15
4 -2 -5 516 5lt 9 41 -8 296 213 9 44 2 566 583 9 I -1 941 925 10 4120 288 264 9
4 -2 -4 4t3 434 I 41 -6 r69 r66 10 44 3 120 121 t0 I 0 585 606 10 412 I 25s 253 l0
4 -2 -3 lO23 I 018 I 4l -5 234 238 6 44 4 ?70 149 Ì1 6 I 425 448 I 4t22 2J5 231 ll
4 -2 -2 995 1009 I 41 -4 42L 426 9 44 5
-t
10 120 t2 82648 639 tl 4 12 3 tlÌ l3r 20
4 -2 -L 662 6't 4 I {1 -3 256 264 6 44 6 50? 501 10 I I 669 662 IT 4124 168 116 1l
4-20125 154 I 4t 292 305 1 44 1 229 225 14 I 4 638 631 l3 4 13 5 260 251 l3
4-2t225 230 6 41 -1 316 3 01 6 41 I 260 261 t4 I 5 299 301 10 4 13 -4 343 331 ìI
4-22892 909 8 4I 0 \6'l 185 1 45 -6 234 238 9 86283 264 t2 4 13 l 315 362 9
4 -2 r 619 616 9 41 I 614 659 I 45 -5 211 213 1 I I 300 310 12 4 t3 -2 100 298 9
4-24532 5 43 11 4T 2 611 606 I ,{5 -4 251 255 7 9 -8 198 t89 13 4 Ì3 -1 210 261 9
4-25265 251 9 41 3 399 l8 I 45 -t I?3 169 I 9 -1 292 253 9 4 13 0 156 3'11 I
4-26253 1l 4l 133 11 14 45 0 155 !62 9 9 -6 104 319 9 4 13 ì 424 426 9
4-21221 236 t4 4t 5 156 14 14 45 I r88 184 I 9 -5 121 I13 1f 4 13 2 190 38? t0
4-28250 235 14 41 6 239 11 45 3 1r 4 146 11 9 -4 238 244 tO 4 13 3 230 ll
4 -1 -10 159 158 19 41 1 218 20 14 46 -11 119 201 1E 9 -3 359 35 9 9 4 13 4 234 251 ll
4 -1 -9 118 198 15 42 -10 23 0 t4 46 -10 235 235 14 9 -2 529 511 l2 4 13 5 286 294 l2
4to2l1 210 42 t 351 3S q 45 t) 265 214 rt 9 -1 434 43I I 4 t4 -l t 75 r 4l t{
4 -1 -l 300 3 08 42 -8 561 54 t2 46 -3 330 343 9 91211 2r5 9 4 74 0 t46 108 1l
4 -t -6 442 460 42 -1 620 6t 10 46 -1 3 98 4r8 10 92211 218 9 4 t4 I r5t 1r9 lf
4 -1 -5 519 509 42 -6 421 434 l1 46 -6 840 851 l1 9 3 395 388 9 4 15 -4 211 211 tl
4 -t -4 152 130 42 -5 581 s75 9 46 -5 801 ?93 10 9 4 325 321 9 4 15 3 209 218 l4
4 -r -3 626 659 -4 1150 It5-l 9 46 -4 703 599 l0 9 5 230 211 t3 4 15 2 r68 119 l6
4 -t -2 920 938 42 -3 113 4 rt52 9 46 -3 501 497 r0 10 -l 219 271 12 4 15 -1 210 209 ll
4 -t -1 143 151 42 1293 12 85 9 46 -2 t059 1065 r0 10 -6 2ll 290 t0 4 t5 0 r6l 155 9
4 -l 0 260 269 42 922 9{0 8 46 -1 9?f 993 I l0 -5 235 254 1l 4 15 ì J24 )t6 l0
4 -l 1 661 669 42 0 1396 1416 9 46 0 1065 1049 9 10 -4 144 342 9 4 15 2 226 233 tl
412693 609 42 I t251 t264 9 46 L f29 1IO 9 t0 -l 315 3 66 8 4 15 4 196 201 I5
4 I 3 593 5t1 2 1049 I066 9 46 2 667 655 10 lo -2 szJ 516 12 4tt-2 150 t62 l8
4 -1 4 333 322 I 423542 555 9 1 6 3 543 624tO 4 10 -r 315 323 1 411 1 200 205 15
{ I 5 110 l{0 12 424604 602 10 4 6 4 586 5f812 4 r0 0 33f 338 I 4t1 0 1l? 191 r6
{-16212 231 11 425152 't24 t\ 4 6 5 615 61513 4 10 1 396 379 9 5 -15 -5 139 tss 22
4-t129s 294 L). 426629 650 l3 1 6 6 311 31510 4 10 2 174 445 10 5 -15 -2 160 151 19
4 -1 9 141 TT2 23 4 2 7 403 399 9 4 6 1 213 253\4 4 10 3 461 4?6 10 5 -15 -r 185 113 16
4 0 -10 150 145 20 4292L9 225 ).6 4 6 A 286 2'1913 4 10 4 294 285 l0 5-15 2 151 111 20
4 0 -9 214 254 10 43-8153 110 l5 41-623t22091105165 186 18 5 -13 -8 188 \12 L1
40-8656 642 12 43-1220 215 9 4 1 -5 218 285 I 1 10 7 198 224 11 5 -13 -7 t 8? 205 18
40-1656 661 10 43-6312 332 I 41-42612628111-?280 216 I0 5 -13 -6 \11 190 l8
4 0 -6 434 424 tO 43-4115 103 11 4 1 -a 161 118 12 4 11 -6 2?0 256 t0 5 -13 -s r62 113 17
40-5129 433 9 43-3442 431 9 1 1 -2 160 181 11 1 ll -s 212 249 11 5 -13 -4 184 2tl 15
4 0 -1 113 l?0 I 43-236! 351 9 1 7 -1 621 592 10 1 11 -4 316 351 9 5 -13 -3 285 293 10
4 0 -3 13't6 ì3 05 9 13-1181 156 't 1 1 0 {23 13f10 a 11 -3 469 152 10 5 -13 -2 255 2Sr 12
4 0 -2 L0?5 1093 I 435246 253 t0 4 't 1 1?5 185 9 I ).1 -2 484 {81 9 5 -13 -1 224 258 13
40-191? 90{ 0 4 3 6 118 102 l7 4 1 2270200 9 4 11 -1 313 311 I 5-13 0 114 181 16
400161 758 8 { 4 -10 299 295 11 41335134t84110120 428 9 5-13 1 249 226 12
401935 94r I 44-9361 3't2 9 41430129391r11535 5J4 t2 5-13 2 250 236 t3
4 0 21065 10{8 9 41-8385 391 9 4 1 5 163 t3{16 4 lr 2 518 583 13 s-13 3 186 201 L1
4 0 3 846 841 9 41-1259 296 I 4 1 6 182 1?116 { ll J 250 2't o t2 5 -L2 -3 159 143 15
4 0 1 507 511 11 44-6624 623 rO 4 8 -9 239 22012 1 11 1 L59 185 Ì8 5 -11 -9 168 155 19
4 0 5 10? 40? 10 44-s992 9? 9 9 4 8 -8 18? 19814 4 11 5 216 224 \4 5 -11 -8 198 193 17
4 0 6 4å6 416 10 44-4939 953 9 4 A -1 2A9 290 9 { 11 6 242 256 14 5 -lt -l 197 189 16
40't361 356 9 44-3583 58? 9 48-63713808{12-5lll 182 16 5 -11 -6 182 190 15
{0a252 25t t4 44-2513 595 9 48-54511569412-4110 184 I8 5 -1r -5 250 26f lI
4 0 9 144 t5{ 24 4 4 -1 1051 1065 9 48-44624199412-3266 214 Ll 5 -11 -4 355 352 I
5 -11 -3 360 3 69 9 5-?0363 374 I 5 -4 3 687 689 10 5 0 1 1326 t322 L0 5 4 -8 212 292 l0
5 -)-L -2 21L 235 10 5-?t296 3 05 8 5 -1 1 330 331 I 5 0 2 t0l7 1038 9 5 4 -f 252 260 I
s -11 -1 288 291 9 5-72201 219 10 5 -4 5 371 319 9 5 0 3 613 609 10 5 4 -6 596 600 10
5 -11 0 21'l 281 10 5-73243 259 10 5 -4 6 2'13 2'11 lL 5 0 4 126 41.7 I 5 4 -5 666 661 I0
5 -11 1 340 340 9 5-l42gl 282 I0 5 -4 1 2A6 2A612 5 0 5 534 532 13 5 4 -4 5 9l 595 9
5 -11 2 215 255 t2 5-1526I 256 11 5 -4 A 200 226),1 5 0 6 578 600 14 5 4 -3 615 635 9
s -11 3 L12 193 16 5 -1 6 143 I39 21 5 -3 -7 121 10116 5 0 I 385 380 10 s4-2 311 340 3
5 -11 4 165 135 1? 5 -6 -10 235 222 L4 5 -3 -6 108 11116 s 0 I 158 L18 22 5 4 -1 94 8 929 9
5 -11 5 150 149 20 5 -6 -9 183 158 16 5-3-5185193951-9195 18 9 1.4 540 1002 1006 9
5 -1r 6 lal 157 21 5 -6 -8 135 131 19 5-3-333?3{6?5r-A2a1 253 10 541 856 452 9
5 -10 -5 108 195 13 5 -6 -7 316 325 9 5 -3 -1 116 A112 5 I -5 137 153 1 542 519 510 10
5 -t-0 -1 189 185 12 5 -6 -6 120 { 0t 9 5 -3 0 15( 1'16 10 5 1 -4 151 485 s43 503 500 11
5 -10 -3 211 240 l0 5 -6 -5 630 528 11 5-3t245235751-3155 164 544 663 642 12
5 -10 0 18{ 165 l3 5 -6 -4 358 365 9 5 -3 2 296 3I1 'l 5 1 0 191 206 545 464 4 60 10

5 -10 1 170 173 15 5 -6 -3 287 285 1 5 -3 4 142 149 15 5 1 L 214 216 546 239 256 13
s -r0 2 t)9 160 l8 5 -6 -2 41t 4?0 10 5 -3 6 150 1271ô s r 3 16ì t64 t2 541 209 180 l6
5 -9 -9 1.71 2L3 20 s -6 -1 703 ?0-, 10 5 -2 -11 L6L 2lO 21 5 1 5 12S 109 19 548 2tt 252 Ì8
5 -9 -0 205 194 15 5 -6 0 't23 141 10 5 -2 -10 119 l?9 L6 5 2 -10 255 243 72 5 5 -11 150 168 2l
5 -9 -6 253 225 t0 5 -6 I 433 431 I s -2 -9 404 416 10 5 2 -9 351 341 9 5 5 -10 220 214 t4
5 -9 -5 29'l 3r3 9 5-623t6 319 1 5 -2 -8 168 461 9 5 2 -8 382 381 9 5 5 -9 141 160 18
5 -9 -4 398 399 10 5-63413 4 68 I2 s -2 -1 503 59s 11 5 2 -1 402 406 9 558 242 235 10
5 -9 -3 308 30? E 5-64400 41t 9 5 -2 -6 550 564 l0 5 2 -6 50? 498 10 551 285 269 I
5 -9 -2 216 211 A 5-65321 330 9 5-2-5152123952-5152 150 9 5 5 -6 615 64 Ì1
5 -9 -1 384 4 04 I 5-66202 205 14 5 -2 -1 75? 768 I 5 2 -4 1004 1014 9 555 521 s2 t0
5-903a2 383 9 5 -6 f 119 185 18 5 -2 -3 1065 1073 9 5 2 -3 986 961 I 554 360 3l 8

5-9139? 395 9 5 -5 -9 195 199 15 5 -2 -2 1191 1191 9 5 2 -2 9L1 940 9 553 619 58 10
5-92256 258 10 5 -5 -8 210 226 13 5-2-18?1817852-r920 90? 9 5 5 -2 6l a 61
5 -9 3 211 218 12 5 -5 -1 254 240 IO 5 -2 0 703 732 I 5 2 01099 1114 9 s 5 -1 960 934
5-94266 262 L7 5 -5 -6 286 269 I 5-21129143952L914 915 9 550 517 513 9
5-95264 251 12 5 -5 -5 2?9 280 1 s -2 2 1068 10?8 10 5 2 2 461 463 10 551 5 64 534 9
5 -9 6 158 166 l9 5 -5 -4 340 342 9 5 -2 3 801 79510 5 2 3 511 500 11 552 419 468 r1
s -8 -9 215 195 15 s -5 -3 306 305 1 5-243433139s246\0 609 \2 553 6t 0 s98 11
5 -8 -8 161 193 18 5 -s -2 499 501 10 5-25365361852555? 654 13 554 430 419 10
5 -8 -l 13? t3? 18 5 -5 -1 699 613 9 5 -2 6 288 30211 5 2 6 44r {35 9 555 322 335 10
5 -8 -6 299 249 9 5-50626 63'' 10 5 -2 ? 356 35110 5 2 'l 248 22't 73 556 10? 2rt t'ì
5 -8 -5 319 322 I 5-5t212 2L3 9 5 -2 I 208 21111 5 2 A 225 183 r5 551 \6'l 203 2r
5 -8 -1 118 422 9 5-522r2 235 9 5 -t -8 149 10'r 15 5 3 -10 216 t 96 14 558 24r 250 15
5 -a -3 269 265 2 s-53280 212 I 5-1-620r2039s3-9266 269 t\ 5 6 -10 142 131 20
5 -8 -2 170 176 11 5-54206 295 9 5-1-51991968s3-1161 161 t2 s 6 -9 170 191 t5
5 -8 -r 130 {53 9 s-55184 190 14 5 -1 -1 1ll 96 11 5 3 -5 300 2A9 1 5 6 -8 246 2s0 10
5 -8 0 404 409 l0 5-58145 119 22 5-1-3294291653-57E0 112 9 56-1 319 336 I
5 -8 I 3{{ 356 I 5 -4 -11 20? 23r 16 5-1-1183155153-4512 531 9 5 6 -6 355 151 8
5-82190 t82 12 s -4 -10 210 213 5 -1 3 LL2 1616 5 3 -f 225 242 1 5 6 -5 353 342 9
5 -8 3 t7l 112 r3 5 -4 -9 175 187 l6 5 0 -11 r49 153 2l s 3 -2 321 320 I 564 433 432 I
5 -8 4 135 144 t8 5 -4 -8 319 303 9 s 0 -10 245 24A 12 5 I -1 555 563 9 5 6 -3 s25 1l
5 -8 5 1{9 1f5 19 5 -4 -'t 508 506 t2 5 0 -9 44I 451 9 5 3 0 123 f 17 I s 6 -2 543 534 10
5 -? -10 1{6 L2\ 22 5 -4 -6 64r 632 10 5 0 -8 582 51612 5 3 1 s59 54 9 9 s 6 -1 603 508 l0
5 -7 -8 204 2t1 14 5 -4 -5 523 520 10 5 0 -l 588 60011 5 3 2 471 425 10 560 345 146 A
s -1 -'t 218 264 tO 5 -4 -4 461 465 10 5 0 -6 1{2 143 I 5 3 3 220 215 9 561 492 4 9? ).0
5 -1 -6 713 320 I 5 -4 -3 834 849 9 50-5?0069?9534398 389 r0 562 346 339 I
5 -7 -5 414 4't8 9 s -4 -2 963 961 9 5 0 -4101?1029 9 5 i 5 34'l 329 9 563 418 4t5 l0
5 -l -4 288 288 I 5 -4 -1 678 665 9 5 0 -310321054 9 5 3 6 235 2T5 L2 564 4t0 396 9
s -'t -3 265 212 1 5-40305 320 'l 50-2936939853'll5l 153 20 565 195 1E9 14
5 -'t -2 304 3t6 'l 5-41581 605 10 5 0 -t 605 696 I 5 4-10 180 190 1? 566 138 t61 23
5 -1 -L 421 { {3 I 5 -{ 2 651 668 10 500666689854-9295 100 10 561 r81 197 r9
5 ? -10 176 169 17 5 11 -2 531 530 r2 6 -10 -7 182 181 16 6 -5 2 13E 118 14 6-t-1 350 35 4 I
5 I -9 L'to 186 16 5 11 -1 409 421 10 6 -r0 -6 215 21L l0 6 -4 -Lt 180 tl9 18 6 -1 -6 210 241 1
5 ? -8 236 235 11 5110594 603 72 6 -10 -5 260 2A4 l0 5 -4 -10 152 t99 2l 5 -1 -5 481 468 r0
5 't -1 429 432 l0 5111545 528 t2 6 -10 -{ 311 310 9 6 -4 -9 219 2s6 12 6 -1 -4 638 651 9
51-6523 489 L2 5112381 387 9 6 -10 -3 18? 185 12 6 -4 -8 28-t 203 10 6 -r -3 861 857 9
57-5{14 403 9 5 11 3 309 325 10 6 -10 -2 260 219 r0 6 -{ -l 51{ 494 12 6-t-2 442 486 10
51-1266 211 I 5114258 253 12 6 -10 -1 252 253 lO 6 -4 -6 531 534 Ll 6 -1 -1. 303 31f f
5 l -l 6?1 705 11 s115354 357 10 6 -r0 0 289 289 10 6 -4 -5 494 486 11 6 -1 0 615 661 9
51-2993 984 10 5 tl 6 296 306 t2 6 -10 1 261 266 l0 6 -4 -4 550 543 10 6 -t I 595 594 10
5 I -1 931. 919 r0 5 13 -7 156 159 18 6 -10 2 278 235 13 6 -4 -3 809 825 9 6 -r 2 55 0 560 10
5 I 0 513 512 r0 5 13 -6 18t t-¿2 16 6 -I0 3 161 162 16 6 -4 -2 129 760 9 6 -1 3 112 151 t2
s?t395 384 9 5 13 -5 328 298 10 6 -10 4 161 159 17 6 -4 -l s52 535 r0 6 -t 4 ll1 361 9
s I 2 680 612 17 5 t3 -4 32r 323 1T 6 -10 5 203 180 15 6 -4 0 442 468 lr 6 -l s 151 343 9
5735f8 682 12 5 13 -3 3Ì2 306 10 5 -9 -'l 135 143 20 6 -4 I 490 510 11 6 -1 6 219 2A6 12
5 f 4 518 519 t3 5 t3 -2 2r3 2t9 t2 6 -9 -6 141 113 r? 6 -4 2 669 100 11 6 -l 1 151 146 21
5 7 5 348 334 9 5 t3 -1 324 128 9 6 -9 -3 175 183 12 6 -4 3 463 451 9 6 0 11 162 119 l9
576242 244 13 5 13 0 455 446 10 6 -9 -2 t9]^ 204 12 6 -4 4 363 J10 9 6 0 10 Ì86 r3
5f1284 298 \3 s13t407 4L2 9 6 -8 -10 201 182 16 6 4 5 205 2t2 14 6 0 -9 112 160 t5
58-5223 233 l0 5132309 305 10 6 -8 -9 211 198 15 6 -4 6 263 254 12 6 0 -8 359 345 9
5 6 -4 214 292 9 5133245 263 13 6 -8 -8 193 tEo 15 6 -4 1 246 245 1.4 601 (08 420 9
58-322L 228 l0 5134245 266 14 6 -ø -1 2A1 266 LO 6 -3 -9 146 161 19 6 0 -6 )62 186 9
sa-2222 199 9 5 14 0 149 150 18 6 -8 -6 429 440 l0 6 -3 -8 318 116 9 605 3t6 326 )
5 I -1 241 243 A s 14 r 164 155 17 6 -0 -5 515 53s 13 6 -3 -1 256 24f 9 604 5 68 518 9
580233 249 9 5 15 -6 rl3 160 18 6 -8 -{ 412 412 l0 6 -3 -6 133 140 14 6 0 -3 624 62t 9
5 8 r 234 229 9 5 15 -5 184 1't 5 18 6 -8 -3 26A 214 I 6 -3 -{ 218 230 I 602 583 5f0 9
582322 311 I 5 t5 -4 18? 209 ll 6 -g -2 4a6 522 t2 6 -3 -3 314 388 I 6 0 -ì 625 645 9
5 8 3 355 379 I 5 t5 -3 t?2 164 t6 6 -8 -1 6L3 63L 12 6 -3 -2 366 354 8 600 1¿5 164 9
5 8 { 210 20r 13 5 15 -2 235 216 12 6 -8 0 541 564 13 6 -3 -r 220 226 I 601 634 641 9
5 I I 190 183 18 s 15 -l 280 286 Ìt 6-8L3023029630314 308 l 602 3r2 317 I
5 9 -10 155 122 lA 5150266 215 12 6 -8 2 226 24071 6 -3 I 240 224 I 603 216 213 t0
5 9 -9 143 140 19 s 15 r 158 170 18 5 -8 3 269 21AtO 5 -3 2 351 3l4 I 604 406 400 8
5 9 -E J20 5rs2tJ2 r25 22 6 -E 4 !0t 30610 6 -l f r11 t4 9 12 605 446 415 1I
59-1434 444 10 5 15 3 2t4 270 14 6 -8 5 2t2 2r0 14 6 3 4 168 160 14 606 3lt 364 l0
5 9 -6 369 310 9 s 16 -1 181 17f l5 6 -1 -t 126 100 16 6 -3 5 ì49 169 t8 601 l9r 1s8 1l
5 9 -5 239 250 10 5 16 0 187 ).1 2 15 6 -6 -10 224 208 14 6 2 l0 206 205 t 4 6 I -10 326 338 10
5 9 -4 183 395 9 5 16 1 t36 118 20 6 -6 9 t72 t94 11 6 -2 -9 292 294 rO 6 Ì -9 330 l3l 9
5 9 -3 159 804 12 5 t1 -2 144 t2ø 18 6 -6 -8 269 21t r1 5 2 -8 416 413 10 618 220 215 rr
59-2559 513 11 5 -t3 -4 181 187 16 6 -6 -f 432 429 lO 6 -2 -1 313 312 I 6Ì1 t72 163 t2
5 9 -l 343 365 I 6 -13 -3 141 r92 19 6 6 -6 511 496 12 6 -2 -6 414 424 9 6t6 420 392 l1
5 9 0 201 192 10 6 -r3 -2 l4A t44 18 6 -6 -5 393 J92 9 6 -2 -5 508 50t t0 6ì5 165 f14 9
591656 612 11 6 -13 1 190 r66 I6 6-5-432933016-24162 185 9 6t4 619 648 9
592690 604 11 6 -r3 3 135 f9 22 6-6343244086-2-3111 184 9 613 472 415 I0
593413 s02 11 6 -t2 -A 144 t24 6 -6 -2 f52 119 lO 6 -2 -2 615 6t4 9 6 I -2 4t5 42r t0
5 9 I 360 348 9 6 -12 -5 15{ 130 1? 6 -6 -1 64t 526 10 6 -2 -t 592 601 9 6 I -1 66r 663 9
5 9 5 267 25512 6 -!2 -4 22I zIL 17 6 -6 0 525 sll 11 6-20553 5tl t0 610 918 922 9
5 9 5 305 308 12 6 -12 -3 231 2I4 1r 6 -6 I 363 377 I 6 -2 l. 817 830 r0 611 141 740 9
5 9 1 250 21t14 6 -72 -2 I19 L61 11 6 -6 2 115 142 t0 6-22634 651 l0 612 355 313 9
5 10 -3 189 180 13 6 -12 0 196 rs8 14 5 -6 3 528 519 13 6-2J114 483 9 613 324 299 8
5 t1 -9 211 198 14 6 -12 1 148 169 20 6 -6 4 389 109 9 6-24354 360 9 614 529 505 I3
5 11 -8 223 243 13 6 -12 2 r7't t60 11 6 -6 5 218 232 L3 6-25262 262 tt 615 393 379 10
5 tt -7 261 211 IL 6 -11 -a 166 1?8 15 5 -6 5 193 186 16 6-26325 301 l0 616 304 3 05 t1
5 L1 -6 245 255 t2 6 -11 -3 181 173 14 6 -6 l 205 1E3 15 6-212t2 222 t6 611 20t 189 I6
s 11 -5 3ô1 356 9 6 -11 0 197 194 14 6 -5 -6 132 119 16 6-28138 I41 23 6 2 -A 221 225 10
5 11 -1 122 426 L0 6 -11 1 l.3t 17? 21 6 -5 -5 109 138 1? 6 -l -9 291 216 tO 62-1 148 t54 13
5 11 -3 {79 {8? l0 6 -10 -9 195 201 1? 5 -5 -2 235 230 I 6 -r -8 294 28r 9 6 2 -6 329 331 I
52-52192L61 6 5 2 109 612]. 6 10 -5 132 115t8 6 t6 -3 201 1?8 l3 1-6-1 254 258 10
62-43?6369E 6 5 3 7{7 f701t 6 t0 -4 316 341 9 6 r5 -2 261 268 tl 1 -6 -6
-l 280 2AO 9
62-a3663588 6 5 1 577 551 13 5 10 -3 261 266 l0 6 t6 -r 212 232 12 -6 -5 t 98 194 11
62-r553s569 6 5 5 308 316 10 6 tO -2 22A 230 t0 6 L6 0 138 t64 20 1-6-4 348 350 I
6 2 0 392 393 I 6 5 6 281 3LOt2 6 L0 -1 2A4 29r 9 l -t4 -{ 169 152 t1 1-6-3 502 509 1t
62L3153221 6 5 7 335 35112 6 l0 0 298 309 9 l -14 -3 132 t62 22 1-6-2 331 33 4 8
6 2 2 t37 130 t3 6 6 -6 r22 r75t6 6 L0 I 3l{ 318 9 l -t4 -2 131 L33 22 1-6-t 214 268 I
6 2 3 38{ 365 9 5 6 -5 23L 221 9 6 10 2 20s r9113 1 -t2 -5 209 2r1 15 1 -6 0 2I1 212 IO
62{1713649 6 6 -4 lfl 157 rl 6 10 3 190 r?4 14 1 -r2 -4 L91 205 14 1 -6 1 332 r35 I
6 2 5 23J 246L3 5 6 2 123 r01L1 6 r0 4 15? 13919 I -t2 -3 183 18? 1s 't -6 2 r1l 32 I
6 3 -11 252 221 13 6 7 -10 2t9 209 L3 6 t0 5 t11 t51 22 1 -12 -2 L34 116 19 't -6 3 269 10
6 3 -10 3t5 332 t1 6 1 -9 228 231 L2 6 11 -9 161 153 16 l -12 -1 151 162 18 't -6 4 151 16 18
63-93012839 5 7 -8 351 351 I 6 11 -8 190 185 13 1 -t2 0 200 186 1{ 't-65 I62 I3 1l
63-02632619 6 't -1 169 464 9 6 11 -7 t47 163 18 't -r2 :. 210 189 t4 1 -6 6 112 1.5 19
53-74574689 6 1 -6 136 429 9 6 11 -6 r85 210 15 1 -12 I 143 to2 20 I -5 -t0 138 9 2r
6 3 -6 812 841 10 6 7 -5 103 390 9 6 11 -5 281 291 tO I -10 -9 lll t51 18 ? -5 -9 156 r'l 18
6 3 -5 855 051 10 6 't -1 745 ?56 11 6 rL -4 330 345 9 7 -10 -8 142 I39 2r I -5 -8 294 2A 10
6 3 -1 6t2 6t1 tO 6 '7 -3 699 ?33 11 6 11 -3 261 255 tO l -10 -7 191 106 ls 7-5-l 331 34 9
63-356155{9 6 7 -2 856 851 10 6 t7 -2 25ø 216 rO 't -L0 -6 261 264 t2 't -5 -6 301 29 I
63-2?75??{9 6 7 -l 512 528 11 6 11 -1 310 316 8 't -10 -5 211 268 10 7 -5 -5 289 I
63-10048119 6 1 0 315 3091,0 6 11 0 123 {15 I 1 -a0 -4 215 261 9 7-5-4 33 6 33
5 3 0 904 91510 6 1 1 555 54011 6 tt I 349 353 9 1 -LO -3 224 216 11 7-5-3 534 54 11
6315846689 6 1 2 644 641t2 6 11 2 325 313 9 1 -t0 -2 224 242 IL 7-5-2 539 54 11
6 3 2 55? 56811 6 1 3 131 102t2 6 11 3 211 24613 7 -t0 -1 333 342 9 f-5-t 3? I 36 9
6 3 3 552 547 11 6 7 4 399 40310 6 11 4 221 24415 7 -10 0 249 281 10 7-50 300 296 8
6 3 4 514 528 r0 6 1 5 251 26213 6 11 5 280 28213 ? -10 1 252 244 II l -5 1 3 45 35 6 8
6 3 s 42r 421LO 6 1 6 291 299t2 6 12 -A 126 9220 7 -10 2 141 146 l8 f -5 2 3t I 383 8
6 3 6 269 266L2 5 1 l 282 3r8 13 6 t2 -5 281 286 11 ? 3 7-53
-t -10
160 162 11 301 309 9
6 3 7 169 18721 6 8 -8 15s 133 16 6 t2 -4 339 351 l0 -10 4 Ì54 115 20 7-54 144 131 t8
6 4 -8 r88 190 12 6 8 -7 157 164 15 6 t2 -3 236 24s \2 f -9 -1 190 r92 t3 ? -4 -10 169 140 1?
6 4 -1 20{ 188 10 6 8 -4 203 200 11 6 72 -2 114 154 14 I -9 0 183 t12 14 1 -4 -9 llt 184 16
64-62562828 6 8 -3 383 392 I 6 12 -1 t9\ 112 12 I -8 -8 188 206 16 I -4 -8 159 t3? 15
5 4 -5 135 12't 13 6 A -2 1?1 14111 6 12 0 317 388 9 I -8 -l 301 2 91. l0 14-f 192 t92 I2
6 4 -4 ¡.98 18{ 9 5 8 | 21r 2'tS 9 6 12 L 290 2A4rO 1 -A -6 213 259 rO 1 -4 -6 250 24r 9
6 4 -3 157 163 11 6 8 2 200 t9t!2 6 12 2 204 22214 I -8 -5 330 338 8 1 -4 -5 349 345 8

6 4 -2 269 25't 1 6 8 4 129 11621 6 12 3 201 19815 1 -8 -4 245 236 9 1 -4 -4 364 3 83 9

6 4 -l 184 1l{ 9 6 9 -10 136 t21 L9 6 !2 4 177 215 19 't -8 -3 318 33r I 14-3 423 419 I
6402982931 6 9 -9 188 187 14 5 13 -s 152 151 19 1 -A -2 324 348 0 1-4-2 290 2ø6 1
6 4 I 187 1?9 10 6 9 -8 289 285 10 6 13 -4 2r5 215 14 1 -A -l 462 471 t0 1-4-l 238 246 9
6 4 2 16r t5212 6 9 -'t 3{8 345 I 6 13 -3 170 15? 15 7 -8 0 313 314 9 1 -4 0 266 256 I
6 4 5 180 1-t9 t5 6 9 -6 297 281 9 6 13 -2 200 180 13 f-8124r 239 l0 1 -4 I 295 29t I
6 4 ? I48 1622 6 9 -5 339 369 9 6 13 -l 20L 2I4 13 ?-8222J 223 lt 't -4 2 331 362 I
6 5 -11 182 193 1l 6 9 -4 546 555 t3 6 rf O 241 251 lr 7-83280 302 10 1 -4 3 20t t2
6 5 -r0 205 23't t5 6 9 -3 552 58t 13 6 13 I 2L5 209 13 7-84225 262 13 1 -4 4 135 114 18
6 5 -9 2L2 2!1 L2 6 9 -2 553 556 12 6 13 2 181 150 16 1 -1 -1 231 241 12 1 -4 5 153 101 18
65-83323325 6 9 -1 386 407 l0 6 13 4 142 112 22 -t -1 -6 231 220 t0 -t -4 6 162 110 19
6 5 -l 38? 381 l0 6 9 0 671 675 11 6 t4 -6 185 213 r8 7 -7 -5 168 158 13 1-3-9 311 312 r0
6 5 -5 63t 639 tl 6 9 L 64t 649 t2 6 14 -5 195 2r3 r? 1 -1 -3 304 305 8 1 -3 8 388 3 83 9
6 5 -5 498 501 lt 6 9 2 s12 364 13 6 14 -4 166 160 tf 1 -1 -2 280 216 I I -3 1 364 3 69 I
6 5 -4 501 510 lt 6 9 3 34r 322 9 6 14 -2 227 228t3 1 -1 -t 129 114 17 1-3-6 t 90 188 r1
6 5 -3 692 692 r0 6 9 4 196 21? 15 6 14 -1 311 328 10 1 -1 I 158 165 14 7 -3 -5 362 363 1
6 5 -2 013 831 10 6 9 5 314 31611 6 L4 0 284 214r1 1-12181 205 13 1-3-4 510 560 10
6 5 -1 1054 1055 10 6 9 6 299 339L3 6 14 2 1?0 19411 113201 189 12 1-3-3 114 789 10
6 5 0 712 ?r8 10 6 10 -9 162 t52 11 6 14 3 238 242 13 l 6 -9 143 r33 21 't -3 -2 409 416
6 5 1 528 529 L1 6 t0 -8 240 2r5 tL 6 ls -r 145 84 18 1 -6 -A 249 225 tl 7 -3 -1 461 450
1 -3 0 420 446 9 7 1 -3 499 49810 7 5 -5 4ra 432 9 184216 206 l4 1 16 -2 t 91 206
1 -3 1 560 567 Ì1 1 r -2 641 626 l0 7 5 -4 482 4ø1 12 185294 269 12 l 16 -1 r42 L61
't -3 2 504 495 12 I 1 -1 947 9s3 10 I 5 -3 610 611 11 't85246 258 ).4 I -14 -4 135 L21
1-333753688 ? 1 0 906 92010 1 s -2 ?99 81411 19-8131 95 1l 8 -14 -1 134 105
1 -3 1 251 255 rL ? I 1 599 59910 7 s -1 66s 67110 ? 9 -? 191 203 13 a -r2 -1 13 8 1r6
1 -3 5 316 325 11 I I 2 43A 443 9 1 5 0 49{ t6211 19-62J4 243 7l I -).2 -5 135 I1?
't -? 6 264 214 !1 ? 1 3 6\S 624t2 ? 5 I 40't 106 9 19-5266 284 10 I -12 -2 r25 t02
1 -3 1 L54 t88 22 1 | 4 599 59013 I 5 2 660 65212 19-4233 209 10 I -12 -1 144 117
't -2 -8 786 202 13 ? 1 5 442 422L0 7 5 3 593 5?913 l 9 -3 313 103 I 8-12 0 140 109
1 -2 -1 189 182 11 7 1 6 205 22't16 l 5 4 391 39? 9 19-2361 371 I I -11 -7 t3l 9I
1 -2 -6 222 2\7 9 1 2 -1 1't5 148 t1 ? 5 5 202 2L6 t6 't 9 -r 218 244 9 I -11 -6 160 150
1 -2 -5 208 2r5 9 1 2 -5 151 14211 7 5 6 250 25014 1 9 0 16? 150 9 I -11 -5 |t2 r52
1 -2 -1 241 238 1 1 2 -4 121 116 13 't 6 -ø 313 312 9 't9L23s 221 It I -rl -1 114 r92
't -2 -3 17{ 18{ 10 1 2 -3 124 105 13 'l 6 -1 318 316 I 792116 196 15 8-11 1 l3s 94
1 -2 -2 294 300 'l 't 2 -2 235 221 I 1 6 -6 23'l 241 l0 1 9 { 164 181 r9 8 -10 -l t 61 r3 6
1 -2 -1 285 282 1 1 2 -r 184 161 t0 1 6 -4 398 392 10 1 9 5 198 2t 0 1? I 10 -6 145 159
1-202362608 't 2 I 106 115 1l 7 6 -3 653 668 11 1 I0 -9 204 220 t3 0 -10 4 l4? 137
1-2135r3718 1 2 3 110 14713 1 6 -2 416 447 9 1 IO -A 229 193 11 I -10 -3 t5? t42
't -2 2 213 261 I 7 3 -11 209 2t1 15 ? 6 -1 252 255 I 7 r0 -5 186 188 l4 I -10 -2 201 214 13
't -2 3 130 136 1l 7 3 -10 207 179 13 1 6 0 161 154 12 7 l0 -5 410 4?E 1t I -10 -1 224 201 12
? -r -10 244 251 t3 't 3 -9 241 244 r7 't 6 I 383 3?4 I l 10 -4 4t9 425 tr 8-10 0 146 I4'l 18
1 -9 349 340 9 1 3 -A 399 40r I l 6 2 388 392 9 I 10 -3 6 I I -9 -8 154 100 18
-t -t
343 35
-1 -8 391 390 9 1 3 -1 482 490 12 't 6 I 283 215 rO 1 r0 -2 266 264 9 8 -9 -l 188 188 l5
1 -t -1 38r 383 l0 1 3 -6 77r ?6511 1 6 4 211 18213 ? Ì0 -1 354 359 I 8 -9 -6 224 222 I2
't -7 -6 {53 459 I I 3 -5 484 49011 1 6 5 223 20514 7 t0 0 499 497 t0 I 9 -5 r52 165 17
l -1 -5 603 526 10 't J -4 604 600 10 r l -10 140 129 t9 I 10 Ì 3E0 3f8 9 I -9 -4 164 118 14
I -1 -4 8t4 816 9 7 3 -3 588 588 10 1 1 -9 149 136 1l -l t0 2 341 334 9 I -9 -3 180 173 13
l -1 -3 546 551 10 1 3 -2 82-t 828 10 ? I -8 249 2J6 lO ? 10 3 2st 249 12 a -9 -2 211 211 10
1 -t -2 596 5-r3 10 I 3 -1 942 942r0 1 1 -1 305 311 9 I 10 4 281 219 12 0 -9 -1 221 228 t2
I -1 -1 740 f41 10 1 3 0 575 58310 't 1 -6 268 210 9 7 10 5 246 33 6 13 8 -9 0 114 178 15
I -1 0 821 837 10 7 3 1 510 506 11 f f -s 238 23r 10 1111742 1l0 1l 8 -9 t 145 rl2 l?
f -1 I 6?6 68? rt 't 3 2 500 49512 1 1 -4 306 311 8 I tl 4 141 r05 2l 8 -9 2 142 141 18
7-Ì228328t8 't 3 3 633 621 1-2 1 1 -3 401 425 10 7 12 -? 183 182 1s 8 -9 3 203 190 t4
l -1 3 409 401 10 ? 3 4 413 39't I 1 1 -2 703 295 I 't 72 -6 291 103 1t 894 159 14? l8
l-14368312a 1 3 5 29'7 308tt ? 1 -r 252 221 9 I 12 -5 354 395 10 I -8 6 t44 80 16
l -1 5 408 393 r0 1 3 5 202 209tf 1 f 0 213 20t10 1 \2 -4 7lO 305 10 8 -8 5 139 t11 16
7 -1 6 268 254 13 f 3 1 221 25075 1 f I 500 49113 1 t2 -3 270 23t t2 a-a-2 174 1?l 13
7 -1 7 168 190 20 1 4 -8 132 11816 1 1 2 {{6 41910 1t22301 7t2 9 I -8 I 150 15s l6
7 0 -8 t36 106 16 't 4 -'t 222 22t 70 1 1 3 230 250 t3 1 t2 -1 415 446 10 8 -8 0 155 161 16
1 0 -'l 127 119 16 1 4 -6 338 351 9 7 l 4 192 19115 1 t2 0 434 433 1t 8 -8 2 150 150 ll
7 0 -4 r28 Lt9 t2 1 4 -5 Ì58 14911 f 1 5 164 t9920 112t219 285 t1 883 136 Ì10 t9
l0-322523t8 1 4 -3 308 31{ 7 l 1 6 23t 245t6 t122219 234 t4 I -l -10 Ì52 r19 20
10-2365342A 't 4 -2 J22 3t4 ø 1 I -9 183 2tl Ì6 1123241 261 t4 I -l -8 225 228 I4
1 0 1 135 113 t3 1 4 Ì 464 410 I I I -8 280 270 10 1124285 290 t2 I -l 1 292 216 IO
ì 0 2 r40 t10 14 1ú4 Il e-1-6 26? 256 l0
l 0 3 144 114 15 1 4 I 162 146t2 I.t 8 -6 229 23310 l 14 6 r91 t92 t6 I I -5 258 255 9
I 0 4 126 A219 't 4 2 216 242 \7 I -5 366 383 9 l 14 -5 180 22) t1 ø -1 -4 302 118 9
l 1 -11 215 206 15 1 4 3 332 321 9 1 I 4 435 44910 I t4 -4 140 I14 20 8 I -3 156 ll5
I 1 -10 306 290 1l 1 4 4 208 18613 7 0 -3 293 323 9 1 14 -3 225 229 13 I -l z 310 312 9
1r-93t62999 f 4 5 153 14319 f A 2 32A 343 I 1 t4 -2 3I1 320 10 8 I -1 22f 222 t1
l1-82122169 7 5 -10 I92 t61 L4 ? 8 -1 428 432 9 7 Ì{ I 309 108 10 I -1 0 215 228 1t
1 L -1 411 405 9 7 s -9 23f 244tL 1 g 0 545 54912 7 14 0 23t 236 ).3 871 268 280 t0
1 I -6 603 590 r0 7 5 -8 260 24rt0 l 8 I 519 581 13 1147228 2r2 t3 812 291 306 t0
l 1 -5 0f8 890 10 1 5 -1 302 312 a 1 I 2 406 412 9 l 14 2 23f 251 tl 8fl 263 248 11
7 I -4 66s 651 10 1 5 -6 298 219 I 1 g 3 240 238t2 I 16 -3 tl4 200 l6 814 l.3l t22 21
I -5 -5 13Ì 135 16 8 -t -1 555 5?0 11 8 3 -10 15{ 159 1E 861683 683 ì2 8 t3 0 1r4 152 20
 8 -6 -4 119 9317 I -1 0 521 523 tI 3 -9 214 2t3 t2 862555 541 1{ 8 14 -4 161 163 t6
8 -6 2 124 9118 0 -1 I 346 350 I 3 -8 245 233 10 I 6 3 300 281 t0 I 14 -3 166 184 17
8 -5 -10 192 15I 16 I -1 2 2r8 22t tl 3-1 134 I28 L6 8 6 4 210 262 t2 8L4-2 206 198 t3
8 -5 -9 299 291 \t I -1 3 310 307 9 3 -5 315 311 I 865212 266 t3 E 14 -1 r51 156 t8
8 -5 -8 362354 9 I -1 4 409 39E l0 3-5 258 256 I I 7 -3 148 153 Ì4 9 -r3 5 t40 t24 20
8 -5 -l 253 263 tr 8 -l 5 300 279 11 3 -4 332 329 I I E -10 185 118 t4 9 -11 -2 178 209 16
8-5-62ø026198-16112 175 r9 3-3 493 4A1 L2 a8-9211 2t3 to 9 -11 -1 230 23' 13
I -5 s 340 345 9 I 0-10 116 119 16 3-2 392 398 9 EE-8301 219 9 9 -rt 0 t2E ls0 21
8 -5 -{ 600 591 1l A 0 -1 222 225 LO 3 -1 42L 429 9 0 I -l 205 223 t2 9 -11 1 r33 t02 21
8 -5 -3 1A9 4A6 !2 8 0 -6 326 33 4 l 30 263 231 A E 0 -6 307 315 9 9 -9 -7 196 200 15
I -5 -2 488 {51 12 I 0 -5 400 4tl 9 3I 354 360 I I I -5 {30 401 t0 9 -9 -6 156 t62 11
I -5 -I 38f 38{ 8 8 0 -4 2t5 222 9 32 403 393 8 I ¡ -4 482 501 l0 9 -9 -5 t42 154 18
8-50418425980-3181 173 10 33 255 283 1t I ¡ -3 {23 422 r0 9 -9 -4 t59 168 15
8 -5 1 422 1301O I O -2 443 423 ø 31 2t0 201 t4 I I -2 484 496 9 9 -9 -3 213 264 LO
8-523814tO980-t322 330 I 4 -11 153 165 19 I E -1 5t{ 513 I3 9-9-2 226 218 12
8 -5 3 252 265!t I 0 0 310 339 1 4 -9 250 251 10 880513 588 13 9 -9 -1 129 131 20
8 -5 4 111 r19\6 I 0 1 154 163 t3 4 -8 3 99 100 I I 0 1 539 511 13 9 -9 1 183 171 11
8 -5 5 116 19417 I 0 2 212 214 l0 1-1 100 381 t 0 8823I9 314 t0 9 -9 2 186 186 16
8 -{ -3 201 19110 E 0 l 181 t12 I4 4 -6 365 369 I 803293 28I lt 9 -9 3 156 153 10
8 -3 -10 t?7 175 17 8 0 4 224 l3 4-5 198 184 r0 I E 4 3tt 311 12 9-1-9 173 165 18
8 -3 -9 213 216LL I 0 5 146 154 2I 4 -4 {15 428 9 I 9 -5 1.39 121 11 9-1-a t86 IE2 L6
I -3 -8 316 309 9 I I -11 195 141 15 4 -3 624 635 lÌ I l0 -9 152 150 t6 9-1-1 184 169 15
I -3 -l 328 335 I I I -10 196 r61 14 4-2 122 11{ 11 I l0 -8 143 t3 9 1l 9 -? -6 201 206 t2
8-3-633032518L-9229 2t6 t2 4 -l 425 {{8 9 a to -'t 223 225 12 9 -l -5 223 221 ).I
8 -3 -5 {99 504 12 8 I -8 259 248 9 40 313 306 E E 10 -6 275 I r0
2't 9-f-4 210 26t 9
8 -3 -4 62A 621 rr I 1 -7 380 361 I 4t 356 332 9 I 10 -5 350 313 9 9-1-3 331 336 E
I -3 -3 175 485 t2 I I -6 525 536 lr 12 5 6'l 566 13 8 10 -4 325 345 9 9-1-2 280 267 9
a-3-23?3383981-517{ { 5E I2 43 {50 {{8 1t I 10 -3 295 303 9 9 -l -1. 201 2t3 ).2
ô -3 -l 415 419 12 I r -{ 366 361 9 44 314 295 10 e t0 -2 299 306 9 9 -1 0 212 203 t2
8 -3 0 605 61711 I 1 -3 435 440 I 45 208 2t5 t6 I 10 -1 311 355 9 9-1 1 250 264 TT
I -3 I 541 56912 I 1 -2 509 507 Ll, 5 -10 l.{7 1.4 2 18 I 10 0 520 500 10 9 -1 2 234 236 12
8-32386396881-1513 511 1.1 5 -9 139 t 0a ll 8 10 1 356 348 9 9-6-3 t68 156 13
8 -3 3 2r5 22612 I 1 0 489 190 t2 5 -l r29 139 1l 8 10 2 2L6 249 14 9 -6 -2 r64 131 t3
I -3 4 294 30911 I 1 1 435 435 9 5 -6 196 186 Ìr 8 t0 3 252 259 12 9 6 -1 132 t29 11
8 -3 5 329 31611 I 1 2 120 421 10 5-5 296 305 8 I 11 -5 211 206 t3 9 -6 0 r52 r36 t 5
8 -3 6 240 26211 I 1 3 313 300 9 5 -1 256 261 9 I 11 -5 193 t77 tl 9 -6 1 tl6 125 18
8 -2 -6 130 14215 I 1 4 303 298 10 5-3 188 185 11 8 Lr -1 213 206 t3 9 -6 2 r25 118 20
s-2-52122439815186 208 1l 5-2 251 24J 9 8 11 0 144 133 19 9 -5 -9 2L\ 183 14
8 -2 -4 233 235 A A 2 -t0 152 r3l 10 5 -1 115 152 14 8 11 3 11? t31 20 9 -5 -8 194 188 14
6 -2 -I 1?1 165 11 8 2 -8 201 199 50 149 t52 t4 I 12 -1 166 111 tl 9 -5 -1 2tr 2I4 T2
s-2021t215982-1301 294 8 51 232 221 r0 8 t2 -6 195 2t9 Ls 9 -5 -6 226 241 It
I -2 1 203 19011 I 2 -6 359 314 8 52 22r 2T1 T2 I 12 -5 rl8 171 l5 9 -5 -5 3t2 3r0 I
8 -2 2 t52 t6t14 6 2 -5 343 35 4 I 53 218 205 t3 I 12 4 Ì75 206 t6 9 -5 -4 304 300 I
a -2 3 13{ 10218 â 2 -4 265 259 I 6 -10 155 139 1? 6 12 -3 220 226 13 9 -5 -3 329 332 ¿
8 -1 -11 139 161 22 I 2 -3 425 41 9 6 -9 238 231 7L I 72 -2 3r2 303 9 9-5-2 229 215 10
8 -1 -10 r94 221 16 I 2 -2 615 62 11 6 -t 399 3-t5 9 I 12 -1 313 310 9 9 -5 -1 29r 218 9
8 -1 -9 252 221 LL I 2 -1 581 58 1l 6-1 4t8 4r0 10 8120233 223 13 9 -5 0 262 266 tO
8-t-82102599820325 32 I 6-6 331 342 1 I 12 r 183 L82 16 9 -5 1 J22 333 9
8 -1 -7 211 21011 I 2 r 24r 23 9 6-5 484 489 9 8122205 209 15 9 -5 2 225 248 12
8-1-61093959822460 46 10 6 -4 598 622 t2 I 13 -7 1s2 150 1l 954 181 t61 t6
8 -1 -5 493 48411 A 2 3 4r0 41 9 6 -3 652 696 12 8 t3 -6 181 lll 15 9 -5 5 168 166 18
8 -1 -4 495 50811 8 2 4 249 25 t3 6-2 410 {87 9 I 1.3 -3 161 152 16 9 -4 -10 ra2 12r t5
8-1-33553629825t42 13 22 6 -l 325 334 I a ).3 -2 214 264 tt 9 -4 -6 159 161 L4
8 -1 -2 463 1't2 t2 ø 2 6 190 169 18 { 83 {80 9 I 13 -1 215 222 13 9 -4 -5 351 354 9
9-1-4300292890-7122 42L l0 42 425 llg 9 99-2222 24r 12 t0 -6 2 140 139 19
9 -4 -3 202 201 LI 9 0 -6 500 501 43 2ga 309 11 9 9 -1 ll2 302 9 10 -6 3 r42 115 19
9 -4 -2 118 11,3 18 9 0 -5 463 461 9 44 239 223 L3 9 9 0 343 356 9 10 -5 -l 133 \2O Lâ
9 -4 -t 2L6 203 tr 9 0 -4 319 328 I 45 214 215 L1 9 9 I 150 184 19 10 -4 -10 161 164 18
9-40262254990-3431 433 9 5-5 150 150 14 992149 164 t9 t0 -4 -9 160 150 18
9 -4 I 184 17813 9 0 -2 541 5 93 11 5 -4 200 210 11 99323e 222 13 t0 -4 -8 r39 131 19
I -4 2 170 15414 9 0 -1 520 503 12 5-3 201 218 11 9 10 -l 156 152 t6 10 -4 -? 200 19s 12
9 -4 3 141 11218 9 0 0 387 397 I 5-2 121 105 t6 9 10 -6 138 L52 18 10 -4 -6 285 282 9
9 -4 4 155 14119 9 0 1 365 31I I 11? 121 18 9 10 -5 185 L99 1{ 10 -{ -5 263 265 9
9 -3 -8 202 20312 9 0 2 329 339 9 50 t-1 1 159 13 9 10 -4 205 221 13 10 -4 -4 28'l 26ø 6
9 -3 -7 243 241r0 9 0 3 391 3S9 9 51 242 228 L\ 9 10 -3 210 t91 12 10 -4 -3 180 t14 12
9-3-52552549904255 265 13 52 153 117 17 9 r0 -2 20r tEI 12 to -4 -2 25r 249 70
9 -3 -5 212 2281O 9 0 5 220 200 1s 6 -10 186 168 14 9 10 -1 249 243 ll 10 -4 -1 350 341 I
9 -3 -4 244 263 9 I l. -9 131 110 l9 6-9 236 218 11 9 10 0 225 20a 12 10 -4 0 133 335 9
9-3-3333331r91-8128 1t4 1l 6 -8 248 243 7L 9 10 2 150 160 20 10 -4 1 228 228 11
9 -3 -2 399 10{ 10 9 I -6 144 151 15 6-1 3t9 329 9 9 71- -1 233 230 12 10 -4 2 t41 130 1?
9 -3 -1 388 385 10 9 r. -{ 189 1?7 10 6 -6 309 300 9 9 7I -6 238 238 11 t0 -4 3 202 t85 15
9-30312326891-3109 to2 tl 6 -5 389 3 94 0 9 rr -5 180 208 1.4 10 -4 4 163 199 19
9 -3 | 201 22L12 9 I -2 11? 108 15 6 -4 416 449 t0 9 11 -3 23r 255 12 t0 -3 -4 t36 118 15
9 -3 2 130 11718 9 I -L 115 108 r7 6-3 395 389 10 9 11 -2 3l? 31 10 t0 -2 -10 141 !61 2L
9 -3 3 15? 16811 9 I O )-42 t-29 14 6-2 4 0-t 391 10 9 rt -1 309 30 10 to -2 -9 I11 146 l5
9 -3 4 225 2L4t4 9 l 3 tzA 52 20 6 -1 426 435 10 9 1l O 201 22 14 \o -2 -8 2t9 2r3 t2
9 -3 5 192 175 16 9 2-1r 136 151 21 60 561 511 t2 9 Ì1 I 1f6 l6 t6 to -2 -1 306 319 9
9 -2 -10 223 226 t4 9 2-10 155 165 18 6I 518 506 10 9 tl 2 265 l2 10 2 -6 385 404 9
9 -2 -9 198 205 14 9 2 -9 233 22't t2 62 263 t1 9 12 -5 159 I3 15 10 -2 -5 321 330 I
9 -2 -8 120 131 19 9 2 -8 310 305 9 63 2t3 200 14 9 13 -4 195 l4 10 -2 -4 ll1 298 â
9 -2 -'t 186 198 12 9 2 -l 358 365 9 64 240 231 14 9 13 -3 308 30 Ì0 to -2 -3 324 319 E

9 -2 -6 390 400 10 9 2 -6 420 412 9 l -10 1s4 141 16 9 13 -2 312 32 t0 IO -2 -2 429 418 I0
9 -2 -5 490 497 12 9 2 -5 305 310 8 1 -9 l6t 155 1s 9 13 -t 232 22 12 I0 -2 -1 761 341 â

9-2-4219218892-4421 434 9 ')8 1{3 133 16 9130191 18 t4 r0-20 319 3r3 0

9 -2 -3 219 213 r0 9 2 -3 635 623 11. 204 20s t2 10 -11 -4 123 10 20 70-21 231 246 tI
9-2-235?351892-2621 612 t1 1 -4 236 234 10 10 -11 -3 131 13 2I r0 -2 2 242 24r t2
9 -2 -r 522 536 t2 9 2 -l 532 551 12 1-3 146 15t 14 10 -9 -l 139 96 19 10 2 3 218 2't2 |2
9 -2 0 137 441 9 9 2 0 360 360 8 1-l 22t 2TI IT 10 -9 -6 140 118 19 r0-24 2r9 224 t5
9-21311322892r42r 422 10 10 2t9 2).4 t2 t0 -9 -4 t24 130 2T 10 -r -2 128 t42 11
9 -2 2 L16 I1r14 9 2 2 460 455 10 7t 241 269 r). 1.0 -9 -3 169 164 15 t0 -r -1 118 't1 ,1
9 -2 3 229 232t2 9 2 3 448 444 1.1 11 i-1 6 131 18 t0 -8 I 169 165 15 10 0 -10 r48 1f0 t8
9 -2 4 232 240t3 9 2 4 256 260 !3 I -9 180 156 14 10 -E -5 123 133 20 1.0 0 -9 l5l 163 l?
9 -2 5 164 18020 9 2 5 210 205 16 8 -8 r5 4 156 16 10 -8 4 170 160 15 10 0 -8 214 214 l0
9 -t -8 128 120 18 9 3 -8 150 154 15 ø -'l 198 195 12 10 -E -3 200 t75 1l 10 0 -l 324 f16 ¡
9 -1 -6 181 189 12 9 3 -5 L68 t62 t2 I -6 236 242 rl 10 -8 -1 162 119 l0 0 -6 335 329 I
9 -1 -5 2r1 22A rO 9 3 -3 140 144 15 ¡ -5 346 335 I t0 -6 0 155 153 ll 10 0 -5 256 250 9
9 -1 -4 139 13113 9 3 0 112 110 18 I -4 206 292 9 t0 -? -6 138 t3 0 18 10 0 4 348 )39 6

9 -1 -3 196 191 10 9 4 -t0 160 158 t 6 8 -3 216 283 9 10 -l -5 144 1.4 6 t7 t0 0 -3 469 460 9
9 -t -2 153 146 13 9 4 -9 782 209 14 a2 26¿ 258 9 l0 -l 4 165 l?t 15 t0 0 -2 491 488 1l
9 -t -1 195 212 11 9 4 -E 309 299 9 I -1 351 346 8 t0 -6 -9 148 Ì60 20 10 0 -1 406 409 l0
9 -t 0 247 221t0 9 4 -7 320 320 I 80 4 01. 392 9 10 -6 8 160 161 tl 10 0 0 211 294 9
9 -1 I 147 15015 9 4 -6 303 303 I 8t 254 271 t1 10 -6 -6 159 15 6 15 10 0 l 296 295 9
9 -1 2 170 15814 9 4 -5 303 29t I 82 244 243 12 10 -6 -s 21s 223 12 10 0 2 360 366 9
9 -1 3 20'l 21L t3 9 4 -4 595 605 12 83 235 224 13 10 -6 -4 353 331 I 10 0 3 30t 299 11
9 -1 4 184 17417 9 4 -3 630 634 LI 9-1 153 15? 16 t0 -6 -3 211 10 10 0 4 208 181 t3
9 0 -11 194 198 15 9 4 -2 381 400 I 96 256 2f1 11 t0 -6 -2 203 188 I2 10 1 -8 t 6l l4l 14
9 0 -10 200 195 14 9 4 -l 249 242 9 9 -5 320 331 9 10 6 -r 202 196 T2 10 1 -l l9l 209 72
9 0 -9 t6? 16315 9 4 0 364 34'l 9 9 -4 262 10 10 -6 0 256 244 t0 10 1 -3 240 221 9
9 0 -8 258 24510 9 4 1 s43 560 13 9 -3 192 t91 t2 l0 -6 | 236 216 11 10 r 2 214 225 ll
L0 I 0 139 13015 10 5 3 llt 171 18 1l 6 -5 200 23t 14 tt 0 -1 216 221 11. 11 1 -2 )34 323 9
r0 1 2 151 t63 18 10 6 -8 133 125 18 11 -6 -4 195 206 t3 tl 0 0 ll5 141 13 tt I -1 123 321 l0
r0 ? t0 133 15€ 21 10 6 -? 140 I35 I€ 11 -6 -3 r44 164 1r 11 0 r r-14 169 1,S 11 I 0 ?62 ?64 )l
10 2 -9 239 226 ar 10 5 -6 186 t62 L2 11 -6 2 t16 164 t{ tt o 2 202 193 t{ 11 I I 203 l9l t4
10 2 -8 223 225 It t0 6 s 162 162 t4 11 -6 -1 220 230 12 11 L 9 201 199 l3 11 f 2 202 209 15
10 2 -1 2Lr 220 1-1 10 6 -4 1s6 116 L3 It -6 0 193 199 14 11 1 -8 268 10 1t 8 -l 121 t02 l6
l0 2 -6 248 260 lO 10 6 -3 158 163 14 11 -6 I 149 13E tl tl I -l 200 224 tl tt a -2 tll 181 15
r0 2 -5 251 252 9 10 6 -2 252 244 t0 11 5 -6 r53 119 r5 lt r -6 t48 143 15 l1 I -Ì Ì 60 I ?0
10 2 -4 431 42s AO 10 6 -1 260 252 10 t1 -5 -5 134 124 18 11 1 -5 rls 168 16 tt 9 -1 712 112 t4
10 2 -3 402 410 l0 10 6 0 216 184 t2 II -5 - 4 r35 46 16 11 I 4 385 311 9 1Ì 9 -6 l8l 202 ll
10 2 -2 380 3f8 8 l0 ? -9 135 1{0 18 tl 4l 1f5 t5t Ì4 11 I -l 371 388 9 11 9 -5 I69 t11 14
10 2 -1 300 302 I 10 r -8 130 135 17 11 46 2I8 209 12 11 ). -2 25r 9 11 9 4 156 )14 1e
10 2 0 22A 241 7L 10 I -l 191 116 \2 1t -4 5 223 235 tI 1l I -1 146 112 15 II 9 ] ??a 240 )2
t0 2 r 259 215 70 10 1 -6 252 256 t0 1,1 -4 -3 196 194 t2 lì r o 221 208 ìl t) 9 -2 ¡l
10 22 364 365 l0 I -5 407 413 10 fl -4 -2 240 241 11 11 | r 292 286 lO 11 9 -r 23L 2IT
l0 23 240 25L 10 I -4 350 352 I 11 -4 -1 214 26S10 1l | 2 25a 25012 11 9 0 ll5 143
10 24 167 112 10 1 -3 2t8 220 ll rr -4 0 204 185 13 11 1 3 l4l 164 2l tl l0 -? t54 l?1
10 3 -9 165 166 10 1 2 246 249r0 11 -4 I 178 131 14 11 2 -1 lrB El 19 ll 10 -6 142 119
IO 3 -8 239 246 10?-Ì361361S1142 t66 t45 t1 11 2 -6 132 rr2 16 lt l0 -3 2t8 203
10 3-1 166 r66 r0 I 0 420 415 9 1r -4 3 t65 164 18 11 2 -5 I39 722 13 tt l0 2 r6l 203
10 3 -5 t26 r68 ro 1 | 253 255 12 rr -3 -l 166 113 15 11 2 2 128 A2 2t 11 10 -l r6Ì 139
10 3 -5 r27 146 10 1 2 234 191 t3 11 -3 -6 149 153 t6 1Ì 3 -10 149 lt6 17 ll rl 4 t62 1?1
10 3 -4 384 3 0l 10 1 3 200 224 16 11 -3 -5 r21 138 l8 11 3 -9 234 208 11 1ì 11 -3 t86 200
10 3-3 381 3S3 I 10 8 -3 125 134 18 11 -3 -3 112 162 13 1t 3 -â 206 202 12 11 1r -2 r99 200
10 3-2 212 183 10 10 I -1 123 91 20 rr -3 -2 229 228 tt 11 I --t 198 2rl. 12 12 -8 0 l5r 91
10 3 -l tf3 154 16 10 9 -8 112 r10 14 rt -3 -l L61 116 15 lt 3 -6 25A 246 9 12 -1 0 t48 95
10 30 211 255 9 t0 9 -1 242 242 ll 17 -2 -9 136 J,2A \9 11 3 -5 351 3s8 9 L2 -6 -2 I74 t20
10 31 262 210 10 10 9 -6 309 306 9 Ll -2 -8 195 179 13 11 3 -4 3El 380 9 12 -5 -1 L62 150 16
10 32 223 2t5 13 10 9 -5 275 300 t0 ll -2 -1 202 L91 L2 11 3 -3 30? 305 9 12 -5 -6 tl0 159 15
10 4 -10 r25 99 20 10 9 -4 204 221 L2 lr -2 -6 205 2t6 L2 lt 3 -2 263 246 9 12 -5 -5 115 125 18
10 4 -8 2L6 206 11 10 9 -3 261 261 l0 11 -2 -5 204 229 12 11 3 -l 322 7I2 I 12 -5 -2 t't 2 164 15
l0 1-1 256 264 IO 109-23133159Ú-2-4 166 169 13 tl. 3 0 375 364 I t2 -5 -l 165 762 t6
10 1-6 200 201 t2 10 9 -1 10? 389 10 11 -2 -3 235 223 rO 1.1 3 I 369 351 9 \2 -s 0 742 111 18
10 1-5 295 29L 9 r0 9 0 283 283 11 ll -2 -2 231 221 70 11 3 2 273 222 ).4 L2 -3 -9 131 85 l8
10 1 -4 219 264 9 10 9 2 259 250 17 1L -2 -1 2r5 204 11 11 3 3 111 151 21 12 -3 -8 ).1 6 15{ 15
10 1-3 295 296 9 10 11 -l 2r2 205 12 L1 -2 0 182 119 13 11 4 -3 r24 98 l7 12 -3 -1 142 1l{ 18
10 4-2 236 211 10 10 11 -6 l8{ 19? 14 )-l -2 2 18{ 190 16 11 5 -9 203 192 13 12 -3 -6 275 19{ 1r
10 4 -1 244 241 10 10 11 -5 160 102 15 1t -1 -8 206 r19 12 11 5 -8 103 191 13 12 -3 -5 L62 148 Ì4
10 40 288 285 9 10 11 -1 201 201 13 11 -1 -? 204 t99 1,2 11 5 -l 150 115 16 12 -3 -4 r92 l?7 13
10 41 305 303 10 10 11 -3 2AO 21r l0 1l -l -6 72t 123 18 11 5 -6 214 21\ rO L2 -3 -3 24ø 230 ll
10 42 231 229 72 10 Ll -2 335 332 10 11 -1 -5 l?5 1?1 13 lr 5 -5 363 357 8 12 -l -2 290 213 9
10 44 165 118 19 10 11 -1 2't't 216 rl 11 -1 -4 189 176 tl tt 5 -4 291 299 9 12 -3 -r 192 119 t3
10 5 -10 t14 140 l8 10 11 0 201 210 11 11 -1 -3 291 2eJ 8 11 5 -3 215 2s4 t0 12 -3 0 149t29 11
10 5 -9 225 227 t2 l0 12 -3 134 96 lt 17 -l -2 213 277 9 11 5 -2 326 733 I L2 -L -9 t62 t56 16
10 5 -8 226 2to 11 t0 13 -3 203 2rL !3 11. -1 -l t8t 200 13 1.1 5 -1 36E 376 9 12 -1 -8 t 94 r84 13
10 5-? 209 193 11 11 -10 -4 128 1r9 20 11 -1. 0 149 149 t6 11 5 0 335 3tE 9 12 -l '1 184 168 13
10 5 -6 242 250 10 11 -10 -3 rS2 126 11 tr -l I 16{ 148 15 11 5 1 297 269 1.0 12 -I -6 181 166 12
10 5-5 380 362 9 11 -0 -6 138 103 19 11 -1 2 205 211 15 lt 5 2 166 181 18 12 -1. -5 186 181 12
10 5 -4 381 383 9 11 -8 -4 188 180 1{ 1r -1 3 23L 195 13 1r I -9 152 139 ls 12 -1 -4 252 239 10
10 5-l 222 2t2 10 11 -8 -2 131 121 19 tl 0 -9 t58 130 16 rr f -8 150 141 16 12 -r -3 28J 219 9
10 5-2 265 26t 9 11 -8 0 170 156 16 11 0 -6 t3? t3o 16 Ì1 1 -1 211 220 12 12 -L -2 239 234 l0
10 5-1 356 368 I 11 -8 I 13? 145 20 11 0 -5 t95 t93 12 11 1 -6 216 210 t.0 12 1 -l 114 t59 14
10 50 152 475 t1 rr -6 -8 142 116 19 11 0 -4 211 t93 10 11 1 -5 2A2 211 9 12 -l 0 r 68 165 ts
L0 51 3t6 319 10 11 -6 -l 191 1?6 14 11 0 -3 195 200 t2 1). 1 -1 228 2J2 Ll 12 -L 1 215 2r2 t4
10 52 243 214 t2 11 -6 -6 2r4 191 12 1l O -2 112 195 t3 11 1 -3 21A 266 9 12 -l 2 210 213 14
t2 I -9 139 t62 19 72 I -t 137 160 19 13 6 -3 241 222 l0
12 1 -8 r90 tl3 13 12 9 -2 t22 6119 13 6 -2 202 230 t3
t2 1-l 156 116 16 12 10 -4 117 215 14 13 6 -r 196 193 13
T2 I -6 242 245 1t 12 10 -3 240 252 ll 13 I -4 189 190 13
t2 1 -5 254 239 10 13 -7 -6 lil 126 20 14 -3 -6 122 55 18
T2 I -4 33r 337 I 13 -5 -l 151 134 16 14 -2 -3 135 109 1l
I2 1 -3 280 264 9 13 -5 -6 L21 129 19 14 0 -6 159 151 15
t2 r-2 1't3 187 14 13 -5 -5 132 106 l-8 14 0 -5 r7t 164 14
I2 1-t 198 196 L2 t3 -5 -2 1?l 150 15 14 0 -2 t58 1.4 0 15
12 10 244 24t 11 1l -3 -8 142 119 18 14 2 -1 r23 111 18
L2 11 249 259 T2 13 -3 -6 165 110 14 Ì4 2 -6 1.5 5 114 15
t2 12 15s 16
169 13 -3 -4 134 r5l 19 14 2 -5 1.89 163 t2
L2 2 -4 t32 t32 17 13 -3 -3 195 195 13 14 2 -4 15 0 130 15
l2 20 150 l.03 t6 t3 -3 -2 149 154 1l 14 2 -2 158 r5l t5
L2 3 -9 L52 144 15 13 -3 -1 13r t24 l8 14 4 -6 156 139 14
3 -8 148 140 1f 13 -3 0 1.32 115 1.9 14 4 -5 l.{ 0 t39 16
t2 3 -7 184 181 13 t3 -2 -8 L46 102 11 14 4 -4 155 145 14
'12 3 -6 223 221 11 13 -1 -0 130 99 19 14 4 -3 l?3 164 r4
T2 3-5 252 252 10 13 -1 -? 143 109 16
I2 3 -4 209 200 t2 13 -1 -5 142 r34 16
12 3-3 199 I92 L2 13 -1 -4 1-t{ 185 14
t2 3-2 255 265 l0 13 -1 -3 169 158 t4
t2 3 -1 290 289 10 13 -1 0 131 140 19
t2 30 299 291 10 13 0 -A 126 11 L8
t2 3t 201 20ø 14 13 0 -5 1s2 132 15
t2 4-6 t32 t22 L7 13 0 -4 177 156 13
t2 { -5 208 192 12 13 0 -3 150 1,38 l5
I2 4 -1 t19 13? 19 13 0 -1 146 123 16
r2 40 164 156 16 13 0 0 t53 165 17
t2 41 133 t20 20 13 I -6 135 120 17
12 5-7 130 144 18 13 I -3 118 131 19
t2 5 -6 r84 t?1 13 13 I -1 161 137 15
12 211 l9? 12 13 1 0 13? 146 19
t2 5 -4 161 17? t5 13 2 -6 ]^9l r13 13
l2 5-3 181 18s 13 13 2 -s 199 100 12
I2 r89 1f7 13 13 2 -4 160 150 14
l2 5 -1 2ta 208 12 13 2 -3 t19 702 19
t2 50 216 201 13 13 2 -2 155 148 15
t2 51 134 137 20 13 2 -! 201 184 12
T2 6-1 150 110 16 13 2 0 201 1f3 13
t2 6 -6 219 222 11 13 3 -1 123 11r 20
t2 6 -5 r32 160 t8 13 4 -8 139 101 16
t2 6-3 r43 144 1? 13 4 -l 160 184 15
t2 6-2 259 246 10 Ì3 4 -6 22t 204 ll
l2 6-1 205 189 13 13 4 -5 220 273 LL
L2 60 159 151 71 13 4 -4 169 153 14
t2 7-5 L52 150 15 13 4 -3 178 154 13
t2 1 -4 115 165 14 t3 4 -2 22t 2r112
t2 1-3 T?O 154 14 13 I -t 234 221 12
l2 1-2 159 116 15 13 4 0 155 178 16
T2 l-1 1.3 3 l3-t 19 t3 5 -5 125 5-t 1?
I2 I -7 209 204 I2 13 6 -7 189 118 12
t2 ô -4 140 163 18 13 6 -6 161 176 L5
T2 ô-3 2't 1 2't 9 t0 13 6 -5 143 r41 16
t2 8-2 246 254 11 13 6 -4 125 Ìs8 19
Table A3: Obsened And Catcutated Stucture Factors For The [(o-Tol)sPAu(6-MP)] .C2HsOH Complex.

10lFlo vs 10lFlc
h k I Eo PcslgE h klFo Fc stgF h k I Fo FcalgE h k I Fo FcslgE h k I Eo EcslgF

0 4 26'16 2460 10 0 2 15 408 384 t0 04 2t 265 245 11 0 6 24 21r 291 14 09 I 't21 715 I
0 6 266r 2520 t0 02t6 902 909 I 0{ 24 613 601 r4 0625 490 461 t3 09 7r 2A2 2A6 I
0 I 358 331 6 o2r1 361 368 I 04 25 308 269 t3 0628 229 234 22 09 12 563 633 9
0 10 1186 L622 I 0 2 18 606 6t6 10 04 28 342 353 15 o629 200 22r 21 09 13 181 LgO 12
0 12 640 650 6 o220 113 3 113 s 10 04 29 212 166 25 0?1 6r1 662 6 09 t4 259 233 9
0 14 1078 1119 l o222 212 203 l4 04 30 219 259 2r 012 1195 1206 1 09 1s 163 184 15
0 16 804 843 I o224 ?58 I61 13 05 1 548 604 5 013 a26 841 6 09 16 313 383 11
0 18 855 809 I o226 256 261 I5 05 502 s50 5 0t1 412 8'ts 6 09 1? 3 98 392 10
0 20 941 1019 9 o22g 283 306 16 05 3 986 1019 6 015 17 r. 163 I 09 18 493 500 14
0 24 915 1030 10 0 2 30 45 9 439 14 05 4 348 317 6 016 500 50t l 09 21 418 391 12
0 26 523 561 1s 031 123 6 1243 5 05 5 350 325 1 0?1 I64 814 l 09 22 431 {11 13
0 28 440 {{0 13 032 211 282 5 05 6 69E 665 6 018 ì001 994 1 0 10 0 163 169 10
0 30 392 433 t2 033 1813 18 81 1 05 1 l'111 1f21 I 0 7 1l 584 545 I 0 10 1 559 546 8
1 1 1403 1560 6 034 242 232 6 05 I 113 9 1085 6 0112 625 51.7 I 0 10 2 152 140 t1
1 2 420 449 3 035 285 269 6 05 9 387 365 9 0 I t3 60? 5?3 9 0 10 3 298 304 9
1 3 3333 315 0 13 036 ?05 603 5 05 10 360 329 9 0 I l{ 315 291 LO 0 10 4 350 34f 11
1 4 r 68t 1?19 l 03'l 2043 202L I 05 1t 1318 1310 ? 0 I 15 J24 293 LO 0 10 5 '161 73t 8
1 5 1615 1635 l 038 952 909 6 05 t2 897 886 '' 0 I 16 334 330 10 0 10 6 354 352 12
1 6 443 4 08 5 039 t't2t 1-r 16 I 05 13 1448 1389 8 0 l 17 466 443 L2 0 10 ? 159 1I8 1I
1 't 2019 2007 I 0 3 10 86{ 862 6 05 14 604 5 91 I 0 7 18 482 413 13 0 10 I 138 134 14
1 I 399 313 6 0 3 11 1641 1680 8 05 15 r62 t6â t2 0120 265 22'l ll 0 t0 9 625 609 9
1 9 740 142 6 03L2 125 698 'l 05 t6 862 825 I 0 7 21 392 316 t2 0 l0 10 199 1f8 r0
I l0 795 154 5 0313 117 7 1169 'l 05 17 899 853 9 0122 5r6 510 t5 0 t0 11 484 485 1t
I tt 922 944 1 0 3 t4 387 34 10 05 18 250 211 10 0'l 23 434 122 t3 0 10 12 115 13 18
1 t2 443 453 I 0 3 t5 370 34 10 05 19 329 331 9 0125 284 249 14 0 t0 13 181 L12 t3
1 13 1395 1437 8 0 3 16 296 10 05 2L s12 196 13 o126 265 243 t6 0 ¡,0 14 239 240 l0
1 t1 210 325 8 0 3 ll 1 615 157 9 05 22 46L 41-t 1t o121 28'l 292 11 0 t0 15 5?7 552 11
1 15 400 405 9 0 3 18 570 58 1l 05 23 J28 31] II 0f28 343 326 t5 0 t0 17 149 134 18
1 1l 1320 1344 I 0 3 19 521 52 t2 05 24 196 181 18 080 856 619 1 0 10 18 326 311 9
1 18 379 316 9 032L 145 't2 12 05 25 229 194 1l 08t 1015 1011
-7
0 10 19 403 401 12
1 19 415 433 12 0322 389 43 13 05 26 216 263 15 082 130 112 10 0 l0 20 230 186 t4
I 21 891 94{ t0 o323 518 5t 15 05 21 314 302 15 083 266 280 I 0 10 2t 393 347 13
I 23 851 920 11 o321 561 54 19 06 0 1tt8 1156 6 084 919 931 l 0 11 I 198 ta2 9
1 24 2r3 215 14 0 3 31 341 355 18 I 1050 6
101.1 085 1049 1043 ? 0 t1 2 500 4 98 9
1 25 331 311 10 040 158I r655 1 06 2 245299 9 086 441 453 8 0 1Ì 3 199 18? 9
1 21 159 802 r3 041 tI2 r24 6 06 3 t82 192 6 089 121 102 1 0 11 4 345 328 9
1 29 252 251 1-l 042 492 511 05 4 12 61 t219 1 0 8 10 631 642 I 0 11 6 491 469 10
1 30 192 r52 23 043 201 215 5 06 5 1054 1041 6 0 I 11 5?4 548 9 0 tt ? 161 l6f 13
1 3t 26'l 291 19 044 r465 1503 6 6 919 6 0 I 13 181 t90 tr 0 Ìt I 53 S 539 10
1 33 286 301 21 0{5 513 541 5 06 'l 6L4 568 6 0 I 14 4 85 469 1l 0 11 t0 120 59 t8
2 o 2494 2409 10 046 t228 1240 5 06 I 926 a22 6 0 I 15 692 616 9 0 1r tl 112 159 Ì3
2 1 119 134 4 041 623 613 05 9 416 1l9 8 0 I 16 Ìt0 tl3 14 0 Ì1 12 512 550 11
2 2 1835 t-824 1 048 765 ?55 6 06 IO I2'12 1242 1 0 I 18 266 265 10 0 11 13 I42 114 1l
3 182 506 4 049 1004 954 6 06 11 809 816 ? 0 I 19 438 412 t5 0 11 14 308 296 10
4 2142 2694 tl 0 4 10 1014 1? 10 I 06 t2 2ø5 286 1 0 I 20 313 310 10 0 11 15 115 14? 15
2 5 1-26'l 1293 6 0 4 1r 632 608 1 06 13 511 529 9 0 8 2t 431 406 12 0 11 16 310 319 r0
2 6 3105 3166 12 04t2 356 364 10 06 14 119 ?53 I o823 236 162 15 0 11 18 435 427 72
2 1 tI24 1159 6 0 4 13 548 542 1 06 15 641 63't 9 o ø 24 391 397 72 0 11 19 t82 144 18
2 I 13 t3 1405 6 o414 1780 1755 9 06 l6 555 633 9 0 I 25 450 456 15 o12 | 326 318 9
2 9 108 8't 9 04ls 848 8?1 I 06 r-l 139 117 16 09r 395 407 9 0 12 3 201 2L2 tO
10 2003 1988 9 0 4 16 731 ?03 I 06 18 340 333 11 092 1073 1094 l 012 5 390 380 l3
2 11 483 4't5 1 041? 455 44s 11 06 19 151 123 t0 093 531 5{5 0 DT2 I 12 9 113 1l
2 12 515 518 l 0 4 18 654 611 10 06 20 124 681 11 094 434 431 9 0 t-2 9 522 409 11
2 t3 214 188 l 0 4 19 431 401 13 06 2I 331 339 096 509 496 I o12 10 186 r40 13
2 14 L232 120? I 0420 526 522 t2 06 23 292 256 091 358 33s 11 0t2 11 4 07 386 10
t2 13 245 276 n I r -4 196 165 6 t2 -1 155 163 133 121 136 5 14 I 1551 1553 7
T2 14 200 190 14 11-3 163 186 4 l2 0 13 31 1309 134 1802 1803 7 1{ I 4 69 445 6
15 496 4'14 14 1t-2 3269 2913 t2 t2 I 153 0 165 3 135 746 801 5 14 9 692 ?11 6
13 2 393 311 L3 1 I -1 180 222 5 72 478 446 136 I61 164 5 t4 10 894 884 6
13 4 239 225 LO r10 2126 200{ 8 12 3 652 611 131 298 322 1 I4 11 1?25 1?45 I
13 6 220 226 LL r11 1.17 9 113 6 12 4 942 9?5 138 2335 2354 10 t4 12 911 915 7
I3 I 331 321 rO Ì12 801 165 4 I2 5 L682 112 4 139 795 810 6 t4 L3 243 249 I
13 11 191 153 14 113 1 003 950 5 t2 6 355 {00 I 3 10 1.002 to29 6 14 14 343 338 11
0 -33 394 318 19 114 2790 21 81 9 t2 'l 2331 2342 t312 1939 1948 9 14 L5 r29'l t216 I
0 -29 105 63't 20 115 r625 15 51 1 I2 I 1{3 159 1 3 13 584 5t3 8 14 t6 556 550 9
0 -21 544 552 16 116 1448 I442 1 l2 9 l1 61 114 0 I 3 1{ llÌ3 I121 I 14 r? 510 533 1t
0 -25 1'11 49t 16 111 874 892 l2 10 285 293 1 3 15 639 615 9 L4 19 348 361 11
0 -23 926 958 15 118 2292 2313 9 I2 1t r 6l.5 1590 I 3 16 3?5 371 t3 14 20 389 388 11
0 -19 801 856 14 119 65L 636 6 t2 12 499 412 1 3 l8 1136 1148 9 Ì4 21 6A2 603 t2
0 -l-1 82'l 't 15 13 I I 10 806 -t 81 6 T2 13 113 131 1 3 19 313 r04 l0 t4 22 ts'l 143 19
0 -15 980 1012 t3 1 I 11 625 621 .I \2 14 211 296 r321 135 1{3 2t 14 25 596 573 16
0 -13 1?34 1?43 13 1 1 12 1636 1100 I t2 15 L442 11? 4 TJ22 126 121 t2 14 26 300 301 15
0 -11 582 548 15 1 1 13 r41 146 10 l2 16 569 549 10 1 3 23 254 230 13 I4 29 296 321 I9
0 -9 2994 3166 16 1 1 14 161 I 16 81 9 t2 t-l 810 833 9 r 3 24 423 423 t3 L4 30 248 23t 23
0 -5 1202 t738 9 1115 50r 485 9 72 18 t52 144 1s t326 251 223 t6 14 31 369 354 18
0 -3 3383 3245 13 1 I 16 404 405 1L 12 19 640 660 1t I 3 28 494 4f5 15 15 -30 223 186 20
0 -1 266 201 4 1117 222 2tø 9 12 20 219 2?1 10 \329 220 209 23 I5 -26 341 31t 12
0 I 3192 3283 t2 1 1 18 157 6 1604 9 t2 21 851 863 1Ì I 4-29 321 351 15 15 -2s 318 293 12
0 3 820 141 4 1 1 20 368 422 IO t2 22 2'12 294 II r 4-21 106 295 14 15 -23 23r 250 14
0 5 1031 1015 5 lI22 ?68 189 11 T2 25 651 654 14 | 4-25 3lt 309 1.1 15 -22 538 525 14
0 ? 1.10 7 tL25 6 r124 160 't 56 t2 l2 21 26r 2't7 16 7 4-24 391 406 1.2 l5 -2r 538 501 14
0 9 225 L12 1 TI26 262 264 14 t2 29 263 25r 19 I 4-23 691 690 14 15 -20 612 622 12
0 11 683 750 6 1 1 28 4l I 464 l4 t2 31 371 378 t6 I 4-22 155 160 21 15 -19 168 143 15
0 13 268 26t I 7t32 298 21I 20 13 -30 343 361 L1 | 4-20 569 538 14 t5 -18 340 305 tl
0 15 15 31 1565 I r 2-33 393 400 t9 t3 -21 233 201 20 I 4 -19 1058 r003 l1 l5 -11 638 611 t0
0 1? 53S 5 87 9 | 2 -29 501 505 t4 13 -26 600 562 l8 1 4 -18 536 411 t2 t5 -16 1489 1448 9
0 l9 819 E10 9 I 2 -2'l 407 369 L3 13 -24 203 163 19 r 4 -l? 't 31 143 1t 15 -ls 561 550 t 0
0 21 131s 1369 9 1 2-26 355 365 14 13 -23 250 211 t6 Ì 4 -16 218 265 9 t5 -14 343 329 9
0 25 1J6 103 t2 t 2-25 368 3 68 13 13 651 651 16 1 4 -15 10 32 992 9 15 13 ll5 731 I
0 2't 572 49? 1l I 2-24 284 304 16 l3 -20 981 984 13 1 4 -t4 551 484 10 15 -r2 901 903 l
0 29 723 322 14 | 2-23 all 893 t6 13 -1S 511 60? 13 1 4 -13 113 { t621 9 -11 745 104 -l
0 3t 252 2t4 20 I 2-21 200 156 18 13 -!'l l0? 68t L2 | 4-I2 418 407 9 t5 -LO 1321 1299 1
1 -32 409 381 l.? ). 2 -20 52r 510 13 13 -76 151 4 t423 lr I 4 -11 810 f31 1 t5 -9 55? 549 '1

t -30 506 471 15 | 2-I9 \434 1409 13 13 15 139 l8 15 I 4 -10 842 80I l 15 a 461 439 1
I -26 al2 195 l8 1 2-18 483 463 t2 13 -14 362 4t3 9 I 4 -9 1395 1316 ? 15 -7 110Ì 1040 6
I -24 514 497 15 I 2-r1 855 825 13 13 -13 3s5 29A 9 1 4 -8 5 86 326 6 15 -6 1108 10?5 6
I -22 100 688 1l 1 2 -15 t241 1190 11 t3 -t2 1862 1682 9 1 4 -? 600 562 6 I5 -5 552 549 6
I -20 952 932 15 I 2-14 644 6t6 11 t3 -10 1369 1250 I | 4 -6 426 319 6 -4 104 08 9
I -79 216 224 73 I 2 -13 t242 L112 10 t3 -9 f19 669 6 1 4 -5 1054 1046 6 15 -3 361 344 6
1 -18 362 357 12 7 2-r2 623 530 9 13 -8 635 618 6 1 4 -4 659 642 5 15 2 1140 Ì141 6
1 -t6 1216 12rr 14 r 2 -11 193 151 9 l3 -1 1r 1l 1019 6 1 4 -3 t{86 t468 l 15 -t 1496 1535 7
1 -15 240 2r2 12 1 2 -10 372 215 I 13 -6 1942 1902 8 ).4-2 353 3r9 6 15 0 5 03 536 5
1 -14 545 416 14 I2-9 7?5 2615 t2 13 241 r91 1 141 1166 Ì114 6 t5 I 319 364 6
1 -12 2rt4 2156 14 12-8 29 283 I 1l -4 2rs 189 5 140 10ll 1086 5 15 2 lf 46 1751 I
1 -11 394 421 t0 t21 T2 114 2 6 13 -l 1053 1044 5 141 2028 2043 I 15 3 I32T 1301 6
1 -10 l910 1930 1t r26 48 463 5 t3 -2 1508 1503 6 142 f22 132 5 15 4 1310 1340 l
1 -9 204 10 l I 2 -s 14 2623 1t 13 -t 1492 14¡l 6 143 688 615 5 15 5 1Ls9 1t62 6
I -8 t040 1103 9 124 20 2to4 9 13 0 65 4 696 4 144 915 915 5 l5 6 808 185 6
I -6 2669 2165 rt t2-3 48 l42A 6 13 1 1543 t545 6 145 l Sll l88l 8 15 1 606 626 6
I -5 249 238 t2-2 52 526 4 I3 2 1386 1446 6 146 1203 1202 6 15 8 I994 1950 9
5 9 624 6r5 1 6 14 465 461 10 ll 452 458 12 I 9 -21 133 388 11 1 10 r 319 319 I
5 Ì0 508 508 1 6 15 388 381 tl ll 23 54f 513 15 r 9-20 3 06 r50 9 I t0 2 410 450 9
5 11 112 163 1 6 16 511 486 10 1l 24 323 344 t2 1 9 -11 3r8 f96 72 r t0 3 426 4t0 t0
5 t2 10f4 1061 r 6 1l 445 428 72 11 25 241 239 tf I 9 16 241 268 8 I l0 4 251 243 I
15 Ì3 1033 1034 ? 16 19 51{ 508 12 26 185 L14 23 9 -Ì5 342 9331 10 5 212 241 E

15 11 11?? 1163 8 16 20 622 504 12 21 L91 2l 9 -13 230 9205 10 6 846 8Ì4 t
15 15 301 312 10 16 21 422 421 11 28 304 2'to t1 9 -12 1f8 9190 10 I 150 ì5f I3
15 16 159 t58 13 16 22 41a 413 l5 -21 285 293 t2 9 -11 660 I630 t0 I 191 t73 l0
t5 t7 {52 411 11 I6 25 J94 400 t2 -24 333 414 11 9 -10 232 239 1 10 9 253 251
15 L8 '194 186 9 16 26 3ge 369 12 -23 210 30? 10 9 -9 I23 108 ll t0 l0 562 548 10
l5 20 202 212 13 16 29 361 333 16 -22 165 182 15 9 -8 265 218 A 10 rt 191 r 91 t1
15 22 55t 532 14 t? -21 321 360 12 309 3{6 9 9-1 818 8{0 l 10 ì2 523 501 t0
15 23 418 406 13 tf -26 323 3 43 1r -19 179 I1O L2 96 506 53 t I 10 13 148 105 T6
15 24 236 229 t5 1? -25 321 379 10 -18 195 129 \2 9 -5 4l1 449 9 10 1.5 260 265 l0
L5 25 226 204 11 11 -24 2r4 228 t4 233 253 I 9 -4 128 r40 12 10 16 526 524 I2
15 26 302 305 15 1'l -22 J21 360 t0 -t4 675 120 I 9 -3 591 605 I 10 18 144 109 19
15 28 392 400 14 1? -21 363 393 11 -13 439 138 10 9-2 {93 495 I 10 19 226 220 13
15 29 253 239 2l 1l -20 3?1 414 10 -t2 351 358 11 9 -l 94Ì 928 1 10 20 329 325 l0
16 -30 113 189 25 17 -17 44 0 47J L2 -tt 143 115 t2 90 359 36? r0 10 2t L61 t2a 19
l5 -26 210 263 15 17 -16 539 549 10 -10 123 132 1 92 368 37S I0 lL -20 160 199 13
16 -25 228 2r2 15 17 -15 28{ 2't4 8 -9 122 135 7 93 813 420 1 11 -tl 386 {51 t2
16 -21 365 316 1l 77 -14 520 511 9 -8 790 8t3 7 91 581 582 I 11 -16 151 146 l2
16 -23 3A3 366 12 \1 -t3 611 666 6 341 366 10 95 216 249 9 11 -t5 256 299 I
L6 -22 318 308 11 r'l -L2 425 448 10 -6 361 3{6 9 96 211 209 A 11 -13 206 234 9
16 -20 221 223 L2 r'l -11 854 860 't -5 699 691 l 91 390 386 10 11 -t1 444 500 10
16 -t 9 676 693 l0 Ll -10 494 470 8 -4 1312 ,346 1 98 412 109 10 11 -8 146 L64 l2
l6 -r8 651 516 10 1? -9 t8? 171 I -3 192 800 7 99 121 591 8 11 -? 434 441 10
16 -17 318 286 11 1? -a 420 411 8 384 3?5 9 912 313 351 t2 tr -6 198 215 9
t6 -15 631 630 9 t? -1 1t82 1178 ? -I 1? 9 195 I 9 13 588 56? 10 11 -5 345 332 8

76 -1 4 631 604 I 1l - 6 1117 1110 l 0 841 a46 1 9 14 t 61 \14 12 11 -3 409 401 tt

15 -13 994 996 I 17 -5 ll5 693 6 1 996 t 0lI ? 9 15 285 210 9 rt -2 151 t49
L6 -11 165 144 9 17 -3 't t1 119 6 2 919 985 7 9 15 352 33E 1l tr -1 443 458 t0
16 -10 896 876 7 17 -2 1309 L32t 1 3 199 222 I 9 1f 369 342 1\ 11 0 346 316 t2
l6 -9 1158 1162 7 1? -r 1295 1295 1 { 143 163 10 9 t8 3?9 376 11 11 1 It0 64 15
L6 -8 555 526 7 1-l 0 35 4 3s6 I 5 316 361 9 9 19 506 s00 14 lt 3 102 682 9
16 -7 542 515 l l? 1 311 307 9 6 8{{ 851 l 922 3t2 3I å 11 11 4 2L9 21.0 9

16 -6 681 659 6 l7 2 941 92A 6 1 r97 204 I 923 369 383 12 11 5 J49 3r2 9
15 -5 1167 1125 l 17 3 86t 880 6 I L2l t2t 13 l0 -23 188 234 13 11 1 4 65 451 1t
16 -4 a023 1022 6 11 4 900 891 6 9 112 115 15 10 -21 159 203 t4 1r I t46 150 15
16 -3 1t13 1125 6 1? 5 820 8t,0 7 10 123 422 tO 10 -20 328 395 10 11 9 626 516 10
t6 -2 59L 626 6 1l 6 293 311 8 11 6t2 600 9 10 -L9 181 203 12 11 13 510 5t 5 L2
t6 -1 660 661 6 1f 1 622 623 1 t2 486 {?1 10 r0 -18 101 314 9 11 15 290 2't I 9
16 0 819 825 6 1l I 755 't4J 1 13 141 103 13 t0 -lf 148 191 13 11 t6 220 2r0 13
16 I 1356 1367 -tl 17 9 120 1L1 'l 1{ 313 324 9 10 -16 164 156 1t 1.1 1l 269 286 ll
t6 2 15{8 1521 1l ro 234 225 1 15 430 398 t2 10 -14 199 562 10 11 19 356 323 t1
16 4 336 307 0 1-' 11 260 259 I 16 575 545 10 10 -13 1?9 1f8 10 T2 -14 431 st2 10
5 119? 1243 l I'l t2 532 5t-2 9 19 358 311 12 r0 -t2 236 259 I I2 -13 2L9 232 9

16 6 1007 993 6 17 L3 1't 2 444 t0 412 12't 14 10 10 458 518 9 L2 -12 198 255 9
16 1 '160 166 6 17 14 739 123 S 2L 231 2)l t3 10 -9 232 225 I L2 I 243 I
16 I 149 115 8 17 15 30? 216 tO 410 381 L2 10 -8 124 759 I 107 62 16
t6 9 562 548 1 t1 t6 4't 3 461 1r 25 321 306 13 t0 -5 266 283 I l2 35 4 388 T2
16 t0 830 825 f 1l 17 433 319 12 25 326 291 t4 10 -4 798 818 I t2 311 314 10
L6 11 1029 1002 l 1l 18 606 643 11 -25 233 262 t3 I0 -3 312 381 11 T2 {4Ì 441 11
16 12 200 180 9 tl 19 525 505 12 -24 234 2AL 12 r0 -2 2Ar 266 9 T2 351 343 9

16 13 268 212 ø 17 20 157 171 18 -23 226 256 12 10 0 666 64 4 8 T2 ll3 324 tO
rt2 5 1S4 146 14 2l -9 1089 r24A 9 -5 606 588 5 I -1 2613 2655 10 4 2692 2lt5 1l
t12 6 543 541 11 -8 369 380 I -4 215 0 2064 9 l0 428 394 5 4 1183 tl70 6
1 12 10 531 506 12 2l -'t 1524 15 95 I -3 356 341 5 31 t801 1622 1 4 668 663 s
1 12 t2 423 4t2 14 2l -6 933 916 6 3t23 3091 12 33 1101 t166 1 4 422 428 6
1L2 11 112 19s t6 2t -5 2't't6 2131 LL -1 425 125 s 34 998 r043 5 4 18 01 1849 I
1 13 -11 358 401 12 21 -4 188 160 6 0 93 4 951 5 35 1934 1991 8 4 1L1 146 6
1 13 -10 136 148 13 21 -7 469 452 4 1 665 68 4 4 36 666 54 9 5 4 1490 15Ì0 l
r 13 -1 301 321 I 2l -2 320 309 5 2 2A19 2836 ll 31 216 315 8 4 245 246 ø
t 13 -5 249 244 9 2l -1 1828 1804 7 3 14 3 131 38 {t0 450 l 4 1004 1009 7
l. 13 -3 231 230 10 2l 0 52 9 519 4 4 530 529 5 39 r926 1990 9 4 858 E35 l
1 13 -1 369 370 10 2t 1 2{1 256 1 108 86 I 3 10 623 638 7 4 951 9A9 1
1 13 3 424 40'l L3 2I 2 154 ?1? 5 6 2r2r 2t30 9 3 lr 166 478 I 4 I3 658 664 I
1 t3 5 208 185 12 2L J 2439 2426 l0 1 586 570 6 3t2 122 324 tt 4 I6 608 611 9
1 13 ? 315 320 t0 2T 4 187 183 6 I 1194 1500 'l 3 13 1208 1 1f9 I 4 1l 439 452 \2
I 13 9 127 393 10 2! 5 1867 1894 I 9 561 5t6 1 3 14 59? 592 9 4 18 329 322 I
20 -32 510 503 17 2L 6 391 399 6 10 121 105 1 3 15 980 1 002 I 4 20 505 478 r3
20 -28 458 461 15 2l 1 319 391 'l t2 1121 1166 9 3 16 209 206 10 4 2l Ll6 161 17
20 -26 140 411 15 2l I 378 395 I 13 119 121 14 3 1-l 243 241 I 4 625 630 13
20 2l 9 2099 2r2t 9 150 t2 3 lE 236 239 11 23 206 225 16
-21 136 484 14 15 156 4

20 -22 571 653 18 10 759 't64 6 t6 111 9 115 9 9 3 19 149 782 10 4 24 204 190 1't
20 -18 939 1104 22 2T 11 688 611 1 1l 204 209 11 320 449 401 10 4 26 6t6 6t1 1'l
20 2l 12 412 4'14 g 32t 255 281 11 214 251 11
-16 566 820 19 18 323 326 9
20 -14 1051 1678 23 2l 13 1635 1635 8 20 't06 126 1l 322 r39 TT4 22 4 30 286 216 20
20 -12 898 1184 23 2t t4 1-t1 166 l0 2T 30? 318 l0 323 5r5 526 rs 5 -30 2L6 230 25
20 -a 2014 3396 L3 2l 15 1511 155s 9 22 148 ?61 l2 516 {90 t2 -29 266 211 19
2l t6 288 216 9 203 1f 321 223 2r 2t3 193 2t
20 -6 750 803 6 20L 206 5

20 -4 3504 3498 13 2l 17 345 308 9 25 219 262 13 329 425 390 t 3 -26 23'l 222 18
2l 79 1234 1249 9 559 565 1l 4 -32 236 220 26 5 -25 620 630 Ì7
-2 3315 3333 13 25
20 0 281 289 5 2l 2t 212 214 tO 28 25t 21r 1E 4 -28 452 429 t4 5 -24 254 241 15
20 2 2114 2L4L 9 2l 23 555 539 14 30 3-t 3 382 t5 1 -21 250 252 t9 -23 200 1?0 I1
4 342 14 -22 244 259 14
20 4 1?11 1188 l 2125538 507 15 -31 241 261 26 -26 329 5
6 1359 1377 6 2 r 2't 226 181 18 -29 338 349 1? 4 -24 ,{ 5l 440 l4 5 -2! 611 6'12 13
20 I 1151 1134 6 2t2A186 126 23 3 -26 32ø 31'l 16 4 -23 511 5 5-7 1l 5 -20 545 536 14
20 l0 -¡15 7r0 6 2r29348 369 t4 3 -25 860 617 I7 4 -22 871 882 14 -19 866 866 lt
154 16
20 12 t5't6 1543 I 2 2 -32 349 340 21 3 -24 22r 2r1 20 4 -19 515 582 11 5 -18 163
20 14 309 297 I 2 2 -29 252 2!2 24 3 239 221 l', 4 -18 1150 t 115 11 5 -I? 431 483 14
20 16 1830 1800 9 2 2 -2A 550 521 t8 l -21 1040 113 f t6 4 -11 542 519 13 5 -16 62ø 615 11
20 18 833 812 9 2 2 -26 34L 353 1l 3 -20 446 441 1l 4 -16 s55 554 t2 -15 1255 1196 9
20 20 854 834 t0 2 2 -25 l9r 209 26 3 -19 1012 978 l3 { -15 t92 158 11 5 -14 22t 200 9
20 22 t009 962 r0 2 2 -24 343 402 16 3 -18 181 I8{ t6 4 -r1 1006 9?3 9 5 -13 358 331 0

20 26 580 614 16 2 2 -22 92r 92a l1 3 -r'l { 98 415 T4 4 -13 141 70I I -t2 485 468 9
28 198 194 2r 2 2 -20 I19 t62 20 3 -I6
409 424 t1 4 -12 r168 1103 I 5 -11 t21 6 t221 B

20 30 286 299 tg 2 2 -r9 403 505 13 3 -15 15?5 151 I 11 4 -11 261 264 1 -10 1083 1049 ?

2l -31 474 430 Ì6 2 2 -r8 1010 1190 16 3 -t4 342 318 IO 4 -10 248 0 5 -9 165 130 1

2l 2 2 -11 5I2 535 12 4-9 501 5 'r52 121 6

-29 592 S4'l 79 3 -13 179 142 10 506 1
6r1 5 9l
2l -25 516 621 18 2 2 -t6 48r 512 15 3 -12 148 299 l1 4 -8 1311 r2s 9 1 5 -6 6

2t -23 212 2ø7 22 2 2 -t5 402 456 t2 3 -11 Ì115 r084 8 4-1 185 ll5 6 5 1111 1093 6

2 2 -r4 7116 1182 12 915 4 -6 631 641 6 -4 623 613 6

2t -22 23t 320 22 3 -10 929 1 5
-) t41
2T -21 557 718 16 2 2 -13 605 628 11 l -9 7022 980 1 4 -5 329 lr6 1 5 184 6

27 -19 666 155 20 2 2 -12 1503 16 71 11 3 -8 1?l 154 6 4 -4 t 13I 1119 6 2r'l
21 -18 402 438 t2 2 2 -tt 354 374 tr 3 -1 108 689 6 4 -3 9ì9 914 5 -1 1584 1603 l
2l -11 554 711 16 22rOl80 185 I 3 -6 a32 196 4-2 1 9sl 1 942 I 5 0 t0f3 1114 6

-15 911 1183 1? 2 2 -9 5'19 528 1 3 -5 2246 2209 9 4 -1 109 101 8 I 092 918 6
2t -14 {96 618 ll 2 2 -8 t9a1 2024 9 3 293 318 'l
-4 40 t061 1,10 9 6 5 2 2tl t63 1
2l -77 2041 24Lr t2 22-6115 't22 5 3 2 904 916 41 891 I9.) 5 5 1405
3 1451 I
25 4 f46 l{8 6 2 6 r0 380 386 l0 1 1l 362 J54 10 9 -16 4 8l 491 11 10 I2 244 235 9
25 5 1936 1.990 I 2 6 11 87r 888 l 1 18 551 550 11 9 -15 296 312 9 t0 13 428 443 \2
25 6 353 3ls I 26721fO 't41 ø 1 I9 530 568 I3 9 -14 368 l6l t2 10 I4 201 222 12
25 1 413 463 1 2613395 413 10 1 20 560 548 13 9 -12 3t3 194 T2 10 15 286 9
I 991 996 6 26t4161 15r ll 1 23 3t0 329 t2 9 -11 385 409 11 10 16 29r 301 9

25 I 1337 13?2 l 2 6 15 ll{ 328 S 1 ?4 ll6 i4{ 12 -r0 651 I 10 1l 404 401 10
25 Ì0 653 -t48
65E ? 261616L 164 9 1 25 195 145 20 -9 355 318 1l IO 20 194 191 r5
25 11 136 l 2671124 12t ro I -21 25 6 2'13 15 1 193 t92 9 10 21 310 334 rt
t2 215 212 9 2 6 18 388 391 10 8 -26 234 290 l5 -6 964 1020 1 1I -20 331 J96 9

13 542 ssl I 2619214 226 t2 8 -23 292 331 11 548 549 I t1 -t6 341 385 10
25 t4 692 615 I 2520462 434 14 I 229 234 t3 -4 {55 451 9 t1 119 156 1l
25 15 481 491 10 2621416 490 11 I -20 Ì 40 121 18 t07 lI0 I l1 -14 219 299 9
25 18 434 436 12 2622389 400 1.3 I -19 t{6 350 11 523 523 I 1l -12 Ìl l 162 14
25 19 636 53I 1Ì 2623426 425 t3 I -18 315 299 9 0 I9t 184 I 11 10 419 417 1ì
20 448 415 14 2624r41 t85 20 I -11 503 519 tl I 216 268 9 tl -9 163 152 1l
23 564 539 15 2626399 405 t2 I -16 223 2r8 10 2 l5t ì41 1I It -6 458 468 t0
25 24 744 145 t2 2621304 252 16 I -I5 1l6 157 L2 3 l0l 69 ì6 I ì -5 t 95 18? 10
2 5 25 221 249 t8 2 1 -25 226 238 16 28 -14 375 3'12 9 2 9 4 616 614 I 2tl 193 191 10
2 S 26 188 153 22 2 1 -24 246 259 14 28 -13 811 825 I 2 9 5 2E1 265 I 2 lr 1?4 155 r1
2 5 2'l 295 2'12 16 2 'l -23 2L1 206 t 5 28 -t2 626 6599296410 419 10 27L 419 463 10
2 5 29 400 405 15 2 1 -27 245 259 12 2g -11 410 11610 2 9 1 280 2A1 9 2tL tr0 r03 17
2 6 -2A 228 211 t9 2 1 -20 260 253 t0 2A -9 I98 f958298282 302 8 2tL 1L1 103 9
2 5 -21 334 332 13 2 't -r9 260 259 rO 28 -8 tt 05 112L1299424 430 11 2 11 149 140 13
2 6 -24 316 32t i-2 2 1 -11 220 226 t0 2a -1 654 664 1 2 9 l0 164 164 I 2LI I41 t28 13
2 6 -23 216 214 13 2 1 -t6 561 s79 l0 28 -6 683 619 1 2 9 l3 531 51f 10 2tr 1ø1 18? I
2 6 -22 625 631 t3 2 1 -L5 559 655 9 28 -5 212 258 8 2 9 14 618 68 9 r0 2rt 43 9 121 11
2 6 -27 149 149 19 2 7 -1{ 309 299 L0 2â -4 489 193I29L5288 288 9 2tr 168 173 1r
2 5 -t9 531 530 12 2 1 -r3 241 254 A -3 193 1a112916234 231 tl 2tL 406 385 12
2 6 -rA Ê65 09? 10 2 1 -t2 901 920 E 28 -2 138 44492911241 293 9 226 194 r0
2 5 -11 511 550 11 2 -7 1 -IL 186 809 I 2a -1 96 8314 2 9 L8 312 384 1l 2 )-l 10 516 541 11
2 6 -16 910 90s 9 2 -10 t0l2 993 1 2a 0 93 9?ls 2 9 19 269 288 11 2 11 11 133 114 t?
2 6 -15 396 3ø6 L2 21-9695 580 ? 28 I 698 59812920310 354 10 2 11 13 225 23t tt
2 6 -r4 {28 408 11 2 't -1 921 918 7 28 169 464 8 2 rO -23 324 400 11 2IL I4 323 333 l0
2 6 -13 896 86? I 2 1 -6 1239 1232 1 28 3 254 248 1 2 IO -22 t55 114 16 2LT Ì6 15 9 151 1l
2 6 -12 10sr 105? 0 2?-5881 ø96 1 28 5 343 315 tl 2 LO -19 212 300 9 2tt 18 256 233 t7
2 6 -L0 231 239 1 2 1 -4 't'tg 196 1 20 6 292 290 9 2 10 -11 35-l 395 10 212 -r 6 131 154 15
26-98f48531 21-3r39 144 9 28 1 631 621 8 2 10 -13 511 549 10 212 -r3 314 360 t0
2 6 -A L242 l2r5 1 2 't -2 331 351 9 28 I 329 314 8 2 l0 -12 261 269 I 212 -11 r64 186 12
26-19038126 2 ? -1 1150 1133 ? 2S 9 1?1 188 10 2 10 -11 233 245 g 2t2 -9 20'l 220 9
2 6 -6 411 444 'l 210120 ?30 6 2A 10 462 411 9 2 10 -10 114 114 15 2L2 -1 252 214 I
26-54264LL8 2 1 1 340 349 9 2a II -r03 709 I 2 10 -9 385 408 11 212 ta2 160 1l
2 6 -4 712'l llJ2 6 2 1 3 499 463 1 28 t2 6t0 645 9 2 10 -8 363 383 11 212 -3 416 416 t2
2 6 -7 1052 1062 6 214646 651 1 28 13 4 83 499 lt 2 l0 -7 483 501 9 2L2 1 621 582 10
26-2790?996 2 't 5 633 619 'l 28 14 1?5 L16 12 2 10 -6 211 2A9 I 2L2 3 5L2 481 11
2 6 -l 534 533 6 2 't 6 314 293 10 28 15 411 t36 11 2 L0 -5 209 210 9 2t2 5 241 288 10
2602562111 211I20 L43 72 2S 15 632 631 10 2 r0 -3 '188 ll5 I 212 1 622 593 10
261192493'l 2 1 I ?36 122 , 2g 1? 100 ?05 10 2 l0 -2 324 306 9 212 t1 296 323 9

2 6 2 1395 1411 l 2 1 9 003 '194 1 28 18 224 222 !2 2 l0 | s29 516 9 212 13 25'l 250 10
2 6 3 987 1009 6 2 1 10 41't 134 9 28 20 l2l 356 l0 2 1,0 2 251 2)6 1 2L3 -10 23e 210 9
2642s12511 21L7312 356 11 20 2t 441 14{ 11 2 10 3 119 419 10 213 -6 330 721 L0
2654654501 2112256 219 9 2S 22 211 237 L6 2 LO 5 293 289 9 2 )-3 -{ 254 2s1 9
2 6 6 1151 11?? l 21t3466 450 10 2ø 23 29L 255 12 2 10 6 290 263 I 2L3 -1 138 82 t6
2 6 7 't00 689 7 27L4835 863 9 29 -22 115 163 19 2 10 1 111 fol I 2t3 -2 307 294 9
2 6 I 680 6?5 7 2 't t5 562 553 10 29 -20 321 32s 9 2 10 :.0 181 383 t2 213 0 442 402 12
2 6 9 154 146 t0 21t6338 330 10 29 -19 144 134 17 2 10 11 5{9 555 10 213 3 128 t3't t9
2 t3 4 16A 460 12 3r3'134 121 6 32 10 251 25t17322I44 24t t1 34 419 488 l5
2 t3 6 232 209 17 3 I 4 1520 1547 7 32 11 929 92413321504 581 t4 34 28 226 236 22
2t382822109 315291 33? I 32 t2 3 96 395 10 3 3 25 26r 2{ 4 Ì5 35 -30 296 296 2L
3 0 -3r 552 500 1l 3 1 6t521 Ì868 I 32 13 131 0 l{0083326369 318 12 35 -29 3?5 345 t6
3 0 -21 416 531 2I 3 1 't 613 662 6 32 15 L2I r29 t6 3 3 28 229 2L3 2l 35 -28 382 364 15
3 0 -23 413 545 20 3 1 I 518 509 ? 32 16 288 310 9 3 3 30 329 309 18 35 314 306 16
3 0 -21 598 818 18 319292 291 1 32 17 1082 t!23 9 3 4-31 3?5 390 t9 35 -24 1t4 691 16
3 0 -17 880 1s2? 29 3 r 10 2559 2540 11 32 18 190 211 13 3 4 -2a 21r 2gr 22 -23 L12 204 23
3 0 -15 468 668 14 3 r 11 507 516 8 32 19 4 8t- 485 13 3 4 -21 53r 596 15 -22 337 358 12
30 -13 1585 1930 14 3112688 119 I 32 2l 611 636 12 3 4 -26 256 282 20 35 -21 352 384 11
30 -11 1598 1867 r1 3 l. 14 1148 1161 I 32 22 160 t22 t9 3 4 -25 398 410 13 35 -20 624 605 14
30 -9 I66 869 7 3 1 16 1429 1464 9 32 23 5 91 603 t4 1 4 -23 J84 384 12 35 -r 9 631 640 13
30 -1 2544 2558 t0 3r]t442 440 12 32 21 480 494 15 3 4 -22 4¿2 485 Ì4 35 -18 929 926 tL
30 -5 522 556 6 3rr0292 260 9 33 -3t 254 L96 28 3 4 -2I 961 t 003 1s 35 -1f 179 rs4 ls
30 -3 1658 L146 1 3t20929 945 t0 33 -30 358 301 20 3 4 -20 322 333 11 61A 612 10
30 -1 905 989 5 3t22159 190 t9 33 -28 {38 4t{ 15 3 4 -18 353 335 11 35 -14 191 116 9
30 I 112 0 1114 6 3r23249 260 t3 3 3 -24 122 '196 21 3 { -17 8fs 86? 11 35 -13 38 4 343 12
30 3 2383 2129 r0 3724489 494 12 3 3 -23 2r3 79'l 2L 3 4 -16 410 3?4 10 35 -L2 110 85 15
30 5 496 493 6 3125232 202 t6 3 3 -20 ?03 73{ 16 3 4 -15 455 421 t3 -1t 296 246 9
30 1 2025 1996 9 3r26293 284 14 3 3 -19 312 396 12 3 4 -13 825 190 9 35 -10 1008 958 1
30 9 628 630 7 3t28216 254 L1 3 3 -18 703 ?15 1{ 3 4 -12 633 589 9 35 -9 642 661 1

30 11 !120 1411 8 3 I 30 349 344 t5 3 3 -16 489 510 15 3 4 -lr rr12 l1t0 8 -0 655
643 1

30 13 2064 205{ 10 3 2 -3t 452 439 18 3 3 -15 429 403 14 3 4 -lO 249 2LA 1 35 154
139 9
30 15 3?6 365 L2 3 2 -28 260 263 26 3 3 -14 1436 1385 10 3 4 -9 5s0 51? 7 35 -6 881 849 6
30 17 14?5 r4?0 9 3 2 -21 590 595 19 3 3-t2 329 32J 9 i 4 -6 245 109 I 35 1023 1002 6
3019815 a92 9 3 2 -25 ALO 481 16 3 3 -11 589 514 I 3 4 -l tl18 1614 I 35 -4 114 5 115 4 6

3021592 s56 12 3 2 -23 628 582 16 3 3 -10 106f 1005 f 3 4 -6 149 152 6 -3 118 0 1113 6
3023159 193 12 3 2 -22 421 461 13 33-9¡38?84134-5149 155 5 35 -2 366 338 1
3021389 311 12 3 2 -21 691 859 23 3 3 -8 908 86? I 3 4 -4 550 543 6 35 LO24 rot2 6

3 0 31 270 234 22 3 2 -20 411 590 I4 3 3 -? 483 4s5 7 I 4 -31113 1l9t I 0 r620 l6't2 1

3 I -30 268 309 30 3 2 -17 1118 12 95 15 3 3 -6 t1?1 1110 6 3 4 -2 985 991 6 35 I 10 51 107 9 6
3 4 -11f70 1?83 I 35 't't 4 119
3 7 -28 42-t 421 t9 3 2 -16 s00 523 16 3 3 -5 921 8ø1 6 2 6
'l
3 I -24 4s{ 603 18 3 2 -r5 625 653 13 3 3 -4 2314 2366 L0 3 4 I 896 098 5 35 3 r-t 6 L17
3 | -22 181 L63 26 3 2 -14 442 452 14 3 3 -3 3ll 300 I 3 4 21L10 It64 6 35 4 1063 1010 6

3 r -20 653 892 19 3 2 -13 1085 113 5 1t 3 3 -2 396 430 6 3 4 31586 1539 7 35 5 66r 686 6

3 1 -r8 543 680 r6 3 2 -12 209 169 9 33-r3683536344A12 878 6 35 6 1373 1471 1
3 4 5 384 358 -l 35 'l 219 264
3 I -1? 234 310 l6 3 2 -11 156? 15 71 10 3 3 024332413r0 1

7 1 -t6 821 975 tl 32-9614 641 1 3 3 110611014 6 3 4 6 598 592 6 35 9 162 1't 9 1
'l
3 1 -15 219 302 15 32-86t2 588 1 3 3 210611090 6 3 4 11031 1050 'll 35 10 r186 r206
3 2 -'l 2295 2230 10 3 3 3 528 500 6 3 4 I 811 823 35 1t 697 668 I
3 1 -14 1653 2000 15
3 I -12 175 194 12 32-6120 6't 0 6 3 3 4181918?8 I 3 4 9 622 a21 1 35 t2 22r 201 8
3 I -11 589 582 10 32-5201 215 1 335626628631101?3 466 8 35 t4 649 658 9
3 I -LO 2532 2596 L2 32-4396 374 6 3 3 6 1419 1388 7 3 4 11 589 552 I 35 15 361 353 9
3 I -9 150 129 9 3 2 -3 1621 15 9l 1 33759858-763412331 324 I 35 16 508 525 11
3 1 -8 160l t628 I 32-2233 222 6 3 3 6 611 616 1 3 4 13 121 f43 I l5 1'l J22 720 9

3 r -7 1?5 442 'l 3 2 -I 216l 2L6 4 9 3 3 9 138 14010 3 4 14 115 t-t1 lt l5 18 339 352 9

3 1 -6 1810 1784 8 3 2 0 138 I29 6 3 3 10 1321 1326 A 7 4 15 266 256 I 35 19 138 150 20
3t-s254 245 I 3 2 I 1481 151 9 1 331130?32083416293 291 9 35 20 631 624 t2
3 1 -4 263r 2611 10 32248r 511 6 3 3 12 520 641 A 3 4 11 14i 751 10 35 2T 4r2 4t2 12
3t-3t42 120 6 3 2 3 t865 1652 I 3 3 14 1119 1146 I 3 4 r8 320 lt5 10 35 24 543 538 1l
31-2456 478 5 3 2 4 632 618 6 3 3 15 246 239 9 3 4 19 315 301 10 35 264 t5
3 I -1 ?04 114 s 3 2 6 190 149 6 331612t13991421481 485 15 35 290 310 T6
3 1 0 1559 1125 1 3 2 11751 r802 I 3 3 18 480 49112 3 4 22 266 243 12 35 26 236 245 22
3 1 I 130 96 1 324942 935 1 3 3 19 341 34110 3 4 23 631 611 14 36 353 328 14
3 I 2 1108 1191 6 3 2 9 898 909 'l J 3 20 881 94811 3 4 25 192 202 22 36 246 2t3 18
3 5 -25 108 385 1r 3 7 -19 438 410 15 3 8 -5 320 332 rr 3 9 1.8 125 r25 2l 3 11 14 135 1s5 18
3 6 -24 269 213 t5 3 I 18 584 607 t2 3 8 -{ 135 132 11 3 9 19 280 312 11 3 11 15 299 294 9

3 6 -23 299 294 L3 3 1-t1 218 218 9 38-3443452939202r4 204 t4 12 -r2 212 303 9
3 6 -22 451 462 t2 3 -16 205 181 72 3g-216811913921282 281 12 12 -6 321 355 10
3 5 -2t 654 635 13 3 I' -15 922 893 9 3 8 -1 3-t6 402 rO 3 rO -22 269 2'13 tt 12 -6 322 319 10
3 6 -18 596 663 11 3 I -14 685 679 9 3 8 0 118 1012 I 10-18 263 286 l0 t2 -4 261 251
3 6 -r? 809 803 10 3 7-13 318 378 9 3 8 | 222 2r8 ? 3 l0-11 119 181 13 t2 -2 569 553
3 6 -15 515 500 12 3 1-12 r29 160 15 3 I 2 849 834 7 3 10 -16 408 420 12 120 t24 r09
3 6 -15 549 62f 10 3 -'I -11 705 694 I 3 8 3 354 336 10 3 l0 -L2 s92 620 9 480 482
3 6 -14 464 455 12 3 -10 819 88f I 3 I 1 606 600 I 3 r0 -11 429 450 t1 t23 rl5 163
3 6 -I3 592 565 9 31-9 1203 r10 0 I 3 8 5 209 216 I I 10-10 160 t63 t2 t24 4J4 43r
3 6 -t2 154 714 8 3'lI 518 534 I 3 8 6 390 39110 3 t0 -8 513 s93 9 t28 31'l 714
3 5 tr 689 650 8 31-1 201 185 I 381694698831,012ø8 2A1 I 12 12 258 26'l
3 6 -10 s19 5t6 9 31-6 381 391 9 3 I I -186 181 8 3 10 -6 508 521 9 13 9 219 111
36-9251 258 I 31-5 840 821 I 3 8 9 422 42lrO 3 l0 -5 250 251 E 361 319
3 6 -8 580 556 I 3 1 -4 169 110 1 38102tO20A9110-4305 313 9 t3 -3 245 220 0

36-1934 9r? l 3l-3 564 584 1 3 8 11 516 53510 I 10 3 222 2r5 9 13 I 108 282 0

36-6912 945 f 3 I -1 349 360 9 3 I 12 805 806 I 3 10 -2 lt8 102 I 1l I 312 362
3 6 -5 141 l3l 9 3t0 889 886 J u rr 4e-t 496 ll I I0 -t !3t r31 9 1l 5 )16 352
3643t6 296 9 3lt 153 f53 1 3 I t4 562 56810 I l0 0 190 116 10 13 1 t1f L14
3 6 -3 1109 1095 l 312 443 439 I 3 8 16 239 23ArO 3 l0 2 515 524 9 o -26 409 499
3 6 -2 1013 995 6 313 201 196 f 3 8 l? 401 {1510 3 10 3 262 251 I o _22 12I all
3 6 -1 681 612 6 314 395 401 9 3 0 Ì8 556 56513 3 10 4 563 562 9 o 20 936 1094
3 6 0 253 280 1 3f5 1010 1011 1 3 A 21 154 18521 3 r0 5 261 265 I -18 338 ls5 t5
3 6 1 299 306 9 316 859 E43 1 3 A 22 291 263L2 3 10 6 300 313 l0 -r6 1184 1979 15
3 6 2 1019 t0t8 6 311 201 186 I 3 9 -25 266 255 L3 I 10 I 190 41 0 12 -14 594 651 1l
3 6 31t62 t202 1 319 696 693 I J 9 -2t 223 264 13 3 r0 I 646 644 9 t2 1241 1143 9
364622 632 t 3 I l0 121 f 49 I 3 9 -19 424 411 14 3 10 1Ì 261 292 9 -t0 r459 1489 I
3 6 5 301 330 ì0 3711 666 615 I 3 9 -18 209 243 12 3 l0 12 523 53{ 11 -8 164 161 0
366663 660 l 31I2 251 25A I 3 9 -15 134 139 9 3 10 13 206 19t t1 -6 1966 2008 9
 3 6 -t 840 846 1 31 t4 6?0 ?05 9 9 14 438 450 11 3 t0 14 30? 319 10 40 -4 683 61s 6
I 6 I 891 8?9 7 31 t5 797 790 9 9 -13 349 352 9 3 10 15 201 221 l3 40 -2 761 184 5
369629 646 I 31 16 390 101 10 9 -11 539 55{ 9 3 r0 1l 156 150 1f 40 0 2059 2lt5 9
I 6 tl 388 388 10 3f L1 132 419 13 9 -10 350 322 12 3 10 18 339 332 t0 40 2 892 965 6
35t2602 609 9 31 18 231 213 11 9 -9 61{ 6E0 I 3 11 -19 249 290 11 40 4 23'tO 2361 tO
3 6 13 552 558 9 31 19 211 266 tO 9 -g 521 544 9 3 11 -15 219 305 6 40 6 703 121 1
36t1114 465 10 37 20 39{ 381 t2 9 -l 11't 156 12 3 11 -13 211 21e 9 40 8 2481 2112 tl
3615223 213 r0 31 21 J11 120 1l 9 -5 0?2 690 E 3 11 -11 265 292 8 {0 t0 712A 1657 9
3 6 16 201 162 11 31 24 241 245 t6 9 -4 387 386 10 3 11 -10 139 153 14 40 1030 10 60 I
3 6 17 701 708 r0 31 25 208 23L 20 9 -3 110 109 l0 3 11 -9 413 49s l0 40 14 12 01 1198 I
36lE678 696 11 38 -22 45'l 418 11 9 -1 51t 536 8 3 11 -E 225 232 9 {0 t8 109 105 10
3620L96 180 15 38 -2L 265 282 72 9 0 503 511 9 311-? 205 208 10 40 20 314 313 t2
362t449 {s? 11 38 -20 2t0 194 14 9 1 789 ?89 I 311-5 655 662 9 40 22 321 310 10
3622291 295 12 38 -18 581 565 t2 9 2 I7l 159 10 3 11 -{ 224 2L 10 40 24 4 83 {69 13
362337A 369 t 2 38 -17 53 4 st8 11 9 4 116 1't4 9 3 11 -3 346 3t 9 40 28 489 439 13
3624202 20s I9 38 -16 4?0 410 t2 956696?{8 3 ll -1 439 43 t1 4l -29 351 406 25
3 6 2s 198 10r 20 38 -t5 220 2\1 r0 9 6 461. {76 10 3 11 0 252 I 4t -21 361 180 23
3 6 21 2'tS 3r5 18 38 -14 210 184 r0 9 ? {61 {?1 10 3 11 1 't 00 60 9 4T -25 336 4L5 23
3 1 -28 246 222 L9 38 -13 497 469 10 98258251¿ 3 tl 1 230 22 l0 4t -23 990 25
3 1 -25 231 265 t5 38 -12 9t3 905 8 9 9 445 161 tl 3 11 5 597 58 10 41 -19 1359 14?9 19
3 'l -24 234 25L t6 38 -r1 593 608 9 9 10 120 402 1r 3 11 1 32'l 322 10 41 942 1052 17
3 1 -23 20L 102 17 30 -10 169 145 11 9 t7 643 621 9 3 11 I 200 t92 11 41 -15 100 3 1068 15
3 1 -22 28L 263 L2 38 -8 741 769 I 9 1{ 329 311 11 3 11 9 323 319 9 41 -14 I49 151 16
3 1 -2L 195 459 1{ 38 -1 632 655 I 9 15 s63 581 1l 3 1t 10 l5l r45 14 41 -13 185I 1888 11
3 1 -20 414 517 15 38 -6 63s 639 8 9 16 156 1?2 16 3 11 Ll 326 3r2 11 41 -r2 203 2t6 t0
4 I -10 313 213 9 42 2 'r94 111 6 3 13 388 101 12 1421 360 315 \2 46 448 116 14
4 1 -9 1804 Ll al 9 42 3 229 229 1 3 14 401 394 12 1124 546 551 1.6 46 -25 IA2 2t3 25
4 I -8 382 315 I 42 4 2279 2200 ro 3 15 797 005 9 1428 333 356 15 46 -24 311 345 !2
4 1 -7 l{54 1409 ? 12 5 718 130 1 3 15 590 60? t1 1 5-29 365 351 18 45 -23 280 28r 15
4 1 -6 517 510 l 12 6 2t9 L1t 'l 3 1? 836 8{? 10 { 5-28 299 265 20 46 -22 239 231 t6
41-5512 542 6 42 1 L62 156 t 3 19 295 293 10 I 5 -2'l 504 169 15 46 -21 530 s08 16
{ I -1 I40 119 l 42 E 1759 1-¡ 68 9 3 20 330 329 l1 1 5-25 22' 164 21 46 -20 633 563 t4
4 I -3 1376 L122 1 12 9 183 I78 9 3 2t 619 610 t2 I 5-21 325 2A1 l{ 46 -18 153 171 18
41-2158 {51 6 42 !0 92'l 938 I 3 22 211 306 12 1 S-23 648 586 l-t 46 -1? 6't o 536 I1
11-17a3 166 6 42 lL 199 173 9 3 25 110 399 12 I 5-2L 261 216 14 46 -16 50? {81 T2
1 l. 0 309 299 A 12 12 565 55I 9 3 26 L92 L16 22 1 5-20 212 206 1l 16 -15 681 65s 10
4 1 1 2001 2043 I 12 1r 112 {25 r1 3 2? 300 2{6 15 a 5-19 512 492 15 46 -r2 644 628 9
4 1 2 413 1't5 1 12 14 1069 10?0 I { -30 479 398 16 { 5 -18 317 293 10 46 -11 8r0 840 I
1 1 3L2L1 11?3 ? 42 1? 470 411 72 4 -26 60{ 500 15 { 5 -17 311 296 10 46 -10 64a 6f8 I
414728 289 8 42 18 877 866 10 4 -25 269 239 19 4 5 -15 326 3t l 9 46 -9 381 l9? 10
4 I 5 1661 1643 I 42 19 231 252 12 4 -24 358 363 15 { 5 -14 r03 681 10 46 433 435 9
4 1 < t'tg 136 I 42 20 42r 41 8 1.1 4 -22 501 461 t4 4 5 -13 945 699 9 -l 525 528 I
4 1 11964 1969 9 42 22 6LO 629 14 4 -2I 272 226 t1 1 5 -r2 4{9 409 10 46 -6 1028 1034 I
{1A2t2 200 1 42 23 244 216 \5 4 -20 506 500 13 1 5 -r1 156 l5l 12 45 691 691 1
4 1 9 't95 111 'l 42 24 46t 492 t3 4 -r9 264 240 L3 { 5-10 141 408 10 46 -4 103 5l 13
4 1 10 316 299 I 42 2s 300 281 13 1 -r1 242 202 12 I 5 -9 1439 L712 I 46 -3 618 60I 1
4 I 11 1920 1900 9 42 28 414 {68 t6 4 -t6 696 616 t2 I 5 -8 111 125 1 46 l0't 6 1065 1
4t122I1 2rt 9 43 -29 428 393 19 { -15 410 388 10 15-7 202 119 1 46 -1 ',5 4 130 1
4 I 13 143 {60 10 43 -28 265 250 26 4 -14 457 400 12 I 5 -6 296 261 1 46 0 1043 Ì032 1
4t14294 264 9 {3 -21 48'l 492 15 4 -13 351 359 9 45-5 r21 g 725 I f 1 159 154 9
4 1 15 820 839 9 43 -25 318 281 18 4 -12 951 903 9 4 5 -4 1t 90 1.18 6 1 46 2 294 289 1
4 r ll 117 692 IO 43 -23 15I 18r 20 4 -11 623 560 9 1 5 -l 1569 I 60? 8 46 3 566 568 1
4 1 21 568 s33 13 43 -22 330 331 15 4 -10 1335 1218 E 15-2 113 403 I 46 4 1020 101 4 1
1L25119 462 13 43 -19 825 81{ 15 4 -8 736 1tA 'l 4 5 -1 269 259 1 46 5 442 446 9
4r26L99 186 21 13 -17 ?95 114 73 4 -7 1115 lltl ? 150 1013 1045 1 46 6 2t1 I
172122A 20L 20 13 -15 50 4 586 13 4 -6 2069 2042 9 {51 r240 L239 1 46 1 450 465 9
4129212 266 20 43 -14 432 393 1.3 4 -5 661 650 6 {52 5{{ 5{9 1 46 8 852 8'16 'l
4 2 -30 411 37? 19 43 -13 1266 1223 10 4 -4 509 500 6 153 691 683 1 46 9 191 802 6
4 2 -26 5s6 551 1? {3 -11 17 t12 ro 4 -3 363 368 I 154 300 30 9 t0 46 10 409 415 1l
4 2 -21 158 363 18 ,{3 -10 93 878 I 4 -2 r54? t531 l 455 699 691 1 46 1t 243 I
4 2 -22 444 509 14 {3 -9 195 1867 9 4 -1 935 930 6 {56 12A 'l3a 1 46 t2 -713
116 9
4 2 -20 8A0 0?8 l8 43 -8 71 61t 1 4 0 1364 115-' ? 151 e91 895 l 46 l3 582 518 10
4 2 -t8 402 433 12 43 -l 119 rt62 1 4 t 158 172 I 458 324 311 r1 46 14 139 129 9
4 2 -16 t495 1500 14 43 -6 29 304 9 4 2 1003 1030 6 459 Ì'13 155 10 46 15 491 500 I2
4 2 -L4 113 75? 11 43 -s 153 1190 7 4 3 452 ø14 6 4 5 t0 314 364 11 46 l6 111 165 14
4 2 -r3 255 246 9 43 -4 7'l '142 6 4 4 1218 t215 1 4 5 11 193 t93 I 46 18 601 611 T2
4 2 -72 1It2 to92 9 43 -3 209 2060 9 4123t2t8ø { 5 t2 460 470 11 46 l9 455 434
4 2 -11 480 5Ì5 10 43 -2 59 595 6 4 8 964 935 -t 4 5 t4 159 134 14 46 20 I65 I84 l9
4 2 -I0 1364 13 42 I 13 -1 13 98 I { 9 513 558 8 4 5 t5 781 111 9 46 4t2 421 ì
42-9692 681 1 43 0 12 lt5 9 { 10 513 523 9 4 5 16 l0t 692 l0 46 23 228 259 L
4 2 -8 441 439 I {3 1 220 2L68 9 4 t2 591 602 9 { 5 1l 458 462 l3 46 24 311 328 1
42-1668 626 5 43 264 682 6 4 13 311 271 t0 I 5 1.8 311 324 9 41 235 2r5 2
4 2 -6 L924 1076 I 43 363 595 6 4 14 1026 1016 9 4 5 19 432 44 11 41 -24 396 395 L
42-5208 [t4 6 43 5 1404 1355 l 1 t5 345 331 1,0 1520 3L2 3l 10 41 23 314 348 Ì
1 2 -4 't96 ?89 6 43 6 506 493 I 4 t6 289 281 9 152r 592 61 1{ 41 -22 258 241 r
42-3a25 119 6 43 1 8't1 868 7 4 t1 212 259 t0 4522 32'l t1 11 41 -20 409 t0? I
4 2 -2 2212 2264 9 43 9 16f L62 70 4 18 1022 1072 10 1525 360 38 4f -Ì9 482 484 I
42-IA28 811 6 43 L0 225 225 8 4 19 101 101 lt 1 526 255 2'l 18 41 -1 I 568 533 12
4 2 0 155? 1518 7 13 11 111 I 1161 I 4 20 319 326 l0 152'l 256 22 18 41 -17 4E4 4'75 13
4 2 I 55{ s33 6 43 L2 202 181 9 1 22 160 506 12 I 6-21 225 23 23 41 -1 169 179 t5
4 7 -15 488 461 11 48 -2 334 3{5 11 10 -17 313 359 11 112-l 505 5l 11 5t 254 159 1
4 1 -!4 115 766 9 48 -1 ?03 707 0 l0 -16 201 22' tl 41,23 371 38 10 51 T6I2 1684 I
4 l -13 849 462 9 48 0 352 316 10 10 -15 35t 3?1 10 4125 281 26 9 5Ì 454 462 I
4 1 -12 415 468 11 48 2 1L9 409 9 10 -14 202 309 I 4L29 259 269 10 5l 603 5 98 1
4 7 -I0 4L2 422 10 48 3 924 904 7 10 -13 180 206 12 4 13 -4 a25 39 14 51 225 191 I
4 't -9 655 635 I 48 4 616 616 I 10 -11 510 5l? 10 413-2 165 1l 15 5l 1610 1609 I
41-9962 IO23 1 48 5 659 640 I t0 -10 375 381 12 { 13 0 298 21 9 5t r469 I4 51 E
11-127r 219 9 48 7 115 402 70 l0 -0 108 109 1? 4 13 2 320 ll 10 51 2'15 302 I
4 7 -6 148 125 10 {8 I 693 588 I 10 -7 552 587 9 5 0-25 580 l1 21 5t 10 359 352 E
41-5142 453 9 48 9 AB2 898 I LO -6 218 266 A 5 0-23 233 21 29 5Ì 11 282 301 9
41-4601 611 1 48 L0 292 214 9 10 -5 469 483 10 5 0 -2t 816 94 51 12 118 6 119r I
{ ? -3 108 164 1 4E 1r t68 146 12 lo -3 215 254 A 5 0 -t9 930 104 ìl 51 14 215 293 I
41-2336 336 10 48 !2 3A1 109 9 lo -2 235 2L2 9 5 0 -11 149 1? 20 51 15 143 146 16
4 I -1 t4{ 119 10 48 13 5?0 556 10 r0 -1 589 572 9 5 0 -Ì5 r136 r ).9 l1 51 I6 8r 9 814 9
4 1 0 519 493 0 48 14 4{5 441 13 10 2 245 22A â 5 0 -13 586 50 l0 51 ll 169 |16 15
4 1 I 786 79Ì 1 48 15 387 396 t0 10 7 569 514 9 5 0 -11 I 051 106 I 5l 18 496 4 90 13
4 1 2 584 511 I 48 t1 2t0 2t2 !3 10 4 233 232 9 5 0 -9 lt40 113 3 1 51 20 r88 310 I2
4 1 3 380 396 10 48 16 252 268 t2 10 5 444 394 l0 50-l t1t6 1t l2 1 5l 22 63I 5 99 1l
414232 2\9 1 {8 19 321 325 10 10 7 397 389 12 5 0 -5 IO52 1099 1 51 520 52 14
4 1 5 593 611 6 49 -24 224 2AO 16 r0 g 265 26t I 5 0 -3 22r 203 1 5t 2A 210 20
4 1 6 913 093 1 49 -22 2I8 242 15 r0 9 56ô 511 10 5 0 -1 25{1 25E9 10 -31 3r2 3l
4 't I 509 5 98 I 49 -20 284 314 11 10 12 195 18{ 12 501 1126 1750 I 52 -29 530 49 19
4 1 I 330 335 9 49 -79 218 291 t0 10 t3 449 48{ 13 503 1530 1560 I 650 61 t9
41932ø 318 9 49 -18 5'r9 606 t2 10 1{ t54 156 16 505 1924 1966 9 -24 263 28 24
41t0621 655 9 49 -t1 426 432 10 10 ls 256 25{ t0 509 1571 1546 8 52 -23 4t8 43 l5
4 7 tt 638 65 I 49 -14 673 698 10 10 18 161 161 lE 5 0 11 934 90? 8 52 -2r 451 47 14
4112188 18 9 49 -13 440 41L t2 t0 19 343 341 11 5 0 13 113 15 4 9 52 -20 263 I6
4 r 15 552 54 11 49 -12 3{0 358 9 11 -18 261 302 10 5 0 15 02t 816 9 52 19 83 6 E5 1l
4 I 16 51? 52 t2 49 -t7 202 201 10 1l -14 3r2 365 9 5 0 1l 245 222 10 52 -I8 291 32 14
4111245 24 11 49 -10 {1? 438 10 11 -13 I88 210 rr 5 0 19 715 121 72 52 -I6 49t 5I tl
4 f 18 235 23 t2 49 -9 31f 323 9 11 -12 222 244 9 5 0 21 298 280 1t 52 I5 1449 I43 IT
4 l 1., 31C lt 10 49 0 62I 61) r 11 -lr 1t2 l9r 1r 5 0 zl 4 ôr 44t r¿ 52 ìl IE9 tl ll
412023I 2I4 13 49 -'t 231 252 I 1t t0 350 365 9 5 0 25 3 85 158 l2 52 -t2 f6l l1 12
412128\ 305 l2 49 5 286 299 9 11 -9 Ì31 1{4 15 5 1 -12 359 110 l2 52 tt 1{60 t41 9
41222\5 204 I6 49 -4 518 586 I 11 -8 522 544 10 5 I -28 412 518 26 52 -10 154 tl II
412416s 140 24 49 -3 388 389 t1 11 -7 202 194 10 5 1-26 581 512 ì8 52 9 r246 t20 1
4125243 23I Ì8 49 -2 500 499 9 11 -6 113 104 tl 5 I 24 ll3 151 20 52 I 321 t0
4 A -25 211 293 15 49 o 421 417 10 11 -4 659 664 9 5t22 644 853 2l 1 1t4 66 1
4 A -24 2r9 I1 49 1 369 347 1t 11 3 190 160 1r 5 I -20 2 01 234 22 -6 196 198 1
4 8 -21 590 605 l4 49 2 15I '141 A rr -2 J40 322 r0 5 1 -19 422 430 l4 t 8l3 1f 8l I
4 I -20 408 402 T2 49 5 5t 0 511 9 11 0 3?9 396 9 5 r -18 9J2 961 Ì 6 52 4 9l0 928 6
4 A -t9 224 210 t3 49 6 642 641 9 11 I 193 1s6 11 5 I -16 983 1041 1l 32 3 198 t87 6
4 I -11 s"1 524 t2 49 ? 419 409 tt 11 2 575 522 tr 5 1 15 511 529 ll -2 l6ì 9l 8
I -16 443 438 13 4982A321A9 11 5 139 140 15 5 1 -14 462 468 L2 I 1906 1937 9
¡ -15 553 563 11 4 9 t0 {60 454 11 11 6 {65 423 tl 5 1 -12 132A 1319 9 52 444 465 I
-L4 236 218 t0 49tL2S92AA9 11 I 201 201 1t 5 1 -lt 3r8 319 9 52 r2Ì r234 f
0
I -I3 221 204 9 4 9 t2 44L 443 12 11 10 263 211 I 5 1 -9 T6J 15 4 9 52 515 528 1
I -t2 482 502 10 4 9 t4 t23 I32 19 11 11 134 119 1l 5 1 -8 I242 1252 1 52 89I 903 ?
I -11 587 608 9 4 9 15 199 186 12 1l t2 239 225 rO 511 396 3E4 I 52 s55 521 8
E -10 500 509 9 4 9 16 397 396 11 12 -11 329 356 10 5 1 -6 953 950 l 52 1556 1483 8
I -? 109 404 10 4 9 20 233 241 11 12 -1 136 156 12 5 t -4 t 05s 1089 6 52 311 350 10
I -6 350 362 LL 4 9 2L 164 lsr 21 t2 -6 t52 117 l{ 5t-3 361 352 I 52 r26 85 t3
I -5 33? 348 11 4 10 -21 289 304 10 a2 -5 362 358 9 5t-2 l7 51 1763 I 52 4'7 0 {61 10
I -4 248 249 I 1 10 -20 166 171 16 t2 -3 211 219 10 5r-1 612 655 l 52 1405 1315 I
I -3 36f 390 t0 4 10 -19 152 161 17 t2 -2 116 93 15 510 296 299 9 52 153 114 13
tt 648 664 9 5 3 23 310 329 11 5 -16 350 336 9 56-1 401 122 t0 5? 525 511 9
2 11 107 699 9 s 3 26 321 324 t1 5 -15 ll8 128 1l 5 6 -6 629 645 1 5? 4 314 329 9
2 t1 258 259 9 s 4 -29 431 383 10 5 -1{ 701 655 10 56-5 1L60 119? ? 57 t28 12r 14
15 894 895 9 s 1 -26 24r 212 21 -13 802 ?09 9 5 6 -4 232 231 I 6 s07 1't3 I
16 241 256 10 5 4 -25 {08 439 ls -t2 875 857 I 56-3 461 {68 S 57 1 837 852 I
2 19 113 l?9 11 5 4 -24 222 208 22 5 -11 111 423 10 56-2 755 169 '' 5l I 4 85 465 10
21 225 216 t4 5 1 -21 415 385 13 5 -9 703 619 I 5 6 -t l.01{ 1065 't 57 9 535 502 10
22 194 2t6 t1 5 1 -2r 530 499 13 5 -8 13?3 l3 63 I 560 692 690 7 IO 363 31't I
2 23 418 416 t2 5 4 -20 123 379 74 5 -1 883 903 1 561 833 826 1 57 t1 414 414 t1
2 25 4 60 459 14 5 1 -19 5?3 558 16 5 -6 103 0 LO12 1 562 103 116 15 5l t2 581 517 t0
3 -28 751 316 22 5 4 -1? 232 227 13 5 -5 202 181 I 563 4 60 401 9 57 13 501 476 t1
3 -26 341 J48 20 5 4 -16 580 573 t3 5 -4 9't 3 950 'l 564 846 835 I 5'l 16 323 332 tt
3 -24 210 222 25 5 4 -15 957 915 10 5 -3 ô01 815 1 565 719 f5l I 57 l1 254 264 tL
3 -23 215 308 19 5 1 -14 357 338 11 5 -2 1L 8l 11 6? 7 566 619 658 I 5'l 18 196 r92 t5
3 -22 ssa 525 15 5 1 -13 1't2 426 tr 5 -1 229 200 1 568 t26 90 15 57 2t 224 230 1s
3 -20 208 202 t9 5 1 -12 241 220 9 5 1 339 354 t0 569 839 83 6 E 5f 25A 248 15
3 -19 {30 420 14 5 4 -11 13ô2 13t6 9 5 to22 996 'l 5 6 t0 920 909 9 23 159 t52 24
3 -18 1017 100{ 13 5 4 -10 905 861 I 5 3 611 632 I 5 6 Lt 25t 273 9 58 -25 301 249 14
3 -r1 462 451 t2 5 4 -9 1468 141{ I 5 4 360 316 10 5 6 13 688 582 t0 58 -24 310 2E 13
3 -16 731 't09 t2 5 1 -1 104 r15 7 5 5 119 ?3 13 5 6 11 513 53? l2 58 -21 250 24 13
3 -15 {29 {35 11 5 4 -6 601 5?6 't 5 6 ?1{ ?09 I 5 6 15 423 419 l4 58 -20 488 49 14
J -14 506 193 L2 s 4 -5 1.7?9 r?44 -tI 1 6{1 625 5 6 16 325 343 t0 58 -r9 380 39 L2
3 -13 821 7?9 10 5 4 -4 513 519 5 I 898 8{5 I 5 6 18 195 196 t5 58 -16 344 33 11
3 - 12 1510 1464 9 51-33583859 5 9 254 259 8 5 6 19 469 168 15 58 -15 429 43 L2
3 -10 156 116 11 54-22332127 5 10 469 (53 11 5620 256 251 13 58 -14 4 61 44 1t
3 -9 345 327 11 5 4 -1 1050 1045 ? 5 11 181 185 L2 5621 249 230 14 58 -13 235 22 9
3 -8 t8{? 1803 9 5 4 0 't33 't36 1 5 t2 1033 1009 9 5623 262 229 15 58 -t2 2L8 225 9
3 -l 1079 t042 1 s 4 1 585 502 7 13 605 606 10 5624 261 246 16 58 -t 1 365 38? 8
l -6 611 609 l 5434954188 5 1{ 151 1,5 2 l6 5 6 25 209 206 2L 58 -10 411 5 0t 9
3 -5 391 334 I 5448211931 5 16 709 104 11 5 1-21 310 261 16 58 -9 291 110 9
3 -4 1322 128r 't 5 4 5 1141 1105 7 5 17 406 3 98 11 5 1-26 254 269 T¿ 58 2t1 221
3 -3 416 {8? l 5465615588 5 l8 461 161 14 s 1-23 44L 42r 14 -6 483 491 9
3 -2 t406 1418 l s412352058 5 20 239 266 13 s 't -22 526 532 t2 58 -5 536 533 8
3 -1 894 954 6 5482021929 5 27 240 235 14 5 1-2L 218 211 1s 58 -4 483 502 I
3 o 24\ 229 A 5499249318 22 416 458 12 5 7 -19 322 309 10 58 -3 t94 180 9
3 L 21r 231 1 s 4 l0 486 46{ 10 5 23 21r 191 5 ? -18 453 426 t0 58 -2 386 400 10
3 2 L6gT 1631I 5 4 11 50S 48{ 11 5 25 230 245 5 7 1? 649 513 II 58 -1 315 375 l1
3 3 262 234ø 5 4 t3 630 63't t0 6 -26 404 3A1 5 7 -16 385 390 l0 58 0 800 809 8
3 { 551 541I 5 4 t4 522 519 11 6 -25 3 90 188 5 ? t{ 32J 293 I 58 1 3 9l 3 8? 11
3 5 229 2L31 s 4 15 1024 105S 9 6 -24 255 235 5 7 -13 5 43 528 rO 58 2 23r 229 I
3 6 9r1 910f 5 4 16 392 11? 11 6 -23 222 193 5 1-t2 ?00 122 9 5E 3 531 532 I
l 1 419 11't
I 5 4 t7 191 tf6 1{ 6 -22 251 269 5 7 -11 {{0 441 10 58 4 059 839 I
3 I 938 936I 5 1 19 704 176 12 6 -2t 260 20L 5 7 -10 155 1?1 t 1 58 5 135 131 9
3 10 31? 3189 5 4 20 3?9 383 13 6 -20 526 515 5 1 -9 f09 f25 9 58 6 5 96 599 9
3 1t 55{ 512 I0 5 4 2t 249 266 73 5 -19 {91 466 5 ? -8 289 21't 9 58 8 399 380 I2
t2 1228 1198 9 5 4 23 289 290 \J 6 -18 230 209 5't-7 551 582 I 58 9 518 50? 10
3 13 195 184 12 5 1 24 210 225 LA 6 -1? 420 410 5 1 -6 452 453 9 58 t0 593 588 t0
3 11 193 272 L2 5 4 25 291 311 15 6 -16 1?8 181 5?-5 134 lls r1 58 11 258 9
3 t-6 08-, 803 10 5 5 -28 353 30? 18 6 -15 113 ?53 5 l -4 255 253 'l 58 t2 148 r44 15
3 11 330 330 10 5 5 -26 425 403 L4 6 -14 614 612 I0 5l-3 710 '123 1 58 13 202 193 l2
3 18 r99 809 l1 5 5 -23 425 411 13 6 -13 135 126 15 51-2-' 61L 661 1 58 14 318 323 10
3 t9 245 26L L2 5 5 -22 617 509 1? 6 5{5 530 9 5 -1 253 259 I 58 15 231 t1
3 20 350 349 11 5 5 -19 368 358 11 6 -10 615 604 9 510 rls 116 14 58 18 23t 228 13
3 21 195 212 t5 5 5 -18 522 498 74 6 -9 695 't23 I 5't1 7l'l 646 I 58 19 180 L8I 1?
22 596 516 14 5 5 -1? 192 450 14 6 -8 20s 196 I 5?2 863 a29 1 58 20 229 201 15
9 -23 741 358 11 510a29a2999 0 20 422 153 L2 5 2 -8 1132 1109 7 63 L2 432 449 13
9 -22 286 291 L2 s 10 9 241 229 l0 0 24 492 458 14 52-1 419 43I 9 63 13 983 9l I 9
9 -21 109 2L¿ 16 5 t0 10 429 434 t3 0 26 436 415 15 6 2 -6 528 53I I 63 14 425 424 l3
9 -20 146 196 20 5 10 11 185 142 13 1 -31 3 98 353 30 62-5 2ør 63 15 r62 141 15
9 -19 3rl 305 9 5 10 1{ 325 326 10 1 500 3SO 22 5 2 -4 1585 1598 I 63 l1 592 591 t2
9 -r0 254 283 11 5 10 15 164 r29 t6 1 -25 559 58-' 18 62-3 755 16t 1 63 l8 1.8 4 183 15
I -1-t {88 503 t2 s 10 16 256 258 12 I -24 210 280 23 62-2 335 311 l0 63 l9 316 378 ì3
9 -t6 {01 132 r0 5 11 -r7 291 32I l0 1 -23 426 {{0 15 62-l 255 I 63 20 258 263 l2
9 -13 435 {81 r2 5 11 -16 150 1?{ 15 1 -21 981 1010 r8 620 13'7 5 r 40? I 63 2l 21ø 290 12
9 -t2 286 261 8 5 11 -13 430 484 12 I -1? 880 901 t2 621 218 280 I 63 23 356 35{ I1
9 -tL 296 303 I 5 rl -12 2!6 23'l l0 I -15 453 121 tJ 622 1009 1009 ? 54 -24 386 314 74
9 -10 179 186 10 5 11 -10 138 153 14 I -t{ 242 208 10 624 511 53? 8 64 -20 546 503 18
9 -9 334 348 I 5 11 -9 312 421 12 I -13 548 5{9 10 625 36'l 142 t1 64 -19 341 334 11
9 -8 229 231 I 5 11 -l 520 554 10 1 -11 1280 1250 I 626 t47t 1409 0 64 -18 194 141 t2
9 -l 458 45? 10 5 11 -3 5?7 549 L0 1 -10 3l6 312 11 628 130 111 14 64 -11 135 1r.) 21
9 -5 108 109 t6 s 11 -1 258 25t 9 t -9 L42 L't 2 t2 629 265 280 8 64 -16 3 5-l 316 12
9 -4 231 23r I 5 11 1 300 294 9 I -1 1357 1343 I 6 2 10 1134 1093 I 64 4 60 440 13
9 -3 528 531 9 5 rt 2 124 123 11 1 -6 545 551 I 6211 r20 11{ rl 64 -14 1Ì86 114 9
9 -2 229 208 I 5 11 3 3{7 343 10 1 -5 788 ?89 ? 62L2 551 524 10 64 -13 458 46 t2
9 -t 126 429 11 5 11 7 330 329 11 1 -1 L28 96 t2 6 2 14 108 123 10 64 -r2 400 38 t2
9 0 261 252 9 5 tl 11 2'19 288 rO I -3 17 83 l8l? I 6215 231 214 1r 64 -11 411 48 11
9 1 502 491 10 5 11 12 L46 151 18 I -2 203 1?6 I 62L6 1r'l 133 11 64 -10 1188 t16 I
9 2 538 539 r0 5 11 13 299 269 9 1 -1 1700 1731 621'l 222 214 12 64 -9 ?85 114 8
9 3 68 9 683 9 s \2 -12 196 194 11 1 0 2?5 2?1 8 6220 611 622 t3 64 -8 1004 995 8
9 1 2t3 180 9 5 12 -10 405 435 12 1 | 62L 63'1 1 6221 205 188 16 64 -6 538 528 8
9 s 221 2t9 9 s 12 -9 115 86 1-' I 2 341 340 lO 6222 261 266 t4 64 433 433 9
9 6 23J 22t 9 5 L2 -6 446 468 L2 I 3 1862 L86r 9 6 7-28 95 105 r1 64 -4 915 922 1
9 1 621 6t2 to 5 12 -4 362 368 r0 I 5 431 396 9 6 3 -2'l 360 360 20 64 -3 343 331 l0
9 I 343 305 t0 5 t2 -2 1{-t 155 15 I 6 355 344 lt 6 3 -25 3 99 314 16 64 246 240 1
9 10 138 91 16 5 t2 0 451 430 13 I 7 1309 1281 I 6 3-23 214 263 t9 64 -1 t28 104 It
9 11 371 3ll 10 5 12 4 286 2'12 9 I 9 981 983 8 6 3-21 164 765 1? 64 0 ?06 138 1
9 t2 203 202 12 5 12 6 15r 165 L6 1 10 159 139 12 6 3 -18 t 6-l rll t9 64 1 442 445 9
9 t3 320 295 10 s 12 0 174 155 t4 1 lL 375 35? 9 6 3 -17 10 0t 980 12 64 2 101 -10
4 I
9 16 201 164 13 6 0 -30 390 2'19 30 1 13 1001 997 9 6 3 -16 519 540 14 64 4 513 491 9
9 1? 363 369 t0 6 0 -24 801 863 18 I 15 207 206 72 6 3 -15 190 1.73 1I 64 489 509 10
10 -20 319 350 9 5 0 -20 104'7 1185 16 1 16 15s 134 16 6 l -13 1 011 994 9 64 6 r266 t226 8

10 -19 26r 211 LO 6 0 -18 f60 800 14 1 17 112 705 1t 6 3-r2 412 413 1l 64 1 301 310 10
10 -17 140 14t 17 6 0 -16 25r 261 tL I t8 235 L92 t2 6 3 -11 1499 1455 9 64 8 151 t 65 13
-t6 402 416 13 6 0 -14 952 937 1.0 I 19 480 488 14 6 3 -8 115 r?4 10 64 9 231 249 9
-15 218 234 10 6 0 -12 448 4s3 11 I 21 311 3t1 Lr 63-'l 1292 1259 I 64 l0 115 8 11 82 9
-I4 281 312 9 6 0 -10 681 716 I L 23 516 514 12 6 3 -6 493 492 I 64 11 565 5tI
-13 240 243 9 5 0 -8 1569 t563 8 -28 502 432 18 63-5 442 4l? I 64 t2 543 s55
-L2 280 308 9 6 0 -6 914 905 7 2 -24 5s8 550 15 6 3 -4 216 285 8 64 14 543 548
-10 5r5 556 10 6 0 -4 t8l4 188? 9 2 -2t 2L6 161 20 63-3 180 l 64 15 24r 244
-8 143 151 1l 6 0 -? l_îl 114 l ? -?0 65t 611 1l .l? 46n 461 I t6 ? 61 1ø6
-6 441 466 10 5 0 0 1-147 t?89 I -r9 3-t5 394 11 6 3 -r a31 66t ? 64 1l 196 113
-5 2t2 223 9 6 0 2 1105 1146 l -18 196 808 14 632 412 412 9 64 19 231 2r1
-{ {34 463 11 6 0 4 1244 124ø 1 2 -17 r3s 99 22 633 t292 12lt 6 64 20 444 480
-2 2t]. 18? l0 6 0 6 1550 1543 8 2 -16 314 398 12 6f4 154 146 1t 64 2l 216 240
-r 214 242 I 60a334291a 2 -15 455 {06 13 635 458 465 9 65 -25 293 285
0 665 631 9 60r0f221169 2 -14 1342 1363 10 636 235 224 I 65 -22 311 358 I2
3 20Ì 213 10 6 0 t2 481 483 11 2 -Ì3 400 316 13 631 93Ì 906 E 65 -2r 454 413 13
4 501 490 1t 6 0 t4 452 424 12 2 -12 203 191 10 638 416 420 1t 65 -20 223 203 15
5 2 99 260 9 6 0 16 634 628 t2 2 -10 1283 1248 I 639 1049 t020 I t8 221 224 l4
6 215 295 8 6 0 18 233 215 t3 2 -9 340 3Ì0 11 6 I tl 606 516 l0 -ìl 84t 816 1I
l6 419 392 10 6 6 2 541 5I3 9 I -8 360 382 11 6 r0 5 4 80 41t t2 lt 16 I5l 165 tl
5 s -15 602 602 \a 6 6 3 r52 l4s 12 6 I -6 252 255 1 6 10 6 201 161 12 18 694 668 12
6 5 -13 569 615 9 6 6 4 161 4621O 6 S -5 853 I91 I 6 t0 I 304 294 rO 20 404 392 13
6 5 -L2 62'1 64'1 9 66566665196ø-4 514 575 9 6 Lr -2 381 366 10 22 311 29L T2
6 5 -rl 1013 1015 I 6 6 6 594 555 9 6 8 -3 495 526 9 1 0 -21 285 122 21 -23 101 665 l8
6 s -10 2't3 213 I 667597583968-1 11ø {f3 10 1 0 -23 191 858 19 -2r 242 301 15
65-8800f988 6 6 t0 629 65010 6 0 0 562 534 9 7 0 -21 368 386 12 -20 196 223 t9
6 5 -l 1092 1091 l 5 5 11 609 59310 6 8 I 860 830 I l 0 -19 518 590 15 -19 4I2 4I1 t2
65-64214319 66!221126096A2 558 522 9 I 0 -1? 882 861 tì -18 313 334 11
65-58028047 5 6 14 131 124t0 6 8 4 335 30r 9 l 0 -15 183 118 14 -11 f01 701 13
65-441L12L9 6 6 15 357 32611 6 I 5 615 665 9 I 0 -13 1093 1052 9 -t5 517 555 l2
65-34464418 6 6 t6 350 34310 6 I 6 310 339 9 l 0 -rl 291 32\ 9 -13 r23a 1229 rO
6s-25816088 6 6 19 220 221L5 6 8 1 463 132 11 7 0 -9 1214 tll0 8 -12 494 488 r1
65-11491581 6 1-22 333 33011 6 I 9 242 221 r0 't o -1 913 996 8 -1t 302 2't5 I
65014542L9 6 1-2t 410 39612 6 8 10 210 254 9 l 0 -5 1164 1181 8 -10 221 2tL 9
6511801539 6 1-20 229 2t114 6 I 1l 351 345 11 1 0 -3 2t43 2154 10 -9 1081 1088 I
6 5 2 381 38110 6 7 -18 185 169 14 6 I L2 170 156 t4 't 0 I 1510 1512 I -8 331 313 9
6 5 3 786 t56 I 6 't -t't 318 318 9 6 I tl 150 r37 18 f 0 3 100{ 992 1 993 980 8
6 5 I ?56 138 I 6 7-16 399 11010 6 I r5 32'l 312 11 1056¿2 ?14 I -6 1s9 191 11
5 5 5 114 13113 6 ? -15 all 199 t2 6 9 -17 161 175 14 ? 0 1 866 850 I 746 8
748
6 5 6 160 149 12 6 1 -r2 481 493 r0 6 9 -16 294 317 I 1 0 9 115 t2t t4 -3 1309 I
121 2
65?8558318 6 7 -1r 163 45{ 10 6 9 -15 2lo 233 11 ? 0 11 563 550 10 2t4 2t4 e
6 5 I 445 439 11 6 1 -A {95 533 9 6 9-12 3 5l 38{ 9 7 0 t3 588 538 11 -t 220 227 I
6 5 9 560 54't 10 5 1 -1 620 630 0 6 9-10 311 365 I f 0 15 115 656 1Ì 0 554 568 8
6 5 11 429 1lO 12 6 1 -6 610 658 I 6 9 -8 352 316 72 1011641 654 t2 I 13 83 I4O4 E
6 5 12 {10 421 13 6 1 -5 353 370L0 6 9 -1 33? 3 68 I l 0 t9 199 r96 1.1 2 t57 149 t1
6 5 13 831 811 10 6 1 -4 165 17010 6 9 -6 a65 196 t0 1021692 61? 1s 3 656 102 I
6 5 1{ {70 512 13 6 1 -3 112 {1110 6 9 -5 t22 135 15 1 r -26 520 533 17 4 314 39f 1l
6 5 16 210 199 12 61-2908951869-4 2r3 201 9 1 1 -24 326 402 18 55I 524 9
6 5 17 181 {9{ 1l 6 1 -1 691 679 I 5 9 -3 311 372 1l 1 L -20 113 112 15 6 t42 138 14
6 5 18 411 {19 11 61020'r200969-2 609 615 9 l 1 -16 6{9 620 t2 1 1093 I
1099
6 5 19 289 285 11 5 1 I 363 352 11 6 9 -1 1L2 394 l1 I 1 -15 194 145 13 8 235 9
214
6 5 -21 310 318 13 6126366449690 218 255 9 't 1 -14 {03 393 10 l1 101 0 1011 9
6 6 -2J 315 29? t3 6 1 3 6a3 802 I 6 9 I 189 204 1t 1 | -L2 121 lI8 9 l0r 2A6 9
6 6 -20 1?7 157 18 5 1 1 538 51{10 6 9 2 112 162 )-1 l 1 -11 332 103 10 13 716 319 9
6 6 -19 506 490 15 6 't I 530 53010 6 9 3 101 318 L2 ? 1 -10 107? 1073 6 14 184 118 1.3
6 5 -18 425 {18 11 6 't I 672 65010 6 9 4 5?3 537 10 ? 1 -9 365 154 12 15 546 560 t2
6 6 -L1 240 262 12 6 7 9 329 30910 6 9 5 20â 201 r1 7 1 -8 413 444 r0 1l 530 520 r3
6 6 -t6 222 204 7l 67r02692øO9696 249 9 1t-1tr2 95 16 18 t9l 195 15
6 6 -r5 294 29L 9 6-t112612469691 r 94 169 t2 I 1 -6 t55E 1681 9 19 I42 L29 2t
6 6 -L1 726 136 9 6 't 12 417 356 13 6 9 I 4 90 159 t2 ?l-5366
-r 1 -4 815 84 0 7
340 1r 27 4 83 503 12
6 6 -13 3{9 3-r8 10 6 7 13 339 320 11 6 9 9 195 183 12 -26 386 {21 r8
6 6 -12 212 286 g 6 1 t1 219 294t0 6 9 L2 J2T 301 10 f I -2 L1,78 118l. 7 -24 319 3 63 15
6 6 -11 292 299 I 6 7 t1 351 316 11 6 l0 -13 301 731 9 7 1 01263 1300 I -23 2't 0 310 18
6 6 -10 661 659 I 6 l 1,8 2A1 305 12 6 10 -11 201 228 LO 11L283 289 9 -22 416 434 1s
6 6 -9 419 {12 l0 6 A -20 153 115 19 6 10 -9 466 516 11 112465 419 9 -21 364 340 12
66-86556078 6 0 -19 3?7 405 12 6 10 --t 156 t66 t2 7 I 4t298 1334 I -20 ?51 118 t5
6 6 -1 157 155 11 6 8 -18 23'l 241 r! 6 10 -6 115 165 10 ?r6310 384 l1 -1'l 222 230 14
66-5A2L9331 6 8 -15 223 242 r0 6 10 -5 390 39? 11 711302 281 rO -r6 840 808 1t
6 6 -4 1000 1021 l 6 I -1{ 219 214 10 6 10 -1 302 301 I 1 r I 582 5?1 9 -15 562 542 12
66-32552628 6 8-r3 260 296 I 6 10 -3 335 340 9 7 I 10 106 .)20 10 -r 4 669 648 1r
66-232232L8 6 I -12 160 156 12 6 10 -1 336 3t3 r0 f 1 11 163 13 8 t3 -12 126 693 9
66-t64?665I 6 8-11 7A2 202lt 6 10 0 438 789 12 1I12382 36t 10 -r 1 29r 219 9
6 6 0 071 850 ? 6 8-10 323 330 9 6 10 I 489 161 11 7 I 14 165 141 10 -10 738 9
6618368328 6 I -9 4?8 51310 5 10 2 246 208 9 7 I 15 328 334 10 -9 446 455 IO
? 3 -8 t72 175 10 1 4 9 t?3 14913 'l 6 -9 622 625 9 l I -14 318 351 9 -t2 L251 l2r1 9
13-128L2599 7 4 10 360 364 10 1 6 -8 425 {31 10 I I -L3 292 291 9 -10 160 139 14
13-696899t8 7 4 11 896 90310 1 6 -'l 691 f14 I I I -12 tlo 392 9 -8 1185 1162 9
1 3 -5 317 393 10 1 4 t2 559 56911 I 6 -5 231 2\1 I 7 I -10 218 2A1 6 -6 846 842 8
't 3 -4 365 355 10 f 4 13 3'r3 356 L0 'l 6 -4 557 615 9 18-9431 460 l0 -4 503 511 9
1 3 -J 15'l 164 10 l 4 t5 36? 36011 'l 6 -3 695 ?13 8 7 8 -8 600 650 9 -2 146 131 I
13-29359s37 1 4 L6 2s3 25511 1 6 -2 451 481 10 18-1416 521 10 0 111 10I 15
7 3 -1 239 254 'l 't 4 t1 3t4 385 12 I 6 -1 166 1t4 11 18-5221 209 I 2 10't 't33 8

1308508937 ? 4 19 150 13320 1 6 0 168 164 r1 l I -4 54{ 566 9 4 601 618 9

't 3 1 185 205 9 1 S-22 251 20115 1 6 I 62t 621 9 78-3{51 44I t0 6 416 48{ l0
13331830?9 1 5 -2L ,106 410 12 1 6 2 918 913 I 1A-2538 552 9 I 519 503 1l
1 3 1 1304 1286 I 1 5-20 458 {2812 1 6 3 335 296 10 7 8 -1 136 111 14 10 202 tø4 rr
I 3 5 180 19911 ? 5-19 183 1741.? 1 6 4 217 252 9 ?80269 269 9 T2 't92 167 LO
'l 18t299 l4 J61 )58 t2
1 3 6 434 4281r 1 S -7't 152 461 lL 6 510 496 11 -¡ 8 2 512 216
5 9
1 3 1 21-5 222 lO I 5-16 132 123LL 'l 6 6 499 19? 11 564 10 l6 13A 699 L2
'I 3 I 1072 1044 9 ? 5-15 311 29310 1 6 1 481 445 11 7 8 3 2'lO 259 9 18 5't0 522 15
7 3 9 599 574 10 't 5-11 450 48013 1 6 8 349 331 10 f85269 265 9 -25 386 394 r6
?310?83?839 ? 5-13 201 1961r 'l 6 9 143 160 l5 I 8 6 350 331 11 -23 403 3A2 li
? 3 11. 226 254 lO 1 5 -)-2 4-t5 482 11 ? 6 l0 244 245 tO 781251 229 lO -:.9 606 580 16
'l J 12 a06 ¡103 13 l 5-11 5A9 62t 9 'l 6 11 541 512 t2 198239 229 lI -I1 168 206 r9
l 3 13 233 243 tl 7 5-10 162 161 I 1 6 12 341 34{ 11 I I 10 t88 169 14 904 8't2 11
r 3 14 829 833 10 75-930230691613 201 173 13 ? I 11 299 2A5 9 -14 331 320 10
I 3 t5 252 246 17 1 5 -1 161 418 9 7 6 15 359 317 10 1812290 216 t0 -13 545 543 12
? 3 18 474 4?8 15 l5-61221J9A1616 290 290 11 l 9 -12 143 144 1{ -r2 186 1?l 14
? 3 19 r12 205 18 75-521922481611 380 391 10 I 9 -11 435 479 II -11 10t9 992 9
1 3 20 333 318 10 7 5 -4 228 22'l I 1 1-20 265 251 t2 l 9 -r0 169 160 rl -10 241 l0
259
1 1 -24 230 t99 2L ? 5 -3 232 232 I 1 7-19 264 280 LL 19-9226 250 9 -9 1209 1196 9
1 1 -21 {2f 415 14 1 5 -2 5{0 538 I ? 1-11 193 229 L3 I 9 -l 405 439 lt -1 399 401 12
't 4 -21 206 206 19 I 5 -r a15 421 10 't 1 -16 242 251 10 19-6299 286 9 I4r0 1422 I
1 4 -20 319 330 12 1 5 0 551 551 I I l-15 394 121 13 19-s542 516 9 -3 506 534 9
I a -19 ?40 ?30 13 7 5 1 108 42010 1 'l-14 215 244 I I 9 -4 153 lt9 13 -2 203 228 9
7 1 -18 351 318 11 7 5 2 111 4491O 'l 1 -13 251 261 9 ? 9 -3 196 211 10 -1 6f2 649 I
't 1 -71 692 689 12 7 5 3 311 283 l0 't 'l -12 130 131 15 19-2280 21t 9 0 196 178 9
7 4 -15 332 3r4 9 ? 5 4 916 906 9 I 7-).1 524 553 10 19-152ø 562 rO 1 921 966 6
I 4 -14 357 349 11 7. 5 5 157 45211 1 1-10 620 644 9 1 9 0 416 391 1l 3 I80 lf9 l0
1 4 -t3 938 943 9 I 5 7 200 2rL71 1 1 -'l 517 525 9 19t279 219 10 4 rg't 209 9
1 4 -L2 162 1't2 tl 758866849911-6 511 9 193448 415 12 5 741 758 6
? 1 -11 429 451 11 I 5 9 509 520 11 'l 'l -5 661 690 I 1 9 4 r70 159 14 1 18? tl9 t1
? 1 -10 320 321 10 ? 5 10 ?00 68510 1 1 -2 500 5r't 9 1 9 5 411 409 13 9 832 827 9
11-98588608 1 5 12 261 26)-10 1 1 -l 693 124 I 195263 235 10 11 644 624 rO
? 4 -8 335 326 8 ? 5 13 330 32810 1 1 0 482 469 t0 199328 328 10 t2 305 300 10
1 4 -1 45¡t 498 10 ? 5 14 620 59111 1 1 I 3r9 305 t0 l 10 I 366 40s l2 415 4 4',t 13
1 4 -6 149 1{7 11 l 5 16 159 t5018 1 1 2 353 351 10 7 10 -? 136 136 r3 t5 108 691 1l
? 4 -5 3{-t 374 11 ? 5 t7 236 251L3 1 1 3 389 755 12 ? 10 -6 121 96 15 l9 549 525 15
1 4 -4 450 440 9 I 5 18 303 326 11 1 'l 4 4 91 484 11 I t0 -4 381 414 l2 -23 263 241 78
1 4 -3 111 192 I r 5 19 303 312 11 f 'l 5 492 {53 ll I 10 -3 302 281 10 565 583 l4
1 4 0 r43 12511 1 6-22 321 33072 1 1 6 146 136 t5 1 10 -2 286 300 9 -2I 269 288 15
14t8829218 7 6 -19 396 398 12 1 1 I 434 433 13 I r0 0 285 280 9 -20 204 195 ì8
1 4 2 429 44210 7 6-18 441 44815 1 1 9 3 96 382 10 7 l0 I 213 204 12 I8 694 669 14
1435405389 1 5-t1 536 55212 7 I Ì0 32\ 30? 10 I t0 2 313 35 10 -l l 38A 360 12
1 4 4 184 152 10 l 6-14 565 60211 1 1 13 298 280 10 l 10 3 206 18 t2 591 584 1l
7 4 5 114 16A 9 I 6 -r3 701 730 9 ? 1 14 364 334 12 B 0 -22 581 58 l9 15 244 215 12
1 4 6 61? 598 Ì0 'l 6 -12 ).69 L14 12 I 7 15 226 229 r3 I 0 -18 4?l 45 T2 l4 483 455 l3
1 4 l 1099 1085 9 f 6-1Ì 221 214 9 1 8-18 366 409 11 E 0 -t6 925 88 1I 936 906 9
14A2522649 I 6 -10 404 404 11 'l ø -71 202 232 12 E 0 -t4 312 35 t2 -11 326 325 9
8 2 -10 348 345 t0 0 4-2r 21r 18811 8 5 0 243 2f0 10 I 7 3 Ì89 L8 l2 -23 20I 2IO 24
a 2 -8 1066 1069 I 8 4-20 t19 18220 I 5 9 569 513 12 8-74253 246 10 -22 244 205 18
I 2 -i t34 101 15 0 4-19 296 26112 0 5 10 r19 10 I9t 10 -2C' rß4 166 t2
a2-69399228 I 4-18 5s8 ?0814 I 5 11 420 4t8 10 E16290 216 9 18 61 6 513 l5
82-52122429 8 4-lf 280 26811 I 5 14 295 304 t0 811t94 209 13 -16 210 Ì44 l5
a2-42192039 8 4-16 626 67012 8 5 15 384 315 t2 E?A231 221 11 -14 940 851 11
I 2 -3 340 346 6 I 4 -14 lf? 187 14 I s 16 209 261 15 819286 261 l0 -\3 2JO 224 13
a2-29489?90 8 4 -13 343 351 11 8 6 -20 236 243 t4 I l l0 360 360 T2 t2 36t 323 ll
a 2 I 505 518 9 a 4-L2 526 642L0 I 6 t9 164 128 I8 8111293 218 t0 l0 836 195 9
a221491154 8 4 -11 225 236 lO I 6 -18 341 343 10 8 8 -r3 16? 319 -9 3r1 242 70
82326t2859 I 4 -10 213 200 10 I 6 -t? 214 294 rO ð 8 -12 169 316 t2 I 915 932 9
a 2 4 534 553 9 I 4 -8 572 585 9 I 6-16 43 9 416 t4 I 8 11 103 325 10 -1 246 226 9
a 2 6 512 538 t0 I 4 -f 389 39411 8 6-14 149 155 15 I I -9 135 376 9 -6 148 l6? ì4
a 2 ? 192 16511 I 4 -6 420 43511 I 6-13 419 448 r3 I I -8 116 719 12 4 851 662 I
28 815 860 9 3 { -4 296 30510 I 6 -t2 606 608 10 EE-? 532 563 10 9 | -2 159 r64 12
29 {{4 150 12 I { -3 s64 5't8 9 I 6 -11 L14 t16 12 E A -6 286 219 I 9 I 0 633 649 I
210 234 253 70 A 1 -2 9?4 1013 I I 6 -10 !25 133 16 8 I -4 210 2966912 648 613 9
212 199 786 10 I 1 -1 t16 1,44 t2 I 6 -9 J2I 726 L0 I E -3 3 01 130 t2 9 r 3 L52 18? I2
213 215 19412 I 1 0 196 21110 0 6 -8 321 J25 9 8a-2 393 3A312 9 1 4 32r 324
2 11 221 279a2 8 4 t 268 213 9 S 6 -1 482 4?8 10 I I -1 3 00 J028916 713
2t6 {65 {6715 8 { 21r461t81 8 I 6 -6 {06 {25 t1 881 ?22 22sI0 9 I 1 135 141
2tg {6s 4{011 I a 3 532 5s210 6 6 -5 15? 133 t2 882 t95 186 t2 9 I I 183 r58
3 -23 15r 42413 I 4 4 13{ 15612 6 6 -4 119 199 10 883 319 3{3 10 9 I 10 801 182
3 -21 159 4581{ I 1 6 602 61510 I 6 -3 565 5-t0 9 086 1E'7 20614 9 I 12 461 411
3 -20 2¿9 307L4 0 ( l 502 18812 I 6 -2 559 580 9 88'l 288 269I0 9 1 14 349 314
3 -19 506 56315 I 4 I 782 75310 I 6 -1 {01 102 tl 888 255 229lt 9 1 t5 141 98
3 -18 209 221t6 0 4 9 397 39910 I 6 r 64 ).62 12 889 223 19012 9 1 16 5t 4 546
3 -16 204 155 14 6 1 t2 555 503 11 I 6 1 224 225 9 I 9 -10 429 49511 9 2-21 458 470
3 -t5 194 114 7t I 4 13 181 189 t5 I 6 2 550 581 t0 E 9 -9 28I 290 8 9 2-11 669 614
3 -14 244 230 \t 8 a 11 22a 224 12 I 6 3 s'l4 562 l0 I 9 -8 151 t6112 9 2,16 2t2 r92
3 -L3 118 159 12 8 { 16 233 230 13 I 6 4 {13 362 13 I 9 -6 332 371 9 9 2-15 578 530
3 -11 453 472 7t I { 11 226 209 L3 I 6 6 361 335 t0 89-5 302 3r1 g I 2-73 356 304 L2
3 -10 158 la1 13 I 5 -21 3t2 305 L2 I 5 'l 129 124 t4 0 9 -4 336 363 9 9 2-i.2 231 218 11
3 -9 55t 552 10 I 5 -20 266 290 11 I 6 I 5t5 4E8 t2 I 9 -3 195 18510 9 2 Lt 151 ?38 10
3 -6 316 4t1 12 I 5 -19 613 640 13 I 6 11 t?9 1?2 t5 I 9 -2 159 15513 9 2 -9 335 291 10
3-5 99I 1018 I I 5 -16 313 323 l0 6 6 I2 363 3 5't 12 8 9 -1 197 183 11 I 2 -A 326 303 10
3 -4 304 300 9 I 5 -15 646 660 11 I 6 13 1El t8t 15 890 357 34910 9 2 -1 83 9 829 9
3 -3 399 30{ 10 I 5 -11 163 152 15 I 6 l4 18r 103 16 891 197 160 t2 9 2 -5 106 124 9
3-2 529 547 9 I 5 -13 375 343 10 0 1 -16 324 335 9 892 138 139 18 9 2 -4 366 359 9
3 -1 8?0 087 8 I 5-11 381 400 9 6 'l -t5 328 331 9 89{ ?16 258 10 9 2 3 593 510 9
30 556 5'r3 9 8 5 -I0 423 442 12 I 7 -14 313 339 9 9 0 -2r 430 38113 9 2 -2 150 164 l3
31 883 923 I 8 5 -9 509 540L0 I 7 -13 t9l 2L4 L2 9 0 -17 1t2 66514 9 2 -l 816 83I I
33 379 361 1l I 5 -8 1ô6 153 10 A 'l -12 220 2{0 l0 9 0 -r5 't38 lt3 Ì2 9 2 0 266 290 9
31 1.69 I92 11 I 5 -6 390 432 t2 I 't -1L 280 301 9 9 0 -Ì3 403 385 tl 9 2 1 245 210 I
35 11901t83 9 I 5 -5 606 625 9 I 1 -t0 529 510 10 9 0 -11 1101 1041 10 9 2 3 184 816 8
36 541 508 10 I 5 -4 102 110 tL 8 l -9 636 66't 9 9 0 -l 965 978 9 9 2 4 33 9 36't 9
3'l 176 16013 8 5 -3 292 293 6 I 7 -8 203 2r8 10 9 0 -5 4 08 390t2 9 2 5 401 395 11
39 703 700 10 I 5 -1 751 't11 6 I 1 -1 18? 186 10 9 0 -3 512 5589926 241 238 9
3 10 333 35311 I 5 0 719 ?{? 8 I 1 -6 396 125 t l 9 0 -1 933 952 8 9 2 'l 5 90 606 10
3 11 1€1 47512 I 5 I 632 646 9 I 1 500 525 10 903 ?45 't55 9 9 2 9 160 129 t0
312 266 215L0 I 5 2 189 19810 ¿ 1 -4 466 501 10 905 412 {1110 9 2 rO 234 211 11
3 t3 3053039853384422987 -L {55 184 ll 901 ? 80 r?l 10 9 2 t3 601 610 12
3 15 1?5 18111 I 5 { {61 13711 I 7 0 401 443 t2 909 ? 98 112rO 9 2 15 155 r?9 19
1 -23 289 27115 I 5 5 856 845 9 I 't 1 42L 393 l2 9 0 13 82t rl61t 9 3-22 318 309 14
1 -22 635 621 1l I 5 6 302 320 ).0 I 7 2 2L0 200 1l 9 0 15 322 322 lt 9 3-20 311 321 t3
3 -19 231 234 76 9 5 -12 249 250 \0 9 1 2 241 258 9 10 2 -6 541 553 rr 10 5 -14 194 163 14
3 -18 512 487 16 9 5 -10 358 363 10 9 1 5 296 2't9 9 10 2 -5 230 22s t0 10 5 -13 385 376 11
3 -17 287 258 !2 9 5 -9 468 {87 11 I 1 6 393 362 r1 10 2 -4 516 488 10 10 5 -I2 253 264 tr
3 -14 {09 388 11 9 5 -8 3s9 315 10 9 1 1 224 2!1 t2 l0 2 -2 460 455 11 10 5 -11 2t5 T94 12
3 -13 219 239 !7 9 5 -7 2L9 244 t0 9 I -t0 246 214 9 10 2 0 541 513 10 10 5 -9 432 429 73
3 -L2 268 256 L0 9 5 -6 201 22L L0 9 8 -8 180 20t l1 t0 2 I 240 280 9 10 s -8 314 401 10
3 -10 561 548 11 9 5 -5 L90 206 11 9 t -1 256 264 A 10 2 2 153 164 13 10 5 7 415 441 t3
3 -9 21¡l 198 11 9 5 -1 651 671 9 9 I -6 280 32\ 9 10 2 4 603 639 9 I0 5 5 162 180 13
3 -8 t14 't03 9 9 5 -3 41? 419 11 9 I -5 226 265 9 10 2 5 282 292 9 t0 5 -4 351 361 10
3 -6 1?5 18112 9 5 -2 224 22A 9 9 I 31{ 320 l0 t0 2 6 253 256 9 l0 s -3 602 610 10
3-5 323 3I810 9 5 0 562 57210 9 A -t 188 189 11 l0 2 I 416 453 13 10 5 -2 242 261 9
3-4 10421057 I 9 5 1 413 13112 9 I 0 180 r 93 12 l0 2 to 4 86 488 13 10 5 0 209 220 LO
3-3 217 295 9 9 s 2 549 58010 9 I 3 21r 245 L0 10 3 -19 285 293t4 10 5 1 365 384 9
3-2 300 288 I 9 5 4 201 181 t2 10 0 -20 535 604 I8 r0 3 -11 {41 407 13 I0 s 2 302 3 05 9
30 857 909 I 9 5 5 396 41210 10 0 -16 801 756 13 t0 3 -13 542 518 13 l0 5 3 335 359 10
31 220 236 9 9 5 6 645 61211 10 0 -14 616 564 13 10 3 -11 322 29210 10 5 6 213 264 70
32 142 161 9 9 5 I 167 1?515 10 0 -L2 423 398 11 10 I -r0 212 181 13 10 5 7 386 388 11
33 250 267 A 9 5 10 364 320 11 10 0 -r0 861 811 10 10 I -9 584 580 11 10 5 8 L61 174 t5
34 323 336 9 9 5 11 183 l,?2 15 10 0 -6 461 416 L2 l0 3 -8 180 186 14 10 6 -\2 r23 109 20
36 142 't41 t0 9 5 t2 256 260 t7 10 0 -4 2ø1 286 9 10 3 -f 698 680 10 10 6 -11 298 301 10
31 341 348 11 9 6 -17 214 2A2 tt 10 0 240 269 9 103-5 305 295 9 10 6-10 239 235 10
38 I53 145 15 9 6 -t6 304 319 9 10 0 0 128 738 9 10 3 -4 299 3209106-9 26r 259 9
3 10 391 39? 10 9 6 -15 353 3?0 10 t0 0 4 1't I 't't't 9 10 3 -3 838 866 9 10 6 -1 150 14S l5
3t2 358 345 12 9 6 -13 215 213 11 10 0 6 353 366 L0 10 3 -2 360 315 9 10 6 -6 {11 433 13
3 14 210 196 13 9 6 -!2 414 142 t3 10 0 I 516 561 12 10 3 -1 239 219 9 10 6 -5 333 348 10
4 -2L 492 493 t3 9 6 -11 399 425 13 10 0 10 588 546 12 10 3 I 5t2 6r? t0 10 6 -4 244 251 9
4 -19 182 201 19 9 6 -10 293 293 9 rO 0 I2 184 115 1l 10 7 2 240 231 I 10 6 -2 2\2 224 \O
{ -18 199 161 16 9 6 -1 431 420 11 10 1 -19 164 439 t2 10 3 l 4 50 465 tr 10 6 -7 332 355 10
4 -11 341 356 11 I 6 -6 490 a96 10 10 I -ll ?35 66t t4 10 ) 4 201 202 I0 l0 6 0 403 420 13
{ -16 232 210 13 9 6 -5 288 280 9 10 1 -13 926 833 l1 l0 3 5 |t1 190 12 10 6 3 288 3 07 I
4 -15 t50 482 14 9 6 -4 160 171 13 10 r -11 335 283 10 t0 3 'l 346 155 9 10 6 4 314 357 11
4 -r2 306 292 9 9 6 -3 323 332 IO 10 1 -9 521 5t8 l2 I0 3 11 314 359 11 10 6 5 2â6 295 LO
1 -11 564 558 11 9 6 -2 380 403 t2 10 1 -1 654 650 I0 10 4 -16 239 13 10 1 -1 248 253 9
4 -10 224 225 10 9 6 -1 418 436 11 10 Ì 136 98 15 10 4 -15 2r7 t8l 1{ l0 f -4 221 232 9
4-1 65663899602242419101 -3 612 682 9 10 4 -14 310 303 10 10 1 3 254 2'to 9
4 -6 386 418 13 9 6 2 2t5 209 L0 10 I -t 350 3't2 9 Ì0 4 -L2 2I6 2L2 L3 10 'l -2 230 248 9
4-5 38ô 36{ 12 9 6 3 4I4 42't L3 10 1 0 154 139 13 t0 4 -11 20I 209 t3 lt 0 -r5 s06 453 12
4 -3 443 45111 9 6 4 294 295 9 I0 I I 478 498 11 10 4 -10 559 566 12 lt 0 -13 438 4t8 12
4-2 351 357 9 9 6 5 321 30?10 10 1 3 535 548 10 t0 { -9 l8{ 203 L4 rt 0 -9 554 508 13
4 -1 888 915 8 9 6 1 24L 2467L 10 1 5 331 385 10 104-1 2r9 t83 11 11 0 5 489 412 12
40 280 293 9 9 6 I 32{ 307 10 t0 I 6 139 131 15 10 4 -6 1't 6 1169110-3 415 416 1{
42 218 2L9 9 9 6 9 438 41115 10 1 1 162 779 10 10 4 -5 295 303 I 11 0 -1 485 464 12
43 860 894 9 9 7 -14 388 409 t0 10 1 I 13 9 91 18 I0 4 -4 334 335 I0 tt 0 1 623 596 10
41 315 313 9 9 7 -13 20L 29A 9 10 I 11 601 564 12 10 4 -3 121 101 16 11 0 s ?00 730 t1
15 326 307 11 9 't -).2 2r2 239 Lt 10 1 13 358 331 10 10 4 -2 42I 44A12 11 0 f 340 345 10
47 38t 378 10 9 ? -10 21A 213 A tO 2 -20 565 530 13 10 { I 314 3{6 l0 11 1 -16 412 {34 13
48 297 286 9 I ? -9 455 495 11 l0 2 -18 2t4 186 18 10 4 0 574 582 r0 11 I -t2 494 485 15
49 370 355 tl 9 I -8 301 322 9 10 2 -16 5'12 535 15 t0 4 I r41 114 13 1Ì r -10 263 245 11
4 10 169 153 t5 9 1 -'t 255 2A2 9 r0 2 -I4 412 402 t5 10 4 3 291 3169111-8 323 28? 10
4 13 J51 341 12 9 1 -6 158 185 12 10 2 -1.3 143 L23 2L 10 4 4 405 431 12 11 I -1 116 155 14
5 -19 258 250 13 9 '7 -5 217 300 g r0 2 -t2 402 3E8 II 10 4 5 20r 214 11 Il I -6 403 396 10
s -18 390 387 12 9 1 -4 323 341 I0 10 2 -11 146 13t 19 l0 4 6 1r6 l8? t4 11 1 -s 183 173 13
5 -15 250 264 )-t 9 ? -3 343 390 9 t0 196 -752 r0 10 4 I 222 12 11 1 243 249 l0
2 -10 224 -4
5 -1{ 491 51113 9 1 0 230 226 9 t0 2 -8 159 { ls1'r 10 4 9 158 t52 16 11 I -2 601 602 10
5 -13 210 270t0 9 1 | 256 211 9 r0 2 --l 2t5 229 tt 10 4 10 241 26610 11 1 2 62I 631 t0
14 {63 459 11 11 3 -2 541 554 11 t2 I -6 178 151 t6
l6 296 296 9 \L 3 -I 231 253 rO 12 1 -5 432 434 r0
1? 134 106 17 11 3 0 135 142 15 t2 1 -3 231 231 11
18 556 533 12 11 3 2 355 364 I t2 I -L 592 555 1t
2 -t5 460 425 !2 11 3 3 197 203 tÌ
2 -t3 429 398 72 11 3 4 261 21\ a
2 -t1 251 250 13 1t 4 -tl 321 299 7I
2 -9 srs 497 13 11 4 -10 355 351 l0
2 -g t21 r32 2t 11 4 -9 585 5't9 12
2 -5 615 585 10 1t 4 -6 21s I95 12
2 -4 299 313 t0 11 4 -5 602 602 II
2-3 293 311 8 11 4 -4 221 244 tI
2-2 L62 163 t4 11 4 -3 250 26't I
2-L 384 384 12 11 4 -1 326 343 11
20 1s0 13? t4 1r 4 0 204 226 t\
71 530 521 10 11 4 I 350 3?1 I
22 180 190 12 11 5 -8 484 439 12
25 561 601 11 11 5 -1 215 2A9 t0
21 223 229 I0 tl 5 -6 414 410 t2
3 -13 262 242 13 11 5 -4 153 129 15
3 -t2 636 595 13 l1 5 -3 265 266 9
3 -10 26'Ì 233 tt 11 5 -2 423 430 12
3 -9 194 155 14 11 5 0 130 r15 t6
3 -8 531 5I3 ì3 t2 0 -8 382 359 10
3-1 240 241 tI 12 0 -4 617 601 12
3 -6 486 4'lt L2 t2 0 -2 232 201 12
3{ 225 222 tO 12 1 -7 481 459 14
Table A4: Observed And Calculated Structure Factors For The [CyclsPAu(6p2'TU)] Complex.

t0lFlo vs I0lFlc page I

h k I Fo FcslgF h k I Eo EcslgF h k I Fo Ec51gF h k I Fo Fc slgF h k I Fo Fc algF

002 32L8 3212 I o222 236 235 28 05 12 s61 589 13 083 1958 198 11 0 10 t52 29'l 1A'
004 3 415 3505 9 031 1415 140t 1 05 13 r 013 1010 t? 084 31'I 31 11 0 IO 83 204 65.
006 2r81 2248 t0 032 652 643 t0 05 14 315 358 15 085 rt42 111 13 0 10 224 324 2A
008 8?0 832 t3 033 111 8 1091 9 05 15 568 560 14 086 6A'l ?0 15 0 1t Ì 62 8? 5lr
0 0 10 2A6 29't 15 034 606 5f 5 72 05 16 189 23\ 29 081 520 5Ì 1l 0 11 2 439 452 12
0 0 ¡.2 136 40 35. 035 820 422 1t 05 t1 322 333 20 0E8 281 31 1l 0 t1 3 3 03 331 16
0 0 t4 4r4 446 15 036 1353 t344 1t 05 18 114 104 65r 089 254 22 t9 0 11 4 192 112 16
0 0 16 465 462 t4 031 t225 t233 11 05 19 86 l3r 78r 0 I 10 2â2 2A l8 0 1t 5 494 s08 11
0 0 r8 401 491 16 038 1690 1654 t2 05 200 3 11t 0 8 Ì1 r32 l1¡ 0 tt 6 424 020 18
0 0 20 466 451 16 039 960 103 6 14 05 2t 1{6 2t 76' 0 8 12 r39 10 35¡ 0 11 1 593 638 15
0022 21'l 32ø 2'l 0 3 10 721 1 t2 48 t4 06 0 1219 1230 l0 0 I 13 224 26 24 0 11 I 853 813 t8
011 l3 6 129 6 0 3 11 1002 1023 L6 06 1 1990 2045 t0 0 I 11 91 93 55. 0 11 9 582 636 13
012 1009 991 7 0 3 12 970 991 16 06 2 2J1 235 t2 0 E 15 280 214 20 0 1t 10 564 575 13
013 494 491 10 0313 682 682 14 06 3 2071 2030 10 0 t 16 r26 I3 9 ?5 * 0 t1 l1 441 508 t3
014 23 67 2301 9 0 3 14 662 626 15 06 4 626 599 13 0 I r? 269 362 0 11 \2 486 4?3 13
015 642 596 t2 0315 50 9 499 13 06 5 1468 1151 11 0 I 18 91 t26 0 11 13 39t 393 15
0t6 225t tO 0 3 16 225 23 06 60 44 58i 0 I 19 318 31I 2t 0 11 t4 4t4 414 15
011 911 934 t2 031? 342 32 18 06 I 989 919 13 0 E 20 115 90 f 5 r 0 I1 15 t52 114 3fr
018 L43 6 14s6 12 0 3 t8 15 11 f8¡ 06 I 165 L52 24 091 682 613 15 0 11 Ì6 318 290 t9
019 215 215 t9 0 3 t9 0 15 19. 06 9 560 525 14 092 191 2t'l 19 0 11 1f 145 46 38r
0 1 10 t296 13Ll 14 o320 0 19. 06 t0 82 106 67r 093 636 656 16 0 11 1.8 185 23t 324
0 I 1l 199 725 23 0321 138 3 80¡ o6 11 0 41 10. 094 4 8l 4'I 2 11 0 11 t9 20 15'
o1t2 to22 989 16 040 114 ? 121 I o6 !2 35 1 15 71i 095 1291 t310 13 0 t2 0 110 6 1114 r5
0 1 13 93 192 14* 041 !121 1698 I 06 L3 261 32r 22 096 339 362 t4 0 t2 I 193 184 11
0 1 14 136 12t 14 042 r624 r59't I 06 1{ 102 111 6lr 091 966 t 002 t5 0 t2 2 1195 tt4l t5
0 I 15 113 2I8 11' 043 1333 135 6 9 06 15 3 66 407 17 098 218 229 0 I2 3 660 590 t 4
0 t 16 {81 410 14 044 t2't5 t23 ø 10 06 16 0 61 74r 099 819 853 1l 0 t2 4 879 835 t 6
0 1 1? 0 158 l7¡ 045 t5l8 1498 10 06 11 2't I 336 22 0 9 10 331 315 15 0 l2 5 163 730 18
0 I 18 199 201 33 046 t 068 1028 1l t8 0 44 11r 0 9 1t 603 623 15 0 t2 6 614 651 t4
0 I t9 0 82 19' 04't 923 883 13 06 t9 235 249 26 o912 323 332 1l 0 I2 1 5ll 592 13
0 I 20 199 61 33 048 66'l 6't'l I5 06 20 106 39 63' 0 9 13 542 58 4 13 0 t2 I 204 t40 26
0 r 2l 132 12 81r 049 246 242 t'l 06 27 26 204 80. 0 9 14 211 228 26 0 I2 9 91 f 5 't2À
0t22 a1 t2 82. 0 4 10 125 42 65r 0l r 1001 958 11 0 9 15 3 88 396 16 0 I2 10 tt1 f9 1LA
o20 3450 3449 I 0 4 11 6l 118 69. 0? 2 805 't't 0 12 0 9 16 238 L62 23 0 T2 t1 r2) t45 l2a
021 381 368 9 0 4 t2 201 22'l 24 07 3 6A1 740 13 0 9 1? 234 2tr 24 0 l2 t2 95 12a
022 2255 2229 I 0 4 13 180 t59 30 07 4 553 5't3 11 0 9 t8 0 90 t5r 0 T2 13 1Ì6 23a 13^
023 168 134 t4 0 4 14 494 511 07 5 1288 130t 12 0 9 19 110 81 58r 0 72 t4 171 t69 32^
024 2810 2925 9 0415 J94 311 15 0? 6 356
-t 318 12 0 9 20 1{3 80 0 I2 15 280 210 20
211
293 11 0 4 16 325 329 18 0? 1651 1633 t3 0 10 0 1545 1535 13 0 t2 16 2-t 1 230 2r
026 1549 1498 10 0411 21r 23'l 2A 07 I 94 85 48i 0 t0 1 2L39 2L59 t2 0 t2 t? L94 224 30
404 364 9 0 4 1E 11? 213 80. 0? 9 1371 1357 14 0 10 2 1336 1341 13 0 12 18 17 4 2tL 33.
o28 120 653 14 0 4 19 0 166 1At 0? 10 102 191 52r 0 10 3 t38'' 1398 13 0 13 I r1l 30 11.
029 0 89 62t o420 0 205 80r 0? tl 1119 1116 16 0 10 4 101{ 961 14 0 13 2 398 393 1s
0 2 10 93 68 o12t 0 13I 19' o'l t2 t24 12 '11' 0 10 5 l-025 1056 l5 0 13 3 0 54 12^
0 2 11 0 83 61' 051 98 127 26' 0? 13 9r4 862 71 0 10 6 4 9S 493 1l 0 l3 4 6t9 652 t5
0212 284 262 l8 92 19 51. 0l 14 0 61 12ù 0 10 1 132 124 18 0 13 5 1f 9 Ì31 30.
0 2 13 64 24 13. 053 866 861 Ì1 0? t5 520 {81 t2 0 10 I 242 224 2I 0 t3 6 199 178 l9
0 2t4 515 510 I2 054 196 800 I2 0l 15 138 128 40r 0 10 9 183 1? 4 2ø 0 13 1 344 390 17
0 2 15 0 54 76r 055 101? 1004 11 0l 17 346 325 18 0 l0 10 261 232 20 0 13 I 921 955 t9
02L6 454 461 14 056 841 8?4 0l 18 0 109 lf . 0 l0 11 0 64 69a 0 13 9 226 244 24
02t1 182 154 32. 051 165 0 1658 I2 07 19 145 129 16. 0 10 t2 0 96 13. 0 I3 10 83 6 894 19
0 2 18 443 452 15 058 655 661 11 o'l 20 1r9 25 32. 0 l0 13 196 260 2a 0 13 11 161 185 33i
0 2 t9 132 r28 4 Sr 0s9 r553 r635 13 08 0 431 4t8 l0 0 r0 14 83 26 12. 0 13 t2 683 110 t5
o220 311 368 23 0 5 10 1006 992 15 08 1 1955 1952 lt 0 10 15 321 33 8 17 0 13 13 10 l4f 64.
0221 0 98 80i 0 5 11 1525 1485 14 08 2 696 6ø6 14 0 10 16 133 145 16r 0 13 14 478 494 r4
0 t3 ls 0 t2 14. 0 17 6 548 566 t5 l0 -2 4346 4266 I r 2-22 281 224 30 1 3 -11 186 192 16
0 13 16 214 251 2I 0 17 1 105 228 83i l0 2 162t L622 s r 2-21 2I8 44 35 1 3 -10 945 986 13
0 13 17 43 't 6* 0 17 I 414 4 93 16 10 { 5?6 587 9 1 2-20 323 114 25 1 3 -9 962 931 t2
0 14 0 908 862 18 0 17 9 244 200 26 1o 5 665 665 10 r 2 -19 160 10 85' I 3 -8 441 4s6 l1
0 14 1 322 333 18 0 17 10 381 3 6'l 19 10 I 332 312 10 r 2 -18 231 239 30 1 3-1 453 463 9
0 14 2 952 920 l8 01711 245 220 28 10 IO 2r2 261 L8 | 2-11 0 34 80* I 3 -6 243 289 I
0 1{ 3 r42 135 75r 0 l't t2 212 35t 25 10 L2 102 104 L1 | 2-t6 181 r86 34 r I 3 -5 256 304 'l
0 14 4 134 102 15 01713 118 149 19. l0 14 848 899 18 | 2-r5 221 155 21 1 3 -4 120 16 LI
0 14 5 !12 154 32' 0 18 0 s62 553 14 10 16 ?59 759 14 | 2 -i-4 0 56 75r 1 3-3 82 31 17r
0 14 5 801 142 20 0 18 1 1t2 659 1? 10 \a 615 626 t6 | 2-L3 126 13 12. I 3 -2 53 9 55 9 7
0 14 1 53 19 't 6a 0 18 2 481 161 16 10 20 46ô 430 16 I 2-12 533 502 13 1 3 -1 13 83 13 93 6
0 11 I 315 328 20 0 18 3 5 31- 491 15 t1 -22 205 t47 42r 1 2 -11 230 145 19 1 30 6r3 601 1
0 14 9 0 21 16. 0 18 4 330 338 22 11 -2t 2t6 90 3?r 1 2 -r0 900 83I 14 1 31 2860 283s 'l
0 1{ 10 102 82 114 0 t8 5 455 418 l7 l1 -20 344 222 23 1 2 -9 r 41 119 24^ 1 32 61r 519 9
0 14 1r t89 110 29 0 18 6 133 t66 70r 11 -19 160 106 84i 7 2 -6 L659 I 653 ì0 I 33 2008 1952 I
0 14 12 0 131 f5¡ 0 18 1 tl2 256 86r 11 -18 421 361 18 r2-1 45? 464 t0 I 34 1895 1822 I
0 14 13 0 t21 l6i 0 10 8 46 40 50r 11 -7't t'12 t1l 39. | 2 -6 2r36 220 0 8 1 1558 1509 9
0 14 14 66 263 ?8r 0 18 9 0 L2't 84. 1I -16 64? 609 14 1 2 -5 1292 1320 1 I 36 L?84 lt84 10
0 14 15 0 ø2 15. 0 18 10 0 32 82r tÌ -15 113 131 ??r | 2 -4 2036 2085 6 l 31 15 65 r529 11
0 14 16 2Is 255 28 0 18 11 lfl 59 31* 11 -14 8lf 7f5 19 r2-3 I611 1694 6 I 38 14 4l 1428 11
0 15 1 116 113 3t¡ 0 t8 12 62 ?1 5?r t1 -13 163 146 32* r2-2 r634 I52l 5 1 39 I2S9 t242 13
0 15 2 355 352 18 0 19 I 0 115 85r 11 -12 8f9 8?5 t7 r21 402 {04 6 I 3 l0 1030 1032 14
0 15 3 126 133 141 0 t9 2 0 93 83r 11 -tt 205 Lsl 22 120 2012 2048 6 1 I 11 918 891 15
0 15 4 396 366 15 0 19 3 245 254 31 11 -10 rl3t 1099 13 121 3A1 319 1 I 312 446 415 t2
0 15 5 16 86 53. 0 19 4 19Ì 220 39. 11 -9 962 643 t3 L22 I 422 t383 6 I 3 Ì3 629 596 15
0 l5 6 ?50 146 I6 0 19 5 346 313 22 11 -8 766 791 13 123 4 05 311 8 I 3 14 I31 55 11.
0 15 1 85 46 16^ 0 L9 6 266 222 21 I1 -7 468 506 10 t24 t262 r283 I I 3 15 25r 224 2\
0 15 I 193 a22 15 0 19 1 292 316 26 1Ì -5 ?59 718 10 t25 190 221 13 I 3 16 0 14 f 5.
0 15 9 138 83 '19, 0 19 I 243 240 11 -5 314 213 I t26 562 535 t2 I 311 61 111 l6 r
0 15 10 I60 130 l6 0 19 9 l.3 t 20a s5i 11 -4 343 369 I I21 820 83I t2 1 3 l8 t25 123 64.
0 15 11 769 131 36r 0 19 10 109 144 ?0r 11 -3 431 436 7 128 f52 694 13 1 3 19 0 49 81r
0 15 12 509 62t 14 0 20 0 263 205 29 1I -2 348 355 6 r29 0 83 59. I 320 131 9l 81.
0 15 13 167 8? 34' o20 I 586 618 t5 11 -1 6?1 665 4 1 2 t0 5t6 T2 1 32t 136 L26 gtr
0 t5 14 322 395 20 0202 260 242 30 lt 0 1845 1?68 5 I2ll 316 298 t4 I 4 -21 I94 103 3lr
0 15 15 164 35r 0 20 3 501 525 18 11 1 506 s83 5 1212 839 s3 5 1? 1 420 165 222 45r
0 16 0 -790
730 15 0204 181 712 43. 1l 2 954 92ø 6 1 2 t3 284 261 18 1 4 -19 0 l5 83r
0 16 1 291 2 4'l 2t 0205 36't 344 2t 11 3 149 154 10 L214 191 1A't 18 1 4 -18 200 149 33
0 16 2 6't a 631 16 o206 t2'l 125 66r 11 4 1346 1356 l 1 2 15 299 341 19 T 4 -11 0 138 8r¡
0 16 3 265 28 020 1 142 222 8-) ¡ 11 5 gf4 870 9 1 2 t6 640 638 16 l 4 16 122 19 4 17.
0 16 4 550 542 13 0 20 8 0 56 86r t1 6 r8r5 1821 9 I2]^1 193 245 32 I 4 -15 0 12 11.
0 16 5 341 315 19 o21 1 89 29 61' 11 I 413 183 9 I 2 l8 510 492 14 1 4 -14 0 33 ?3i
0 16 6 345 334 19 021 2 0 t-l 90. 1l I 142 813 13 r219 221 194 2A 1 4 -13 4r2 406 14
0 16 1 345 311 19 02t3 99 112 89. tl 9 326 254 Lt 1220 342 345 20 I 4 -12 424 398 12
0 16 8 155 116 18. o2t4 0 80r 11 10 1tl6 1142 13 t221 53 l 81r I 4 -1t 510 508 t2
0 t6 9 108 r82 6fr 021 5 304 240 25 11 11 166 r59 25 I 3-22 118 6 88. Ì 4 -10 131 149 74
0 16 10 t4f 9 42r I O -22 311 294 29 11 12 101 l3t 1l 132I Il0 16 88. 1 4 -9 1050 l0f3 l2
0 16 11 t0t f4 I 0 20 324 296 26 1t t3 303 310 ll I320 0 14 85. I 48 921 926 rO
0 16 12 22 83 78r r 0 -18 241 255 30 lÌ 14 319 382 15 I I -r9 340 i0 22 I c -1 I2'r 5 t256 I
0 16 13 95 I 0 -16 t49 119 19* 1t 15 r61 156 31. I 3 -r8 332 29 2L I 4 -6 1Ì00 1134 I
0 16 14 103 166 53r I 0 -14 f1 58' 11 t6 161 100 l4' I 3 ll 460 15 1 45 115 6 1209 1
0 1-t 1 104 31 l9* 1 0 -12 606 514 15 11 tl 98 ')4 5l' I I -16 531 53 13 l 44 111 4 72IO 1
0 1? 2 281 334 24 I 0 t0 708 't34 I6 tl 18 0 109 7lr r 3 -15 5?5 54 14 t 43 t 411 14tl l
0 rl 3 46 49 79. I 0 -8 2300 2311 11 1t 19 141 3? ll. I I -11 8ì9 849 ì9 I 4 -2 1059 1053 I
0 1l 4 500 438
15 10-6 2t62 2t2A 9 1l 20 151 119 80. I I -13 665 642 1{ 1 4 -1 1566 1580 l
0 1l 5 156 81r
101 I 0 -4 2A2A 2801 I 11 2). 0 19 81. 1 I -Ì2 121 f2s t8 Ì 40 161 1 1616 ]
141 1314 1300 't 1 5 13 431 453 13 1.7 -18 0 134 80. l. I -4 521 509 1I t 9 10 440 423 13
142 122 688 9 I 5 14 2la 178 24 T] -1? 494 48ì 14 ì 8 -3 I9 46 1913 10 I 9 11 624 595 l5
143 113 0 1088 9 1 5 Ì5 t22 225 l5 ¡ 1l -16 91 108 l3r 182 620 590 l4 1 9t2 25r 254 2l
144 151 f25 11 1 5 16 0 50 l6r 1l -15 601 681 13 181 2 013 1979 t0 I 9 t3 492 483 l3
t4 5 146 t46 1l 5 1l 167 21 34r -r4 41
133 59. E 1 40 119 13 9 14 151 201 11.
14 6 t6l 121 18 5 18 0 58 16r -13 931
913 16 s 1085 tt23 11 9 15 161 140 35.
14 1 4A2 496 12 I9 fl 11 1ø' -t2 222
196 23 I I096 1040 11 9 16 0 89 11r
14 I 370 3ll tr 5 20 149 A1 14. -11 930 842 \4 I 1022 1034 T2 9 I7 I30 58 l5r
1{ 9 310 34t 12 5 2L 0 99 f9¡ -10 338 368 l1 I 608 637 11 9 I8 92 52 11r
14 10 ?05 ?t4 t6 6 -2t 114 182 82r -9 1006 1080 10 I 65 151 50. 9 t9 0 13 0 19.
14 11 51? 495 12 6 -20 56 19 81. -8 335 360 9 I r99 238 19 t0 19 180 194 32r
t4 t2 114 795 l8 6 -19 21{ 183 30 -1 653 658 13 0 22â 2I9 18 10 -18 33 30 11.
l4 13 686 679 14 6 -18 111 21 ?8* -6 316 386 9 E 28t 21r 16 10 -l? 220 160 2?
14 14 481 490 t3 6 -17 t21 t4't 48' -5 203 203 11 I 314 305 l6 10 -16 42 64 14.
11 15 123 416 14 6 -16 o 21 63' -4 {30 r25 1:. I 0 5f 1Lr 10 -t5 0 64 16.
I4 16 1't 9 380 t6 6 -15 t44 70 3lr -3 0 103 51i I 11 754 111 19 10 -14 0 41 52r
14 1? 3?5 384 17 6 -14 69 93 50* 428 384 10 I I2 0 152 l3r 10 -13 109 135 63i
1{ 18 216 244 22 6 -13 432 398 13 -1 1202 1185 10 8 l3 549 564 l4 10 -1.2 259 215 16
11 19 t24 1?6 51i 6 -12 241 190 18 0 551 550 13 8 14 0 58 l5r 10 -11 236 275 t9
14 20 162 162 3't * 6 -11 8L? ?73 1{ 1 12T3 1202 l0 t5 611 650 13 LO -I0 229 243 20
14 2L 175 136 35i 6 -10 185 146 19 2 524 514 10 I t6 206 I29 2ø t0 -9 014 E85 16
15 -27 t1? 140 'r 1i 6 -9 1079 1080 11 3 r548 1613 I 0 I 1l 553 54r 13 10 -8 684 615 tl
15 -20 0 Ì0? 84¡ 6 -8 t32 130 t 8 4 4t2 382 10 I 18 202 I24 29 10 -7 t0?8 10?9 14
15 -19 420 386 l7 6 -1 1491 1532 9 5 18 4l I84f Ì1 I 19 369 39t l6 l0 -6 980 984 14
15 -18 233 266 29 6 -6 536 5t2 12 6 210 15? 1l I 20 o 11 l8i 10 -5 1324 1329 l3
15 554 539 14 6 -5 173 5 L152 9 1 1112 1533 l3 9 -20 0 102 10 -4 Ì003 992 14
15 -16 265 325 23 6 -4 268 302 9 I 0 32 65ù 9 -19 t87 215 32. 10 -3 rf46 L190 t2
15 -15 816 923 L9 6 -3 1344 1310 9 9 1482 1490 14 9 -18 84 113 54 r 10 -2 130s 1312 13
-14 501 524 t2 5 651 62t 10 381 367 11 9 -11 2'14 340 22 10 -1 1885 t892 12
-13 1083 1063 15 6 1685 168 8 9 11 842 a22 16 9 -16 116 l1 I 14r 10 0 999 968 1l
15 -r2 624 645 14 6 0 300 265 9 12 0 42 10r 9 -15 {30 3f9 I4 10 1 1l?5 1195 13
t2t1 1258 13 6 I 1285 t280 9 13 492 12r t2 9 -14 56 153 62. t0 2 450 460 10
-10 506 512 L2 6 2 89 46 49r 14 163 t55 33r 9 -13 f09 718 13 10 3 't19 ?70 16
15 -9 8l I 890 L2 6 3 1019 1043 10 1s 212 2r1 25 9 -12 262 213 15 l0 4 99 181 65r
15 -8 535 540 13 6 4 161 100 18 16 0 21 15t 9 - 1.1 161 41L l0 10 5 244 216 6
15 -1 470 419 8 6 5 55? s55 10 17 6'l 16 ?1r 9 -10 39 70 10 6 193 193 3
15 -6 139 139 14 6 6 491 468 L2 18 93 25 65. 9 -9 ?5? ?95 15 10 't 110 24
15 161 I19 L2 6 1 84 148 62r 19 0 130 79¡ 9 -8 192 rs6 2l t0 I 138 r22 1¡
15 -4 82 55 23* 6 I 0 33 62r 20 161 100 37r 9 -1 849 831 1{ 10 9 80 96 2r
15 -3 325 3{7 I 6 9 66L 635 t2 -20 15 69 10r 9 -6 o 16 63i l0 t0 2t1 221 4
15 2A2 263 I 5 10 13t 115 674 -19 18 2t5 32' 9 -5 20a 214 t0 10 1t 5r2 541 2
I5 -1 213 266 I 6 11 184 182 t'l -18 40 16. 9 -4 t59 t23 20 t0 12 117 r06 2*
15 0 510 562 11 6 l2 86 59 ?0i -tl 101 ?6i 9 -3 280 260 13 10 13 488 4 91 3
1 9ø2 98? I 6 13 865 069 I8 -15 51 14. 9 3 99 396 10 ro 14 292 l1l 1
2 1039 7021 9 6 t1 138 21-5 14r -15 5 12' 9 -1 894 930 13 10 15 488 501 4
15 3 1146 71A2 9 6 t5 594 546 t3 -Ì4 15 1Ì 5 31. 9 0 515 486 11 t0 t6 303 309 I
15 4 1352 1312 1 0 6 t6 r82 r62 31r -Ì3 22 155 23 9 1 t238 1243 \2 10 1? 384 404 E

t5 5 2248 2242 lO 6 441 452 15 -t2 t 21 148 66r 9 2 f08 l1? 14 10 18 295 215 I
15 6 980 100s t2 6 18 0 54 -11 431 459 l0 9 l 1364 t41? I2 10 t9 214 28f 3
1.5 1 2030 2038 11 6 19 266 266 24 -10 3 63 400 10 9 4 53t 626 15 11. 19 0 89 9r
l5 I 904 913 14 6 20 46 2t '11 * -9 841 811 t3 9 5 r25t t269 13 11 -18 228 250 I
15 9 1558 1s l3 13 6 2T 168 r92 38r -0 523 502 t2 9 6 330 l0? Ì3 1Ì -t? 149 185 3.
15 10 619 693 12 1 -21 0 135 82* -1 1517 1503 11 9 1 97Ì 1011 16 1t -16 365 299 g
15 l1 L7L2 1101 15 1 -20 0 39 81i -6 311 304 10 9 6 240 289 20 t\ -rs 261 313 0
15 I2 289 33t t8 1 -1 357 335 19 1902 I 905 11 9 9 622 659 14 rr -14 330 343 4
1 1t -I3 349 {1? t4 l2 42r 458 t3 -10 608 562 t4 15 { 18 41-l 16 1l 9 250 242 E

1 11 -I2 446 445 12 72 t3 6 26 7r, t4 -9 0 36 16' 15 13 0 38 1l 10 429 392 1

1 11 398 4t8 14 T2 0 16 12' t4 -8 691 688 15 15 I4 186 1t8 33 r tl 11 0 149 5r
1 11 -10 494 466 L2 t2 131 183 11 -l 0 111 r3r 15 0 59 t8r 1f 12 31 199 3r
I 11 -9 314 401 14 72 326 345 18 74 -6 125 't55 t4 16 -14 0 4? 84* lf t3 4t 142 0¡
1 11 -8 587 620 12 290 320 20 14 -5 131 5 6 71. 16 -t3 112 t0? 83 r 18 -t2 96 59 2t
1 11 -1 133 153 37. l2 11 323 35 199 74 -4 ?39 ?13 11 16 -t2 2L1 206 32 l8 -11 155 19? 5r
I 11 -6 315 345 l6 L2 l2 402 385 16 14 -3 115 164 ?3r t6 -11 2t4 231 1S -10 1s1 90
1 11 81 10 61. T2 13 385 392 16 14 -2 715 805 t9 16 -t 0 212 211 28 18 -9 281 216 4
1 11 -1 87 10 65. t2 14 386 391 l1 14 -1 0 68 l3r l6 -9 269 302 25 t8 I 225 256 I
t tl -3 r06 r01 10. r2 15 24'l 236 24 t4 0 't28 't22 11 16 -8 {51 443 16 18 -l 456 446 6
r 11 433 {3t t1 T2 16 320 352 20 14 1 154 ?0 34r 16 315 305 27 18 -6 359 394 0
t lÌ -1 320 32r 14 T2 1t 182 1't 9 33i 11 2 62'l 628 15 T6 -5 690 698 16 18 -5 515 414
1 11 0 628 597 13 t2 l8 t98 212 32 t4 3 0 30 ?5. :.6 -5 248 251 25 18 4 469 481 6
1 lt L 604 613 13 13 - 1'' 125 t9 38. 14 4 583 541 l3 16 -4 661 663 l4 18 3 632 598 5
1 11 2 1I4 129 11 13 -15 363 418 Ì5 14 5 0 95 16. -3 211 2t9 28 18 -2 444 451 1
1 11 3 576 588 1{ li -15 50 'I 5l ì4 6 l9 l5 ?4. 16 164 113 15 lE I 599 516 4
I 11 4 199 192 71 13 -14 582 5rI t3 14 1 131 70 40. T6 -t 352 340 1l l8 0 160 348 0
1 11 5 82r 8l-t 1l l3 -13 0 t62 I9r 14 I 2\9 24! 21 16 0 513 516 13 Ì8 I 456 418 1
1 11 6 83I 846 1l l3 -12 613 606 1{ 14 9 0 98 78. 16 1 265 286 24 18 2 95 179
1 11 'l 790 801 18 13 -11 100 19{ 78. 14 10 3r 9 363 2l 286 304 22 18 3 316 352 9
1 tt I 530 485 13 13 -10 600 610 14 14 11 111 142 )1. I6 3 302 3r9 2t 10 4 r41 21 5r
I tt 9 3 4'l 368 r6 13 -9 203 155 21 \4 12 445 4?5 15 16 4 248 201 25 18 5 110 t53 5¡
1 11 10 706 6?5 14 13 -8 {05 420 14 t3 ?8 105 -l6r 16 5 268 245 24 r8 6 0 89
1 11 1t 354 3 86 1l 13 -7 111 1! 12r r4 14 350 389 19 t6 6 116 90 19^ 18 l 0 56
r lt \2 3 6'l 375 16 13 -6 104 66 61r 14 t5 0 16 18. 16 1 0 t8 81. t8 6 183 148 9r
1 lt 13 t3 9 12 39r 13 -5 120 58 71. r 14 16 2't 0 28r 22 16 I 198 218 32 18 9 0 1.9 86.
I 11 L4 33 4 3{5 19 13 -4 t21 84 71* 15 -16 381 381 19 16 9 r54 84 18 10 0 131 81'
1 lt 15 0 43 l8* 13 -3 0 62 70r 15 -15 185 ?3 3?r 16 t0 210 259 28 18 11 68 132 84.
I 11 16 135 1-r3 ? 8* 13 -2 282 263 18 15 -14 41L 498 1l 16 ÌL 0 lt 9 83. 18 12 1s3 226 84*
I 11 17 0 't4 11. 13 -1 120 111 71r 15 -13 0 23 84* 16 L2 249 305 28 19 -10 0 183 85 ¡
1 11 18 ø2 19 l7i 130 142 ?55 13 L5 -L2 542 s62 15 16 13 168 144 38. 19 -9 88 203 83i
t12 -18 136 89 83* 13 1 t32 109 71r 15 -11 t29 32 19r 16 1{ 328 324 19 19 -8 0 157 46.
t72 -1? 202 t96 32 13 2 1001 1055 i.1 15 -10 523 566 14 17 -t3 0 138 85. 19 -l 157 155 84r
1 12 -16 Ì34 18 68i 13 3 166 108 30i 15 -9 130 33 {5i 11 -L2 2AO 295 26 19 -6 155 ls 0 44.
tt2 -15 102 t22 6S* 134 921 9I1 18 15 -8 411 425 t5 r? 11 0 90 82. 19 -5 0 63 83 ^
t12 -14 147 88 35* 13 5 218 280 20 15 -? 121 115 l6i 17 -10 359 392 20 t9 -4 r32 10 82.
t12 -13 0 46 l5i 13 6 t261 1253 I6 15 -6 0 113 l4r Tf -9 0 8{ 79r 19 -3 144 9A 05.
t12 32A 258 t'l 13 1 186 t89 31 15 -5 0 19 f 4r 1l -8 382 394 18 t9 -2 102 19 84.
tt2 -11 105 I-t 4 13i 13 I r062 1042 1l t5 -4 51 4'l 12" 1? -1 0 1l 6f, t9 -t 291 305 24
r72 -10 466 444 13 13 9 0 110 f5r ts -3 0 18 14. 17 -6 216 236 l0 19 0 143 161 85.
t12 -9 412 476 13 13 10 738 750 15 15 -2 322 281 t8 l7 0 94 8l' t9 1 3lô 187 2\
t12 -8 666 6?8 r4 13 11 0 19 16ù 1't 35 13. l? -4 062 81. 19 2 312 265 23
r 12 514 613 13 13 t2 538 545 13 15 0 578 602 14 tl -3 0 5l 18. 19 3 {30 3 85 19
t12 -6 840 860 18 t3 13 0 89 11' Ls2 91 35. 1f -2 306 219 21 19 4 282 232
I 1.2 -5 594 583 15 t3 t4 259 204 23 t5 2 819 748 19 1l -t 191 154 32. 19 5 180 355 20
112 -4 1054 120 16 13 15 139 65r 15 3 0 98 16' 1l 0 513 512 13 19 6 221 253 33
r12 -3 533 5t6 12 13 16 t22 t02 65. 1s 4 106r 105? 1E 1l 1 t94 181 33. t9 1 302 212 24
IT2 932 919 15 13 1? 0 89 75. 15 5 146 21 1l 2 626 600 15 19 I 0 155 86r
I 12 -1 668 65E 13 14 -16 83 71. 15 6 1032 1008 18 1l 3 154 231 63 i 19 9 203 254 38.
I t2 0 651 638 r3 14 -15 0 99 82' 15 1 290 24e 22 1l 545 650 15 19 10 0 118 86.
rt2 I 645 645 13 14 -14 0 108 82* 15 I I63 I93 2I L1 5 398 348 18 20 -8 0 154 g?.
I12 2 601 604 l4 14 -13 133 96 81i 15 9 199 135 31 17 6 562 536 t4 20 -1 316 431 21
Ì t2 3 669 630 13 t4 -72 320 2't 1 2r 15 10 58 6 644 1? r-l 1 38r 321 18 20 -6 84 141 87r
7t2 4 341 306 15 14 -11 85 61 78. 15 11 1.8 8 l0? 33. 1f 8 471 433 l6 20 s 514 533 16
t 20 -4 2t2 t82 34 1 -12 404 401 l3 2-l 1448 1418 6 11 559 61 9 t-7 5 -20 124 r64 83¡
r20 3 5rt 568 17 1 -11 322 380 14 20 t24a 1250 6 l2 269 309 l8 5 19 402 434 tl
t20 104 170 8l* 1 -10 355 364 t2 2T 406 3 85 9 13 TT2 59 51. 5 -18 252 258 26
120 -1 500 541 17 1 -9 321 330 11 718 116 1 I4 141 ì63 14. 5 -11 565 606
120 0 156 20-r I8. I -8 213 204 11 23 135 111 13 15 83 23 lI. 5 -16 341 314 18
I ?O l 40? 424 ?1 1-l lot 24 ln l6 3t I ?A1 t8 5 -15 510 6)2 t4
r20 2 88 150 6f¡ 1 -6 185 801 9 25 446 436 I 17 66 Ì45 5l' 5 14 314 30 18
t20 3 r 03 211 9t¡ 1-5 301 29r f 25 \425 13 91 9 l8 5t 20 ?8. 5 -t3 638 61 t4
1 20 4 0 l6 B8r 1 -4 950 963 1 21 r21 161 22. 19 245 20 25 5 -12 185 t8 13
120 5 18{ L41 42. 13 t22l 1231 6 28 1211 1294 20 t2t 20 80. 5 -lt 413 42 1l
I 20 5 0 10 89¡ t-2 416 0 4064 I 29 4 01 313 2l 0 ll 81. 5 l0 323 31 t2
I 20 1 0 3 90¡ 1-1 254 254 6 2 t0 131 1 tl88 105 I 84. 5 9 138 4 23
L20 I 90 14 66' 10 t22l t2r9 6 2 lt 411 459 -20 08 83. 5 -8 118 2 22a
I 21 -5 0 32 A6. t1 286 243 6 2t2 t154 114l -19 04 81. 5 -l 158 34 9
1 21 -4 0 I 84r l2 3300 333 9 l 2t3 525 545 -18 0t 81. 5 -6 452 44 9
I 21 -3 0 99 88* 13 308 ? 2 74 139 '116 - t-, 0 tt 18. 55612 63 9
1 21 0 10 8l* 14 2292 2299 I 2 15 313 243 -16 215 1l 2f 54202 22 Ì0
2L -1 153 173 88i 1 5 10r 61 19r 16 619 615 13 -15 382 344 5 -l 1214 123 A
2\ 0 105 29 85* 1 -l 6 1338 1358 9 t1 205 225 2A -t4 324 343 5 -2 911 952
21 1 216 21r 29 I 553 568 12 18 391 364 16 -13 f07 68Ì 51 2191 2204
2T 2 0 26 88' I I 't08 't29 L2 19 108 65 54i -t2 691 ?18 50 r210 L222
2I 3 305 350 21 I 9 169 210 19 200 187 f9. -11 812 842 51 2929 2951
2T 4 0 41 ø1. I 10 691 689 15 2t0 35 66r -10 687 615 52 1553 1523
0 -22 0 112 91* r tt 294 3t2 14 -2t 2r9 203 34 -9 1081 t 066 53 3 091 3I3 0
0 -20 t 01 45 87i 1 12 69 30 66. -20 23L 2t1 3l -8 845 E91 54 1408 1430
0 -18 0 115 ?t* 1 13 94 154 51r -19 354 333 20 -7 9å2 1 021 55 26L2 25'tt IO
0 -16 249 2t3 26 L 14 220 226 22 -18 331 345 2l -6 929 939 56 914 970 L2
0 -1{ 494 4f5 14 1 15 0 48 69. -11 396 413 1l -5 1120 I 116 I 57 13?1 Ì363 11
0 -r2 8r7 819 17 t 16 376 376 l5 -16 {s6 489 11 -4 801 850 ô 58 444 456 9
0 16 31 15 81 12 I 17 0 107 r3i -t5 192 192 t3 -3 917 925 1 59 959 985 L4
0 -8 2233 2191 10 t 18 364 392 t8 -1{ 394 423 Ls -2 919 948 1 5 10 461 413 11
0 -6 201 1 2093 6 I 19 120 104 77. -13 531 555 l3 -1 159 11¿ I 5 11 313 351 15
0 -4 240'l 2436 'Ì I 20 320 304 20 -t2 215 263 t9 0 525 581 9 5 12 13 68.
0 2023 2045 6 7 2t 0 96 78¡ -11 660 6't 9 t2 I 400 395 8 5 13 144 44 33.
0 0 957 9-t8 6 2 -22 0 t22 Sâ. -10 179 108 20 20 20 43. 5 14 43 28 59i
0 2 1263 t245 6 2-21 0 785. -9 2A2 292 t2 3 115 194 12 5 ls 6f 31 1L.
0 I 952 93't 1 2 -20 to3 91 8{. -8 r92 113 14 4 521 494 t2 5 16 0 1t6 16"
0 6 5 8? 611 r0 2 -19 163 51 83r -l 353 3't6 6 s 1231 1 1?9 t0 5 rl 198 t14 29
0 I 1506 1517 10 2 -18 0 3? 83i -6 525 502 l0 6 991 911 11 5 18 145 159
0 l0 1367 13ß7 12 2 -11 122 54 50r -5 {53 114 t0 r 981 951 t2 5 19 245 2t'l 26
0 l2 L423 1449 r3 2 -16 265 252 24 -4 112 152 I I 1084 1 050 t2 520 130 65i
0 l4 112 8 rl21 15 2 -15 133 118 l4i -3 1503 L618 ? 9 1011 L 025 l3 6 -21 0 55 80r
16 143 738 14 2 -r4 526 514 L2 -2 lL45 1169 '' 10 1111 t 13 13 6 -20 t29 34 78.
0 18 452 421 L4 2 -t3 220 2r4 23 -1 1916 1956 7 11 705 ?1 17 6 -19 13 4 22 78r
0 20 2L1 2r1 29 2 -12 812 8't9 t5 0 Ls62 1056 7 12 540 62 14 6 -18 0 9
1 0 188 90* 2 -lt 348 320 tJ 1 2018 2012 1 13 603 63 14 6 -t1 r41 136 't 1.
1 -2I 0 't 2 90' 2 -10 1251 1203 12 2 1565 15?8 l L4 123 40 13 6 -16 2A 54 ?5.
1 -20 292 239 26 2 -9 ?88 791 13 3 1519 1152 I t5 {7{ {9 13 6 -15 450 422 1{
I 0 109 05. 2 -8 1737 1760 10 4 1128 1739 I l6 319 31 L8 6 -14 0 5I 1L.
1 -18 263 266 21 2 -'t 862 91r 10 5 1122 1419 9 11 244 24 23 6 -13 420 8\2 1?
1 -1? 153 106 {rr 2 -6 18't4 rE99 E 6 1598 1631 10 I E 215 1l 21 6 -r2 95 178 't 0.
t -16 416 120 t6 2 -5 819 089 I 1 tL11 11 11 11 t9 2r1 t4 2A 6 -11 921 I45 1{
I -15 105 L?8 ? E. 2 -4 2059 2!OL 1 E 618 609 14 20 t31 1t f 8. 6 -10 108 114 61.
1 -1{ 444 423 t4 2 -i L254 L232 5 9 1025 1011 13 2l l7 1 19. 6 -9 L245 L2't 2 11
1 -13 186 202 28 2 -2 t836 1801 5 10 r84 t90 2l -2t 208 24 33 6 -8 410 42'l 9
6 -1 t21 9 1298 t0 -, 7 1420 1404 13 -19 230 r99 28 -3 1096 t 08 t3 11 14 6l 65 ¡
6 -6 405 423 10 ? I 369 361 12 -18 0 65 80. 10 -2 5{3 552 12 11 15 l9l 197 3I
6 -5 118 7 t204 9 ? 9 718 6?4 1? -t1 296 214 23 lo -r 669 662 15 11 t6 190 t2f 32.
6 -4 433 390 9 7 10 398 372 13 -16 12 59 ?9. 10 0 209 2t2 l8 1Ì tl 126 2t2 52.
6 -3 t6t2 161? I 1 17 244 t35 2t -15 414 403 l6 10 I 208 111 18 lt t8 l0 r56 80¡
6 t16 184 13 1 72 0 t25 1r' -14 0 166'76r t0 2 7t2 140 34r 12 -18 0 31 08i
6 -1 845 I03 9 I t3 100 21 69* -13 33s 378 16 10 3 298 262 l4 t2 -r1 0 3 E1^
6 0 t85 14't t2 1 14 89 3't 60. -t2 0 00 66r 10 4 t0( 14 53. t2 -t6 0 L61 16.
6 1 0 52 49. 7 15 0 210 16. -11 386 386 t2 10 5 396 410 I2 12 -15 t lI ts6 3t.
6 2 381 388 9 l 16 141 41 37¡ -10 99 26 62* 10 6 165 162 21 t2 -L4 29f 283 t9
6 3 269
219 L0 1 11 265 29t 23 -9 2t4 192 19 10 I 54? 581 T2 12 -13 254 24t 2L
6 4 38?
322 10 ? 18 1r9 ?4 ?8* -g 162 L6I 24 10 0 30s 316 Ìl t2 -t2 430 440 l4
6 5 L241 1225 17 1 L9 202 211 32 -1 J2L 313 t3 t0 9 606 683 tl t2 -11 344 3J1 16
6 6 151 L14 22 1 20 14 13 11r -6 3?0 351 11 to to 414 411 l3 l2 -10 649 6t 6 r4
6 'l 1319 t369 L2 ø -20 r8 30 59r -5 817 806 13 10 11 810 814 19 12 -9 561 558 13
6 I 3't 2 355 12 8 -19 14 3 11* -1 384 42'l 10 10 12 5t5 530 11 \2 -S I60 151 l9
6 9 r236 1250 14 I -18 83 36 ?9* -3 t3lI 131 6 11 t0 13 631 656 13 \2 -1 449 424 I3
6 10 136 89 32. 8 -1? 191 102 32r -2 524 492 11 10 14 464 428 15 12 -6 959 920 L5
6 11 1163 tt91 15 8 -16 0 121 65. -t 1142 1l13 11 10 15 499 469 I4 725 4ø6 504 12
6 T2 161 178 30r I -t5 212 258 23 o 626 626 T4 1.0 1.6 359 155 19 t2 -4 879 a26 t6
5 1J 't
3'l ?11 18 I -74 2t5 r81 26 I 14 05 1357 11 10 17 131 296 82. t2 -3 665 616 13
6 14 251 290 22 I -13 554 532 13 2 4r2 439 10 10 ta 213 r92 26 12 -2 573 580 r4
5 570 547 1{ I -t2 329 305 15 3 1118 t245 l2 11 -19 0 L23 E?T \2 -l 5?3 625 t4
6 16 0 123 75. I -11 866 820 14 4 311 124 1I :.1 -18 122 tE? 68r 120 254 254 19
6 1? 356 342 t8 I -10 396 383 10 5 1091 1105 13 tL -r1 245 206 28 t2 I 282 221 ]^'I
6 t8 99 61 50' I -9 1286 1316 11 6 303 260 t4 11 -16 141 191 81. t22 15 45 68r
6 l9 236 22t 26 I -0 281 314 13 1 624 6{3 13 11 -15 0 198 t6. t23 134 174 35r
6 20 0 24 18' I -1 1131 1122 tl I 35 9 350 14 tt -14 256 253 20 t24 112 101 30r
1 -20 0 42 80r I -5 354 324 10 9 421 488 13 tr -13 185 221 26 L25 384 418 t5
1 281 341 23 I -5 1533 1537 11 r0 183 169 28 t_r -t2 21r 23). 20 t26 661 64ô 14
1 -18 741 81 r6* a -4 296 321 tt rt 252 254 11 -r1 0 112 69r 12 1 616 666 14
1 -17 413 435 16 I -3 1621 ls82 t0 t2 r32 165 14* Lr -10 228 222 128 5 90 600 t3
1 -16 6J 90 l6i s -2 6L8 625 L3 l3 tl8 29 45i 11 -9 192 16S 26 129 418 519 14
1 -15 5II 512 13 I -1 381 388 9 14 36 33 f6i 11 -8 0 1l 68 r t2 to 689 649 15
1 -t 4 0 92 12' I 0 ?9't 789 12 15 259 241 23 11 -l 159 145 21 12 ll 505 502 73
1 -13 514 5t6 t2 8 I 467 453 11 r6 128 55 78r 11 -6 38r 3?1 t3 !2 12 620 516 14
1 -t2 {30 4t4 t2 I 2 511 560 14 11 3a6 3't 5 t'l t1 -5 l?9 379 13 12 13 235 268 26
1 -11 358 361 13 I 3 519 465 11 18 69 63 ?8. t7 -4 '182 166 t2 14 450 428 t-5
1 -10 341 322 Ll I 4 103 145 5rr L9 269 259 23 11 -3 680 692 t2 12 15 0 161 78r
'l -9 262 232 t3 I 5 674 691 15 -19 0 39 84r 11 -2 958 993 15 t2 16 320 3ft 2t
'l -8 323 316 10 0 6 63 112 63* -1 I t15 85 84i t l -1 781 ?51 15 t2 t1 1?1 15? 3?*
1 -7 300 215 tO ¡ 7 864 860 t5 -1? 110 5? 58. 1t 0 993 l00s 1{ 13 -r? r44 61 3 9i
'l -6 139 r52 2r I I 151 151 29i -16 69 L29 191 11 r 136 ?83 16 1l -16 329 365 18
't -5 999 9?9 11 I 9 889 951 tl -t5 241 2r0 25 11 2 888 936 l5 l3 -15 0 58 -t8¡
1 -4 0 69 51¡ I LO 206 t82 24 -t1 249 252 2t 1l 3 985 989 15 t3 -14 313 319 L1
1 -3 1 491 t491 9 I 11 1026 10s6 r7 -t3 3?8 319 t3 lt 4 E13 844 16 t3 -13 r21 31 l5r
'l 928 921 10 ø t2 92 65 10' -t2 356 355 l3 11 5 692 103 I3 13 -12 2ø6 310 21
1 -t 1994 2006 9 8 t3 193 824 19 -11 69? 730 l7 l1 6 610 611 Ì4 13 -11 119 l0 75.
1 0 531 416 l3 8 14 126 176 45i -10 612 582 13 11 1 249 250 2l 13 -10 216 18L 26
1 1 24r8 2391 10 8 t5 614 6?9 16 -9 1038 1045 t4 Il I 104 146 1.4 13 -9 100 41 60.
1 2 109 590 11 8 16 38 r22'11. -8 889 889 15 11 9 182 210 30 t3 -8 0 80 f3l
1 3 t't 61 Ì829 t0 I 11 441 424 15 -1 t211 t243 14 lt t0 259 266 1l -l 96 92 ll.
1 4 111 111 21. 8 18 0 14-t 66. -6 918 909 15 11 11 122 160 12. 13 -6 240 296 22
? 5 1{ 8l 14 9?11 8 19 t51 206 81r -5 1120 ll06 I3 11 12 t3l 264 16. 13 -5 0 28 ll.
1 6 180 L6 9 -20 154 96 16. -4 196 194 1{ 11 13 196 205 l0 t3 -4 534 539 l3
13 -3 1l4 224 30¡ t5 -t4 328 3A8 22 11 218 t14 29 19 -9 140 23 8l' 0 4 Ì315 t32\ 8
13 -2 058 848 1f 15 13 111 12 8r* t2 410 391 18 19 I 0 31 82. 0 6 1359 lf64 9
t3 -1 2 60 2t0 20 15 -t2 338 34Ì 20 Ì3 0 t26 83. 19 -l ).06 rÌ5 l1r 0 I 176l lllt 10
t3 0 1340 t321 t5 15 -11 189 71 33r t4 296 309 23 19 -6 164 96 83. 0 r0 1710 113 4 11
13 I 230 210 23 15 -10 202 260 33 tl -t3 0 19 86. t9 -5 244 21 4 30 o t2 1228 t236 1l
13 2 118 0 118 9 l6 15 -9 0 1f0 80r ).1 -12 119 248 65. 19 -4 191 114 35i 0 14 154 116 ll
13 3 429 411 L4 t5 -8 0 lt 76r 17 -11 0 23 83. 19 -3 425 418 l8 0 16 333 366 15
13 4 1394 14 41 16 15 -7 ll3 21 32. 1-7 -10 214 234 32 t9 -2 268 241 21 0 t8 112 111
t3 96 233 15 -6 118 1f3 32¡ 1f -9 0 109 83. 19 -1 465 4s6 1? o200 2l f1r
13 6 890 900 18 15 -5 0 rO2 13. 1f -8 0 54 82r 19 0 3.79 r55 20 | -21 r29 49 I6r
13 1 50 32 l3i 15 -4 4t5 398 14 1? -? 156 165 81. 19 I 4{5 40s tð r200 2L3 90r
t3 8 708 136 15 15 -3 113 11 12. 1l -6 135 174 68r 19 2 2'13 268 21 1 -19 139 60 03r
l3 9 118 r42 49¡ 15 2 693 1r'l 15 1? -5 161 t49 39i 19 3 318 354 20 I 18 203 238 l6r
t3 10 449 388 l4 15 -l 12 t9 73r ll -4 412 430 16 19 4 309 281 r -11 0 a2 81.
13 11 235 251 26 15 0 994 1004 r8 1l -3 224 211 30 19 5 303 293 25 Ì -16 259 26r
13 t2 r46 99 78* 15 1 0 4514r 1l -2 661 666 L1 19 6 ?l r8l 88r I -15 Ì12 1t7 56.
-ì6
t3 l3 0 204 a2' 15 2 1109 tllS l8 ll -t 363 334 19 19 1 211 228 29 1 -14 0 l6r
t3 14 0 41 l8i 15 3 2t9 tql 21 17 0 641 632 t5 19 I t86 8l 1 -r3 0 59 ?3.
1l 15 150 t0l I9. 15 1 r10r 11ú2 10 17 1 119 291 21 t9r0¡08 90. r 12 109 149 7li
13 t6 t 65 69 31. 15 5 222 218 21 1l 2 640 608 14 20 -8 29 t29 84' Ì -ll 169 19 26
13 tl 161 a2 3 8r l5 6 887 856 20 ll 3 439 402 11 20 -l q40 453 t8 1 -10 915 929 t4
14 -16 t 04 L62 11r 15 I 169 115 3lr l1 4 499 181 15 20 6 104 ì63 86' Ì -9 15? 137 24
14 -15 108 52 55r t5 I 5Ì2 514 15 r1 5 351 336 2t 20 -5 3lì 434 22 1 -8 t4-73 1451 It
14 -1{ 349 308 t9 15 9 0 9580r 1l 6 4s1 430 16 20 -4 165 l4l 86" I -l 463 454 t0
t4 -13 0 6l t8r 15 10 311 345 22 Ìl 1 126 197 I5r 20 I 341 364 r 6 1966 t980 9
14 -12 481 465 1,5 15 tl 0 36 80r lf 8 399 359 19 20 2 29 r13 88. r -s 630 601 l0
14 -11 0 40 ?8r 15 12 0 102 80r 1? 9 109 11s 85¡ 20 1 219 246 21 I -4 2A91 2848 I
t4 -10 6t6 625 14 15 13 163 41 38' 1l 10 126 20t 59¡ 20 0 125 t19 I -3 611 592 9
14 -9 110 26 f4. 15 Ì4 0 30 f9r 1l tl 15r 62 20 I t8 50 lÌr 1 2 2303 228 4 1
14 I 580 5?2 13 l5 15 0 60 l9r 1l t2 26 26 84r 20 2 I54 28 81' I -l 845 839 1
t4 -1 1{1 39 73. 16 -14 262 246 2 la -t2 15? 129 83r 2 20 3 19 9 8l i 0 lf01 1733 1
14 -6 525 541 t2 16 -13 168 2t2 12. 2 13-11 2t6 26131 2 20 1 0 9t 89i I 94 68 18.
14 -5 0 115 13. 16 -12 151 302 86¡ 2 l8 -10 r19 285 85. 2 20 5 0 119 88r 2 1869 187? 1
14 -4 121 ? 04 4 16 -11 't6 2t9 85. 2 la -9 390 426 20 2 20 6 161 159 49. 3 42't 430 I
t4 -3 L26 53 2. 16 -10 452 466 16 2 18 -8 350 37? 21 2 20 7 16s 156 89i 4 1090 1095 8
t4 -2 532 543 2 16 -9 299 235 22 2 t8 -1 115 111r8 2 2L -4 0 6 86. 5 5{3 525 11
14 -Ì 57 3r t6 -E 608 630 t5 2 18 -6 406 420 rø 2 2l -3 24J 269 32 6 6t9 629 1I
14 0 398 389 5 a6 -1 233 1't 3 25 2 18 -5 {5t 165 17 2 2I -2 113 24 A1. 1 383 381 9
t4 I 0 '13 3. 16 -6 5 81. 591 13 2 IA -4 302 333 23 2 2I -l 336 340 24 I 232 225 13
14 2 181 148 0 16 -5 22I 20L 2 18 -3 397 421 18 2 21 0 L22 43 12. 9 r2t 132 26.
14 3 263 235 2 t6 -{ 651 659 15 2 IA -2 112 205 10r 2 21 1 393 380 21 10 211 216 1{
14 4 380 363 6 t6 -3 229 221 21 2 18 -t 235 211 30 2 21 2 165 61 88. 11 0 4t 62.
L4s 90 2LL 8¡ t6 -2 366 382 18 2 r8 0 0 3382¡ 2 21 3 363 364 23 l2 6t5 61l 13
t4 6 666 661 6 16 -1 310 214 20 2 t8 I 152 183 80. 3 0 -20 156 167 891 13 222 261 2T
14 1 L21 210 8r 16 0 t29 110 16ù 2 tø 2 0 11183¡ 3 0-18 315 362 20 t4 627 62ø l4
14 I 668 661 4 16 1 18-l 190 32. 2 ts 3 0 283. 3 0-16 652 620 L4 15 202 t88
t4 9 106 203 9. 16 2 0 46 16. 2 18 1 0 19s 86. 3 0 -11 1020 985 18 16 649 643 Ì5
14 10 614 639 { 16 3 140 10{ 2 18 5 120 97 8{r 3 0 -L2 t636 15 61 11 71 113 151 48¡
14 ll, 121 1?3 0i 16 4 202 246 33 2 t8 6 203 234 J6' 3 0 -10 1947 1940 12 18 443 460 l5
14 t2 {5I 165 6 16 5 0 61 19. 2 I8 7 0 13685¡ 3 0 -02072 2012 tO 19 106 91 ?5r
11 13 93 55 16 6 3't 6 366 19 2 LA A 308 21'' 21 3 0 -6 1190 113 6 9 239 25L 25
11 14 139 344 20 16 1 137 752 59* 2 L8 9 291 23025 3 0 -1 661 6't9 9 -21 0 39 87i
14 15 136 17 45r 16 I 399 391 18 2 18 10 321 320 25 3 0 -2 394 393 I -20 157 112 46.
14 16 203 245 32 16 9 220 203 32 2 18 lt 256 25230 3 0 0 ?98 2't à 'l -19 83 83 8{.
15 -t5 0 10 80r 16 10 431 444 18 2 19 -10 161 1.10 41i 3 0 2 1186 II11 1 -L8 311 335 23
2 -t1 0 79 80. 3 -4 319 1387 3 4 9't59 79315 3 6-20 0 56 84r -6 0 t23 50¡
2 -16 589 602 15 3-3 286 L262 3 4 10 131 131 11 3 5 -19 153 201 85r -5 1445 t402 10
2 -L5 146 110 4 0* 3-2 494 2419 3 1 11 620 55313 3 6-18 0 12 82. -4 350 342 9
2 -L4 ?10 191 15 3-1 L29 118I J 4 12 311 339 13 3 6 -1't 41.4 433 18 -3 1900 1880 10
2 -13 212 234 20 30 lf0 178{ 3 1 13 169 19012 3 6-16 0 88 80i 104 144 15
2 -r2 11? 4 1102 14 31 269 1308 3 4 11 J63 322 11 3 6 -15 635 63L L4 -t r?63 1763 10
2 -tL 451 {54 11 32 651 1630 3 4 15 252 263 21 3 6 -14 188 192 31 0 0 16 51..
2 -t0 L2L6 1250 13 33 141 1458 3 4 16 0 16415¡ 3 6-13 78? l?9 18 1 r5l6 1527 l0
2 -9 259 244 14 34 9't 3 982 3 4 t1 122 98 75. 3 6 -r2 252 286 2r 2 56 3 52r
2 -8 135? 1355 11 35 5?3 596 1 3 4 18 0 a211' 3 6-r1 891 846 16 3 98s r066 t1
2 -'t 210 19? 11 36 191 221 t5 3 1 19 1a3 L4 11. 3 6-10 30{ 219 t4 4 185
205 1E
2 -6 1115 113 4 9 31 04 6 103 4 t1 3 4 20 0 1371r 3 6 -9 861 880 14 5 1028 1074 t2
2-S 386 360 9 38 244 253 L4 3 5 -21 235 239 30 3 6 -8 304 303 12 6 485 487 t1
t242 1249 8 39 256 216 l5 3 5 -20 ?4 146 84. 3 6 -1 906 913 lt 1 419 438 t1
z-3 1231 1203 I 3 r0 526 512 t3 3 5 -19 306 763 23 3 6 -6 117 tl9 t6 8 428 4r3 I2
2-2 3A0 322 8 3 11 t22 111 56r 3 5 -18 145 233 {61 3 5 -5 643 639 12 9 11 3 0 56r
2-1 510 550 9 3t2 470 441 1L 3 5 -17 292 336 21 3 6 -1 256 242 rl l0 296 330 r7
20 156 r65 11 3 13 104 22L 69i 3 5-16 0 22L19. 3 6 -3 415 387 9 11 320 312 Ì?
143 lt6 12 3 1{ 482 482 !2 3 5 -15 162 190 3?r 3 6 -2 ll4 rsL 22' r2 102 145 48¡
22 !221 1253 1 315 331 304 16 3 s-14 00 92s1. 3 6 -' t44 110 1l 13 543 480 T2
23 609 625 9 3 16 3?8 365 15 3 5 -13 150 112 35i 3 6 0 285 301 9 14 0 17
24 1804 1801 8 317 289 216 20 3 5 -12 118 1{3 34i 3 6 1 589 592 72 15 499 493 t3
25 404 {03 10 3 18 361 341 t6 3 s-11 261 230L8 3 6 2 736 326 9 16 116 56 ?5*
26 1430 r482 10 3 19 202 231 30 3 5 -10 20t 112 2L 3 6 3 1215 119 3 10 1l 442 439 16
21 630 620 13 320 254 30t 25 3 5 -9 519 557 11 3 6 4 75 't 6 54r 18 13 6 11 't 1*
28 1518 15 73 11 4 -21 107 12r 61' 3 5 -8 {r3 1{110 3 6 51261 1206 11 19 330 338 20
29 146 't 41 14 4 -20 0 81 83* 3 5 -7 9{5 gLlll 3 6 6 525 506 12 -20 0 31 85r
210 1316 13 73 I2 4 -19 l3 9 199 70* 3 5 -6 495 516 10 3 6 'l 1364 t3a't 12 -19 143 148 12.
2tt 699 680 T6 4 -18 226 2t2 29 3 5 -510151013 9 3 6 6 269 261 15 -18 144 105 04r
182 16 4 -r1 334 324 2l 3 5 -4 848 818r0 3 6 91153 112 f l4 -r1 351 290 2I
2t3 226 200 20 4 -16 405 411 r6 3 5 -3 21062L48 9 3 6 10 0 99 61. -r6 18 1.49 93 à
2 14 690 1t2 Ì3 4 -15 460 481 14 3 5 -2 121? 1189 9 3 6 l|142 121 r8 -15 603 581 15
215 204 169 24 4 -14 412 442 L5 3 5 -1 2023 2023 I 3 6 12 208 282 2s -t4 210 203
2t6 246 309 20 4 t3 't44 120 13 3 s 01.3{01291 I 3 6 13 5?5 563 13 -13 610 654 15
211 68 12.
49 4 -12 510 601 12 3 5 r25312517 9 3 6 14 0 56 ltr -12 164 L24 30*
2L8 70 125 16. 4 -r1 6{3 616 t2 3 s 214111120 9 3 6 ls 328 316 18 -rt 1050 1068 15
2L9 108 83 5't ¡ 4 -10 556 536 13 3 5 323192315 9 3 6 t6 0 8l l8^ -10 2AA 2'19 L6
220 0 t5 5* 4-9 7t1 695 14 3 5 4 652 65812 3 6 71 246 140 23 -9 rt2l 1139 13
3 -21 0 |12 5i 4 -8 64 0 619 13 3 5 5 920 90811 3 6 18 111 151 ?8r -8 302 284 14
3 -20 138 199 5i 4-1 595 600 13 3 5 6 126 1L0L0 3 6 19 5l 56 l8r -'l 889 894 13
3 -19 245 256 9 4-6 484 4 98 9 3 5 1 662 6'1915 3 6 20 0 90 18. -6 261 25'l 14
3 -18 254 265 1 1-5 350 363 9 3 5 8 r11 10861. 3 1-20 0 61 85. -5 685 692 14
3 -17 209 2)3 1 4 -4 691 6?9 10 3 5 9 225 23r19 3 1-19 219 249 25 -4 319 386 10
3 -16 0 L63 9. 4-3 438 423 I 3 5 10 0 33641 3 7-18 131 9t 82' -3 10 58 5 6*
3 -15 226 6 0 2A 45' 3 5 11 t66 L10 2'l 3 1 -t'l 212 292 2'l 449 41s 10
3 -14 38 66 f5. 4-1 25t 264 9 3 s 12 118 139 39. 3 7 -16 211 200 31 -1 250 24s 13
3 -13 210 242 20 40 399 393 I 3 5 13 0 9169. 3 7-15 142 t51 81r 0 112 131 2't *
3 -L2 355 346 4T 63'l 626 r0 3 5 14 112 159 36. 3 I -L4 193 168 3r 1 606 621 I4
3 -11 0 31 65. 42 298 1287 I 3 5 15 321 351 tl 3 ? -13 131 I 74. 2 348 334 11
3 -10 401 411 11 43 034 1064 9 3 s 16 216 248 26 3 1 -)-2 351 J13 L6 3 868 845 13
3 -9 1r1 4 01 10 4a 2AA t213 9 3 s rl 336 335 19 3 1 -ll 216 4 528 514 T2
3 -8 182 '192 l2 45 4a6 1515 10 3' 5 t8 102 16E 65i 3 I -10 06 104 64r 5 1032 1088 13
3-l 111 ?95 t2 46 391 13't-' 10 3 5 19 32A 31420 3 I -9 689 680 15 6 559 563 13
3 -6 13 91 13?4 9 41 181 119-l 1t 3 5 20 l-{5 139 42. 3 ? -8 190 205 19 1 t269 1296 T4
3-5 813 922 9 48 080 1074 t2 3 6 -21 t24 r23 Al. 3 I -? 1115 11 01 12 I 243 2f9 19
89 116I 111 2 t5 10 -r3 604 594 13 3 tl 5 0 131 71r 3 13 -11 152 135 ?lr 14 11 154 l5 11à
8 10 2t9 230 24 10 -12 509 459 12 3 tt 6 502 521 12 3 13 -10 260 2t1 22 14 L2 104 323 23
I 11 10 41 1101 1-t 10 -11 798 l8
866 3 11 / 112 103 61. 3 13 -9 91 153 74. l4 13 0 39 82.
812 126 261 16. l0 -10 't89 771
17 3 1r I 229 2r3 23 3 13 -8 523 501 12 L4 14 222 254 30
8 13 641 659 L6 l0 -9 945 962
L6 3 1t 9 242 231 23 3 13 -? 133 t1 0 ?3. 14 15 0 14 83.
8 14 132 234 ? 8i 10 -8 588 6t2 14 3 11 :.0 115 102 l4* 3 L3 -6 611 663 t4 15 -15 't4 54 84.
I 15 399 385 16 l0 -7 791 ?f4 16 3 11 1t 385 358 16 3 13 -5 344 361 16 15 -14 190 110 36.
I 16 241 234 25 r0 -6 451 447 11 3 tl 12 286 259 21 3 13 -4 925 924 16 15 - t3 0 L22 84.
s 1l 208 122 29 10 -5 583 566 t3 3 11 13 29L 29A 22 3 13 -3 434 44 4 13 15 - I2 130 1l 8lr
8 t8 t63 155 38r 10 -4 205 t16 20 3 lt 14 28L 100 24 3 13 -2 1115 10'7I 16 15 - 11 0 106 83 r
I 19 159 14 39. 10 -3 28r 289 15 3 tt t5 330 299 20 3 13 -1 343 285 L6 10 2r1 156 30
9 -t9 216 145 35 10 -2 0 60 63. 3 11 16 21ø 285 24 3 13 0 1141 115 6 16 15 -9 111 20 59r
9 -18 0 25 I9. t0 -1 10 132 63' 3 11 l? 215 236 21 3 13 I {13 373 14 -8 421 361 t6
9 -1? 2J1 2t1 32 10 0 383 409 11 3 12 -18 210 151 3ôr 3 13 2 ll31 1089 16 t5 -'l 5't 2t
9 -16 49 9 81* 10 I 103 113 11 ) t2 -a1 136 1?1 85r 3 13 3 0 rl8 74i 15 -6 539 492 13
9 -15 0 158 82. 10 2 310 296 t1 3 12 -t5 2A2 290 25 3 13 4 660 691 t5 15 -5 LL2 25 l5r
9 -t{ 8l 54 78. 10 3 795 798 16 3 12 -15 209 269 31 3 13 5 59 3 6 56r 15 -{ 105 836 15
9 -13 0 13 l5r r0 I 357 365 t3 3 12 -1{ 411 403 t6 3 13 6 414 {01 15 15 -3 119 144 32.
9 -12 93 100 69r r0 5 882 910 15 3 12-13 318 36416 3 13 7 0 237 11. I5 -2 1001 971 10
9 -11 316 250 15 r0 6 488 462 tI 3 t2-12 508 51113 r 13 8 0 181 l?r 15 -). 133 19? 78r
9 -10 320 296 15 10 1 912 923 11 3 t2 -1t 351 396 t1 3 13 9 21I 240 22 15 0 1030 1052 1E
9 -9 608 640 13 r0 I 817 801 t8 3 12 -10 569 513 13 3 13 10 133 119 46r t5 1 148 r51 16.
9 -8 401 3 t0 t2 10 9 992 989 18 3 t2 -9 4tt 465 14 3 13 lt rlt 241 81. t5 2 1006 10I ? 19
9-1 10 21 99r 1l l0 10 638 603 15 3 t2 -8 515 5Ì1 12 3 13 12 l1f 167 l9¡ 3 2r2 22s 29
9 -5 491 4't 9 t1 10 tl 1't 3 111 t9 3 12 -1 521 529r1 3 13 13 0 169 80. 15 4 628 615 14
9 -5 1434 I436 I2 r0 12 592 518 14 3 ),2 -6 453 441 13 f 13 14 241 2t9 21 t5 s 1ll 114 45r
9 -4 661 679 15 10 13 48f 501 14 3 12 -5 54? 56311 3 13 15 0 1rl 83. 15 6 333 334 20
93 Ì548 rs21 11 10 14 380 342 r8 3 ),2 -4 r93 t92 26 3 13 r5 252 245 21 15 140 28 19^
9-2 4 65 48t t1 10 15 84 214 42. 3 t2 -3 495 189 12 3 14 -16 258 291 21 15 a 204 r 63
9 -1 t0?8 1085 t2 10 t6 112 188 3l¡ 3 12 -2 246 224 20 3 14 -r5 58 24 82. 15 90 29 81.
90 551 553 1l 10 tl 0 121 81 . 1 t2 I 0 9269. 3 14-14 383 381 19 15 10 0 55 84.
iú i6 0 15 ?0 8_5^

92 399 4t2 10 lt -18 80 120 90r 3 12 I 104 63 52. 3 14 -12 {63 442 t6 15 t20 l6l 85 *
93 9l0 932 l4 1t -17 110 86i 3 t2 2 388 351 14 3 14 -rl 56 t04 llr I5 L3 I24 6l 84.
94 284 260 L4 11 -16 129 14 0 ?0. f 12 3 681 600 14 I 14 -10 453 421 15 15 r4 tt8 115 10.
95 634 536 t2 11 -t5 121 4? 51. 3 12 4 905 886t-l 3 14 -9 0 r40 l0r 16 -14 220 213 34
95 218 190 20 -14 0 4t 11. 3 12 5 638 610 15 3 14 -8 311 350 19 r6 -13 0 105 8lr
91 385 36r r3 -13 139 20 38r 3 72 6 648 6?615 3 14 I 99 63 14. L6 -12 33 6 351 22
9E 0 26 fO. -12 8l 6'1 6r. 3 12 1 4s2 461 14 3 14 -6 381 l5l I5 16 -11 0 101 81*
99 13 6 8l 7tr -11 249 265 22 3 12 I 815 8E020 3 14 -5 0 69 l5 r 16 -10 4Ì6 4I6 18
9 10 0 6 59i -10 324 296 11 3 12 9 493 528 14 3 14 -4 264 242 21 16 9 0 8? 81r
9 11 283 319 20 -9 342 358 rs 3 t2 t0 516 612rs 3 14 -3 0 2 14r 16 -8 3r2 336 22
912 106 124 51. -8 688 648 13 3 t2 11 2].A 22128 3 14 -2 0 54 15" \6 1 154 140
 9 13 50f 490 13 -1 538 500 t2 3 12 t2 411 102 1s 314-l 0 13t 75' 16 -6 33I 354 t9
9 14 26 154 16* -6 950 955 16 3t2 13 211 1?9 30 3 14 0 304 335 19 16 -5 109 190 62.
9 15 552 556 14 62r 63 4 13 3L2 14 309 342 22 3 14 1 33 82 56r 16 -4 0 t 1l 19r
9 16 t54 :.5 9 41i -4 110I 1111 l4 312 t5 {8 150 80i 3 14 2 68-t 681 l5 L6 -3 144 191 34.
9 1? 366 412 20 -3 956 952 t5 3t2 l6 r 85 151 36' 3 14 3 0 t 12 11a L6 -2 173 '19.
9 16 13 9 101 46. 923 909 t5 312 17 t26 66 I9¡ 3 14 4 960 t0ll 19 t 6 -1 88 1r5 78.
l0 -19 5{ 131 90¡ -1 199 820 16 3 13 -17 0 16 a2r 3 11 5 1â 93 65i t6 0 10? 222 82.
t0 -18 2L1 124 36a 0 953 961 15 3 13 -L6 0 lf0 83i 3 14 C 8If 865 20 16 I 0 22 19.
L0 -t7 214 233 29 1 816 8r3 17 3 13 -15 0 I8 I0i 3 14 1 65 133 5E ¡ 16 2 466 452 15
10 -16 293 2Sr 25 2 614 62t 13 3 13 -t4 0 l0t 80r 3 14 8 669 661 1{ 16 3 232 193 2a
10 -15 401 4 48 3 530 63 0 13 3 13 -13 0 51 't 9r 3 14 9 o 12 42. t6 4 s1I 509
I0 -14 393 316 16 4 659 6EJ t3 3 13 -L2 161 60 35* 3 14 10 5t 6 533 L5 165 181 243 38.
16 6 555 552 11 10 303 2A1 21 40 20 0 99 15r 12-9 l,0l :.04 5{ r 34 338 315 9
t6 1 250 181 21 -9 262 253 28 41 -21 0 3l 90i 4 2 -ø 664 63t 15 35 394 396 10
16 I 562 522 15 -8 0 136 69. 41 -20 139 05 58r 42-1 251 20L 14 36 420 423 t0
16 9 198 199 3f* -7 J3'l 336 23 4t -t9 0 63 87* 42-6 48{ 494 11 3l 20t 149 t7
16 10 432 420 19 -6 148 2r0 66. 41 -tE 0 5? I6i 4 2 -5 t056 1056 10 38 001 't65 t4
16 I1 150 156 86* -5 396 435 20 41 -t? 0 65 85i 1 2 -1 430 t61 10 39 411 404 l1
t5 t2 282 295 2'l -4 206 242 36r 41 -16 154 12 a2. 12-1 192 ?5{ 10 3 10 623 633 t2
L6 t3 111 t24 86i -3 {01 425 l9 41 -15 0 8 80. 42-2 912 856 9 3 11 63 0 5E3 13
1t -13 30 101 85. -2 330 299 22 41 -l{ 253 260 25 42-L 999 981 9 312 644 6J2 L4
T1 -T2 t24 61 85r -1 380 367 20 41 -13 0138 l9r 420 L644 1618 I 3 13 465 431 t2
17 -tt 150 110 s6* 0 190 221 39. 4L -12 199 132 19 421 541 {9r ll 3 14 5 9l 581 12
17 -t0 0 103 85* I 216 213 21 41 -11 311 309 1l 422 2012 2033 9 3 15 311 381 15
tl -9 229 L96 31 2 160 220 87r {1 -10 10{6 1055 1{ 123 651 651 l1 3 16 412 412 t3
1? -8 200 305 25 3 294 293 26 41 -9 192 405 72 124 1 695 r 6?3 9 3 ll 299 218 20
)-'t -'t 1 I 161 84. { 0 r38 88r 4L -8 1229 1205 L2 425 a29 838 I1 3 18 3-ì 4 340 16
1? -6 159 {{1 l6 210 204 36 4L -1 610 594 l4 126 15 45 1559 10 3 19 14 6 t94 ?Sr
t1 -s 292 288 24 6 110 50 86i 11 -6 i.?39 16 6? 10 421 813
-7
9l L2 320 251 2I1 23
1r -1 573 584 14 'l 1't 3 151 90. {l -5 ?E6 111 11 128 13 87 1360 11 4 -2r 69 190 90r
17 -3 310 324 23 E 0 31 90. a1 -{ L382 1382 I 129 663 541 15 4 -20 0 t66 E9r
17 -2 589 563 13 -1 211 258 3l 41 -3 196 383 10 42L0 7t8 122 15 4 -19 300 256 26
17 -1 311 3t2 2J -6 0 111 ¡6. {1 131 I 1311 I 12LT 0 95 61. 4 -18 251 26L 29
t? 0 5r8 489 l4 -5 106 184 61r {1 -1 129 391 9 4212 598 586 ll 4 -r1 l2r 3L6 23
1? | 362 361 19 -4 0 114 47. 41 0 112 0 10 81 9 12L3 101 30 {5 r 4 -16 349 32L 20
1l 2 391 110 18 -3 53 70 86. 41 1 426 108 9 12t1 1t1 131 21 4 -15 423 424 t1
L1 3 215 233 32 -2 31 69 86. {l 2 610 693 10 4215 I9r 194 4 -14 309 294 2l
lf 4 336 J33 22 -1 0 58 88r 4L 3 4 05 397 Ì0 4216 0 16 t3¡ 4 -13 4t 4 459 16
17 5 164 139 83r 0 0 23 86. 41 4 0 22 50. 42tl L13 162 32' 4 -t2 496 446 12
1? 6 263 253 21 I 0 L49 88r 41 5 296 205 l0 { 2 18 195 128 28 4 -11 398 )61 14
17 ? 0 41 85* t29 105 4t 6 55{ 538 13 42t9 0 t 00 4 -10 133 401 12
l? I 57 111 61i 3 265 233 30 41 7 50 1?0 56' 4220 133 156 16. 4 -9 293 2-t5 15
17 9 0 28 89i 4 2't 2 179 29 41 I 880 E50 13 4 3-2t 0 113 90. 4 -0 252 268 16
1l 10 119 108 90i 5 29s 284 26 41 9 tl1 L14 2\ 4 3-20 131 19 88r 4 -1 155 80 22
1? 11 0 50 86r 6 t't 6 155 92' 41 10 1205 t236 13 4 3 -1.9 101 132 89. 4 -6 320 214 11
L1 12 264 227 29 -1 t't 9 408 22 41 tL 41.3 122 11 4 3 -18 rlt 21 65i 4 -5 212 235 12
18 -11 350 326 22 0 L18 40 08. 41 L2 902 913 t6 1 3 -).1 o66 86r 4 -4 340 329 9
I8 -10 244 294 31 -20 2r3 245 39. 41 13 0 191 68i 1 3 -L6 103 83 58 r 4 -3 990 101? I0
18 -9 284 319 2'l -18 435 444 19 41 1{ 8't 2 851 4 3 -15 56 23 80. 4 -2 955 916 10
18 -8 20r 290 26 -t6 653 641 15 41 15 L43 215 35r 4 3 -11 330 325 19 4-r r334 1310 9
18 -7 3I9 299 22 -11 868 880 20 41 16 556 551 13 { 3 -13 t12 t65 12. 40 tt40 IL36 9
18 -6 138 160 521 -t2 114 5 11 64 16 {1 l7 0 63 4 3-12 385 387 16 41 1613 L629 9
18 -5 210 239 35 -10 L094 to 42 15 41 18 294 306 20 a 3-11 566 523 12 42 1410 1425 9
lt -1 0 50
83r -8 755 140 14 {1 19 0 26 ?5i 1 3 -10 616 6A1 L3 43 1988 1963 10
10-30 78
84r -6 412 410 11 41 200 181 29 { 3 -9 880 846 t{ 44 111 4 1r 63 10
18 -2 161 10
a2. -4 15s 21! 16 42 -2r 0 13 89. 4 3 -8 1039 1033 12 45 t1Ì5 1tt5 11
10 -1 r59 19
81i -2 330 346 1 42 13 221 91. 43-1 1236 1192 rl 46 lt 8 r40 13
18 0 -t3 170 85r 0 1114 113 6 9 42 -19 0 93 66. 4 3 -6 1313 1299 t0 41 1019 1005 12
t8 I 13't 113 81. I 618 7646 9 42 -18 391 391 19 {3-5 1161 1t99 10 48 682 683 l6
18 2 239 200 29 4 1989 Ì9?8 9 42 -1? 189 1l 38* 4 3 -4 r99t 2000 9 49 54s 542 13
18 3 241 22't 29 6 l.860 1849 t0 42 -16 518 53 t5 43-3 91.4 852 1.0 4 10 250 264 tS
18 4 205 2A4 iA. 8 183 5 1846 II 42 -15 0 2I 03* 4 3 -2 L461 t424 9 4 1r 232 242 20
18 5 305 283 25 1.0 961 LO2A 13 42 -14 605 63 14 4 3 -1 1224 L229 9 4t2 261 211 19
18 6 310 294 25 I2 481 485 I2 42 -13 394 31 I6 430 1099 1092 9 { 13 168 202 29.
18 l 359 333 22 14 13 200 ?0 * 42 -r2 't 41 16 13 431 955 993 9 4 14 105 60 4'1.
18 I 352 350 23 t6 0 38 42 -t- 1 25 11 12* 432 3'r3 396 9 4 15 0 36 55.
18 9 402 363 22 Ì8 0 r48 ?5* 42 -10 690 6'l 13 {33 335 340 I 4 16 156 16 34.
4 L1 210 191 28 -8 170 151 24 4'l 1 499 l8 10 4 9 -r5 0 92 88. l0 3 t049 1080 15
4 18 0 125 79. -'l 262 208 t5 4'1 I 122 61 36r 4 9 -l{ 92 131 10. r0 4 570 548 12
{ 19 1?5 180 36¡ -6 194 I21 Lø 41 9 924 451 l6 4 9-13 358 329 19 10 5 98 6 986 16
5 -20 140 101 55. -5 166 t32 2r 41 10 212 24r I9 1 9-72 301 219 20 t0 6 84 9 892 \1
5 -19 0 135 88. -4 442 411 12 41 11 a12 663 18 4 9 -11 691 611 15 l0 1 929 941 r7
5 -t8 I33 99 56. -3 866 856 12 41 L2 83 L2 61r 4 9 -10 438 44{ 1r 10 8 645 629 L5
5 -17 0 15 t5. -2 452 421 tt 41 13 422 11 1.9 4 9 -9 946
9?9 16 t0 9 662 703 t6
5 -16 0 34 ø2' -1 151 0 1536 10 41 14 0 1 161 4 9 -8 189
448 L2 10 10 603 6T2 L4
5 -15 200 141 32 126 123 10 4'l 15 618 58 14 49-1 1095 1095 11 l0 11 302 3't2 2r
5 -14 104 55 59* I 1880 1923 10 11 16 l{0 5 16t 4 9 -6 469 475 lt to t2 282 265 22
5 -r3 211 194 24 2 255 211 L3 41 1't 421 42 l6 1 9 -5 1220 1185 ll I0 l3 0 L83 82.
5 -12 111 99 ?5* 3 1?83 1802 10 4'l l8 0 80r 4 9 -4 314 34t 12 10 14 133 107 ?8.
5 -II 583 5?0 12 4 611 646 14 41 19 289 {9-3 958 941 t4 10 15 0 9 8t.
5 -10 439 409 t2 5 t{94 1492 11 4E -19 60 231 93r 49-2 122 330 t4 10 t6 0 16 81.
5 -9 ô48 824 15 6 358 368 L2 {8 -18 0 L05 0 9. 4 9 -1 73{ ?39 16 t0 l? 0 60 8tr
5 -8 584 595 12 1 113 9 1126 t3 48 -71 443 418 20 490 255 211 15 tt -18 129 38 93.
5 -l 118-' 1165 12 I 23'l 2r9 ).9 48 -16 L2ø r62 66r 491 507 533 Il 11 -tl 0 ta 92.
5 -6 151 ?61. 13 9 563 537 t { 48 -15 517 510 16 492 252 216 11 11 -r6 0 55 85.
5 -5 1784 1709 10 10 86 45 67. 40 -14 156 9t 12r 493 343 J2J 13 11 -15 96 12 65.
5 -{ 812 189 t2 I1 462 424 12 48 -13 682 657 16 494 193 223 21 11 -t4 115 r?3 8lr
s -3 lglt 1084 10 l2 1I8 91 41* 48 -t-2 294 261 20 495 95 28 65. 11 -13 r9l 211 f4.
5 -2 902 906 11 13 189 175 28 48 -11 624 685 1s 496 49 12 58. 1I _I2 349 361 19
5 -1 1601 t605 r0 14 0 L41 164 48 -10 250 261 2t 491 598 600 15 11 -1Ì 311 301 17
50673 635 t2 15 ?1 52 l5* 48 415 108 13 {98 154 94 31. 11 -10 588 t5
5 1 1233 t244 l0 16 26J 243 23 48 -8 216 261 t1 499 113 194 t9 11 -9 456 462 t4
5 2 198 193 t5 1? 113 t24 66* 48 -1 222 l8{ 20 4 9 t0 1r1 146 32. 11 -8 105 102 t4
530 't9 55. t8 752 171 41r 48 -6 311 265 L4 4 9 1l 124 154 ts l1 -7 6r 1 581 t2
540 90 55r t8 4 33. 48 321 t3 4912 1t9 216 18. t1 -6 't59 758 t9
19 193 -5 33 {
55242 245 14 -20 0 02 91r 48 -4 255 250 t6 4 9 t3 1t5 't24 16 11 -5 81f 196 ll
5 5 230 208 15 -19 1?3 110 90r 48 -3 799 166 t4 1 9 t4 184 205 34. 11 -4 193 801 ll
51492 490 11 -18 184 1lr 43. 48 -2 142 138 26. 4 9 15 480 495 15 11 -3 12A 128 ll
5 I 140 35? L3 -r7 0 38 88. 48 -t 10 81 1055 t2 1 9 16 165 155 38i l.1 -2 102 698 1l
s 9 592 554 13 -16 01 117 S5* 48 0 r45 68 21 1 9 1l 243 296 26 11 -1 410 410 T3
5 10 210 186 21 -15 238 193 30 48 I 13 21 1294 L2 4 9 18 151 92 19r tl 0 416 466 t2
5 lt 4S0 463 t2 -14 0 t65 82* 48 329 335 12 4 10 -l-8 r04 160 93. 11 I 455 4't 2 t2
5 L2 761 311 t- 4 -13 303 26e 2r 48 3 r500 1509 12 4 t0 -11 3!9 32r 21 l1 2 592 t3
5 13 635 605 14 -t2 r42 113 l3 ¡ 48 4 400 412 t1 4 10 -16 283 291 J0 11 3 2IT 2i6 24
5 14 320 331 18 -11 ?00 699 t4 48 l4 61 r4?1 1l 4 10 -15 464 469 t8 11 4 214 l9l 24
5 15 52? 525 13 -10 119 93 69r 48 6 250 20 4 10 -14 366 374 20 11 5 440 i65 ll
5 16 tl5 202 33a -9 10 81 1039 14 48 t268 1255 14
1 4 10 -13 598 593 ls 11 6 0 45 12'
5 11 493 456 t4 -8 103 63 54r 48 8 243 283 2L 4tot2 433 414 rs It 1 l4l ll
5 18 185 183 33¡ 1t242 t234 13 48 9 1012 1009 16 { 10 -tl 595 655 11 t1 8 249 221 2J
5 19 291 3\r 23 -6 t27 31 31. 48 10 381 370 15 4 t0 -10 3?l 359 l6 11 9 515 544 l4
6 -20 r12 52 45r 664 1643 tl
1 48 11 493 489 13 4 10 -9 530 5-70 ì2 1l l0 491 515 l4
5 ly Jul 2LJ r v5 TI 4ü T2 !41 JAY LI 4 tu -ö l12 ìJI 61. 1l ì1 ! 9t 40! ìl
5 -18 123 49 88^ 3 1545 162 t 11 48 13 91 164 16r 4 10 1 285 256 t8 11 12 396 455 l9
6 -t1 119 395 2l 131 48 24r 48 14 342 336 19 4 10 -6 0 5t 10. 11 13 149 353 20
6 -16 0 t2r 85. 1 13?9 t366 11 40 t5 165 92 31* 4 10 -5 0 3l 68. 1t t4 424 419 1f
6 -15 499 4?9 15 0 119 21 21r 18 16 211 20t 30 4 l0 -4 0 125 68. tt 15 296 301 24
6 -14 0 180 80. I 164 781 13 48 I1 129 130 49r 410-3 243 251 19 11 16 0 86.
6 -13 514 46? t3 2 294 300 l2 48 18 0 108 81. 4to-2 223 794 20 t1 17 254 208 2l
6 -12 198 1?9 28 3 265 294 14 49 -r9 t32 ?3 93. 4 10 -1 453 441 t1 t2 -11 42 153 92.
6 -11 516 499 t2 4 205 195 18 49 -18 t26 29 65. 4 t0 0 410 4t5 12 t2 16 f24 24
6 -10 l0 92 10* 5 211 231 t5 49 t? 0 54 91r 4 10 I 895 840 15 Ì2 -15 249 229 29
6 -9 435 436 L1 6 0 148 65. 49 -16 0 105 88. 4 10 2 435 462 t2 t2 -r4 I0l 104 2'J
t2 -13 1?8 241 74. 9 291 306 4 15 4 13 41 61. 4 11 1 148 119 89. a -12 )16 f34 l8
4 12 -t2 219 216 24 4 13 10 311 3 4'l 22 15 5 62 20 80r lt 8 205 249 28 50 l0 12 55
4 12 -tI 292 2AO 22 {1311 0 196 a2ù 15 6 0 61 42. 11 9 t19 t54 91 r 50 -8 431 424 L2
4 12 -10 LLz 233 80. 4L3T2 396 ll t9 15 'l 0 49 81r t7 10 346 365 26 50 -6 rt92 II59 t2
4 12 -9 386 319 17 4 t3 13 0 I3 83. 15 I 14 234 85r r? 11 119 149 64r 50 -4 150 8 03 13
412-69438 76r 4 13 14 380 38 20 15 9 1,5 0 43 18 -10 110 14 4 63. 50 -2 1145 1015 10
4 12 -1 359 389 17 4 13 15 13{ t5 83i 15 10 215 300 21 t8 -9 16t 151 80. 50 0 1 1935 10
936
4 t2 -6 t2L 66 46i 4 11 -15 0 88. 1.5 1l 0 ,{0 88i 18 109 31 86. 50 2 t965 1900 10
4 12 -5 161 196 31* 4 1{ -14 265 21 29 15 12 308 319 25 18 -1 0 88 87. 50 4 17t0 t?4s Ì1
4 12 -4 387 39¡ 15 1 11 -13 t30 6 8{r 15 13 0 85i 18 -6 0 59 88r 50 6 I31 4 t426 11.
4t2-3231a 60i 1 74 -L2 301 28 24 16 -13 L37 55 89. I8 -5 0 4t 8?. 50 I ?5Ì 196 Ì5
4 12 -2 155 1t9 4 t4 -11 80 89 82. 15 -t2 248 264 18 -4 0 169 87ú 50 10 110 33 6{r
1 12 -7 383 3ll 4 14 -10 225 223 30 16 -11 !12 50 53r 18 -3 222 r20 32 50 t2 0 84 61.
4 t2 0 613 7ls 4 14 -9 0 43 8ri 16 -10 t9l )-62 39' I8 25'l 242 30 50 14 214 261 18
4 t2 1 826 189 414-8 0 13 980. 16 -9 99 101 60i t8 -1 223 208 33 50 I6 181 242 31r
1 t2 2 1019 1029 414-7 119 111 ?9r 15 -8 136 107 84* 18 0 252 256 30 50 1g 15f 115 3 6r
4 72 3 528 ss5 114-6 24 11 66. 16 -? 0 99 84* 18 I 328 310 23 51 -21 153 26 51.
4 t2 4 906 869 414-5 5'l 14 11. 16 -6 0 t2r 85* 18 2 40t 366 20 51 -20 134 l8 96.
4 12 5 425 400 15 411-4 315 291 t9 16 -5 t29 35 81. 18 3 430 400 l9 51 -Ì9 0 30 92'
4 t2 5 956 1000 19 {11-3 t13 14ù 16 -1 323 360 23 18 4 3-t I 35r 22 -18 258 206 34
4 t2 1 393 424 16 414-2 653 578 13 16 -3 0 85 42. 18 5 314 4r5 23 51 14 29 89i
4 t2 A 610 641 T6 411-1 0 22 ?5. t6 -2 4t8 1't 0 17 18 6 350 343 24 51 -16 424 352 20
4 t2 9 116 t42 11r 4 11 0 191 032 t5 16 -1 37 l3{ 63. 18 'l 388 403 23 51 -15 08 t26 85i
4 12 10 1?5 1?8 15 { 14 1 199 83 30 16 0 s65 604 14 18 I 198 261 45* 51 -14 145 122 t7
4 12 11 12s 179 l9r 4 11 2 1120 1 118 18 16 I 330 311 2l L8 9 411 354 22 51 -13 r49 233 a2r
4 12 !2 232 2L3 28 4 14 3 1J2 91 ?8. 16 2 531 613 15 19 -8 0 186 90* 51 -12 997 98? t9
4t2138691 52' 114 1 885 008 20 L63 261 219 21 19 -1 301 358 21 51 -11 223 t41 25
1 12 11 144 12 a2a 111 5 0 56 19' 16 1 633 622 15 19 -6 201 190 3r* 51 -10 114 0 1165 l6
41215028 42. 1 11 6 612 66I I6 16 5 95 156 85. 19 -5 346 348 23 5I -9 0 133 70r
4 t2 16 125 32 81i 1 L1 1 105 57 56* 16 6 550 539 15 19 -4 t91 225 40' 51 -8 1164 r 121 14
4 13 -16 73 2t 8?* 4 Lt I 485 496 16 16 'l 167 153 86r 19 -3 222 275 35 51 219 256 15
4 13 -15 0 21 E?T 4 11 9 0 1l a2* 16 I 129 {06 19 19 110 163 44i 51 -6 110l 101 9 T2
4 t3 -t{ 123 l4l 5 8. 1 l,{ I0 269 289 26 16 9 211 t 66 35 19 -1 3l 222 88r 51 88 41 59r
4 13-13 0 35 85* 4 14 tl 0 61 84¡ 16 10 2t1 218 3lr t9 0 t {6 110 E?i 51 -4 521 545 1t
4 t3 -12 326 213 2t 4!412 1s1 1?4 83 | 16 t 1 0 160 89r 19 I 160 225 89. 51 -3 321 294 l0
4 13 -11 0 80 82' { 14 13 109 83 03* t6 12 0 ?8 86. 19 2 l0 67¡ 51 -2 402 375 10
4 13 -10 103 394 L1 { 14 14 138 116 52r t1 -r2 116 L82 16. 19 3 55 140 89i 51 -1 204 218 15
4 13 -9 0 34 78r { 15 -11 0 't8 89r I? -11 119 191 90. 19 4 104 65 44* 51 0 r61 148 17
4 13 -8 639 651 14 4 t5 -13 112 112 42r t7 -10 280 325 29 19 0 38 93i 51 1 105 93 55 r
4 13 -? Ig't 204 3l 4 15 -12 25'l 246 29 ¡.7 -9 2L4 r92 35 t9 6 160 t58 93r 51 2 589 582 t4
4 13 -6 656 837 19 1 15 -11 0 63 86. 1f -8 402 415 20 19 1 0 113 95r 51 3 156 111 20
4 13 -5 3r2 291 19 { 15 -10 393 4 03 20 1l -'l 309 290 24 20 -5 0 24 88¡ 5l 4 1045 10{1 t2
4 13 -4 839 883 19 415-9 50 94 81r ì.7 -6 415 488 1-l 20 -4 t03 47 13r 51 92 90 58i
4 13 -3 293 305 20 4 15 -8 549 564 14 1? -5 349 3t2 2t 20 -3 94 I08 90¡ 5l 6 13t4 1369 t1
4 t3 -2 905 897 18 4 15 --' 43 83 a2r t? -4 431 451 18 20 63 92 90r 51 1 423 391 10
{ 13 -1 2t9 t24 25 415-6 161 810 16 ll -3 269 294 21 20 -1 206 201 39r 5t 8 t62A r595 t2
4 13 0 824 83I 19 415-5 219 197 23 17 402 371 10 20 0 0 108 89r 9 419 411 12
4131122I 53r 4 15 -4 060 865 20 1? -1 26L 26L 2A 20 1 264 241 32 51 t0 104? t062 14
4 13 2 409 4t9 415-3 211 241 24 1? 0 322 3L2 22 20 2 292 2t8 28 51 1l 165 171 21
4 13 3 230 2rA 24 415-2 839 804 15 1? 1 L2 101 85r 20 333 162 21 51 T2 915 952 16
4 13 4 0 18 16. 415-t 187 109 33r 1? 2 153 196 4l¡ 4 94 161 94i 51 13 240 244 2T
4 13 5 411 374 L6 4150 'to7 126 16 L) 3 t12 27 04r 0 -20 29'l 2'10 3l 51 T4 501 524 t2
4 13 6 154 ?0 7 8r 4 15 r r06 136 81. 1f 4 0 e2 84r 0 3?1 405 24 51 l5 0 3t 71.
4 13 1 261 270 23 4152 350 339 19 I7 5 18 l0 87i 0 -16 462 4A2 19 51 16 331 32f 1-l
{ 13 8 385 360 18 4 15 3 21 ?9r t1 6 159 52 84r 0 -r1 463 529 1l 51 L1 0 18 ?5.
s 1 18 t09 t2'l 16. 5 3 -8 893 861 15 4 'l 411 183 L2 6 -11 305 21r 28 5? 0 4?1 425 12
51198?94 53* 53-l 786 I98 15 4 I 22L 22L 20 6 -16 r12 89 90r 5-7 I 40 144 63.
5 2-21 A2 84 93r 53-6 1282 t256 t2 4 9 tl1 86 56. 6 -15 228 249 34 5f 2 3 91 426 T2
5 2 -20 2t4 221 42' 53-5 500 494 10 4 10 131 ll5 67r 6 -t 4 I44 131 85r 57 3 555 13
s 2 -L9 95 t22 65* 5 3 -{ 531 516 !2 4 11 r25 106 38r 6 -13 r20 t1 4 82' 51 4 149 8t 28'
5 2 -18 231 3t2 6 53-3 833 1't 0 I2 4 L2 95 95 70r 6 -12 69 13 19. 5'l 5 681 614 t2
5 2 -L1 LL4 t42 9r 53-2 48 6 470 11 4 13 10t 168 75i 6 -11 0 30 l9r 57 6 0 40 68r
5 2 -t5 334 314 4 53-t 128 731 13 4 14 198 t94 28 6 -10 249 222 23 5l 1 906 929 1l
5 2 -15 125 130 8r 530 212 218 t2 4 t5 726 326 19 6 418 391 14 57 I t40 141 l1i
5 2 -1{ 255 309 I 531 240 253 14 4 16 291 254 2l 6 -8 264 289 20 5? 9 ro21 103 0 17
5 2-13 0 51 1r 532 s4'l ø32 t2 4 17 343 311 18 6 -1 691 694 13 57 t0 159 8l 31.
5 2 -r2 268 222 4 533 114 113 57r 4 18 284 301 23 6 -6 459 440 11 5? t1 873 854 t9
5 2 -11 313 289 9 534 181 163 13 4 19 249 213 26 6 -5 1120 t452 L2 5? t2 0 1 ?5¡
s 2 -10 119 25 3i 535 152 424 tl 5 -20 L29 31 95¡ 6 -4 401 401 11 57 13 731 1?A
s 2 -9 39I 12'l 4 536 895 851 1l -19 22L 12 3Ar 6 -3 1639 t623 L2 5l 14 0 18 78r
5 2 -8 328 338 5 53'l 645 634 16 5 -18 0 50 92. 6 -2 415 42r t\ 5? 15 42ø 429 |l
5 2 -1 566 56E 3 538 941 950 t4 -r'l t2'l 203 90r 6 -l 1832 1803 11 5f 16 0 52 19.
5 2 -6 ø45 862 4 539 ?39 152 17 -16
5 101 t03 62' 6 0 331 150 12 5l r'l 31r 211 2T
5 2 -5 55? s3t I 53t0 106 611 1l 5 -15 352 362 23 6 1 1565 1589 r2 5l 18 0 16 8ri
5 2 -4 ll55 1490 I 5 3 11 539 530 L2 5 -14 111 209 65. 6 2 551 502 t2 58 -19 116 216 56.
s 2 -3 643 664 3 53t2 818 011 1l 5 -13 513 506 t5 6 3 L283 t2a5 L2 58 -18 0 43 96.
s 2 -2 1185 1142 0 5 3 13 431 468 1{ 5 -I2 341 316 19 6 4 469 464 t2 58 -17 30 9 298 30
5 2 -t 665 650 2 5 3 14 s24 542 t2 5 -11 055 862 L9 5 5 861 915 r5 58 -r6 t19 52 92.
5 2 019331899 0 5315 310 314 19 5 -10 5 0't s41 t3 6 6 290 219 16 58 -15 123 32t 26
52t941941 I 5 3 16 29'l 322 2L 5 -9 110 9 1090 15 6 ? 578 586 l4 58 -14 160 83 85.
5 2 2t5291543 o 5 3 17 22! 215 21 -8 525 533 12 6 80 9 48r 58 -11 240 220 30
5 2 3 093 885 72 5 3 18 r42 163 1't. 5 L223 r240 14 6 9 348 360 15 58 -12 0 I92 84r
s 2 413851315 11 5 3 19 l-11 l{9 65. 5 -6 652 621 ll 6 IO 245 2a0 22 58 11 lt 8 46 601
525162165 14 5 4-20 180 165 93* 5 L24 1 )-284 l3 6 11 105 143 12. 58 -10 254 26t 24
5 2 6 914 965 13 5 {-L9 131 200 93r 5 -4 512 523 t2 6 12 86 I22 13^ 58 344 319 1l
52?{I7406 t0 5 4-18 0 tl5 93* 5 -3 692 696 15 6 13 152 180 ll. 58 231 242 23
528615634 t2 5 4-1? 0 232 924 5 -2 2't 0 214 14 6 14 306 283 20 58 5 91 6t5 12
529ø229 55r 5 4-16 194 157 39* 5 -1 350 299 11 6 15 310 309 21 58 169 184 30.
5 2 10 282 261 t6 5 4-15 249 220 29 5 0 0 56 59. 6 t6 200 154 31 58 903 911 16
s 2 tl 246 268 19 5 4 -14 168 169 11i 5 1 231 235 6 1? 370 35 4 t8 58 t 03 30 68.
52t2063 69¡ 5 4-13 0 120 82r 5 2 0 41 59. 6 t I 101 111 6lr 58 1 151 \112 14
5 2 t3 290 281 18 5 4-L2 180 166 34* 5 3 492 537 10 1 -19 1?0 ?8 95r 58 85 31 6f.
s 2 14 106 2tE 73. 5 4-LÌ 150 10 39. 5 4 62r 5'r8 16 1 -18 0 41 924 56 t26l t2a2 13
5 2 15 196 226 28 5 4 -10 0 3 5 5 640 64 0 T6 1 -t'l 254 230 34 58 141 ll6 31.
5 2 t-6 321 295 l7 5 4 -9 312 34 15 5 6 4)-2 421 11 1 -16 0 43 91. 58 135I 1328 13
52t10166 'r5i 5 1 -8 255 24 19 5 1 685 711. 1f 1 -15 437 184 19 50 19f 194 22
5 2 18 281 21A 2T 54-l 599 5? I3 5 I 434 122 t2 1 - 14 121 60 65. 58 ).336 1393 14
5 2 19 tlf 114 51r 54-6 480 41 11 5 9 583 610 13 1 -13 671 65r 14 58 198 t25 23
5 3 -20 tl9 62 92' 54-5 13 41 732 t2 5 Ì0 4 9t 500 T2 1 -12 155 I06 ?9r 58 t032 1023 r5
5 3 -t9 0 13 93r 5 4 -4 112 5 115 t2 5 II 412 839 1f 1 - 11 815 818 19 58 25\ r93 20
5 3 -18 149 144 ?5. 54-3 J-221 122 11 5 12 342 384 17 1 -10 95 165 7l ¡ 58 751 155 19
5 3 -tl 148 121 75r 54-2 t214 115 11 5 13 690 683 I4 1 -9 919 961 1l 58 195 t56 21
5 3 -16 239 263 3l 54-1 1544 L54 1t 5 14 240 252 1 -8 91 l3 12. 58 232 234 24
5 3 -15 339 215 22 540 I 410 137 11 5 15 590 568 14 f ? 1063 t 03 15 58 Ì0 265 212 2I
5 3 -14 452 429 16 541 1583 t51 2 1l 5 76 156 181 7 9i 1 -6 101 l 69. 58 11 0 50 74.
5 3 -13 423 418 16 5{2 t02{ t 03I 1l 369 316 18 1 -5 951 93 15 58 T2 234 2r2 26
5 3 -12 sl4 570 14 543 801 846 t3 t8 121 82 50i f -4 11{ 3 66^ 58 1l 28I 298 22
5 3 -11 624 603 13 544 104 668 14 5 -20 0 14 94i 1 -3 682 62 I6 58 14 0 141 81 ¡
5 3 -10 783 l?8 t9 545 1030 1009 I2 6 -t9 262 241 35 1 -2 310 29 t4 58 15 245 211 28
s 3 -9 184 149 I8 546 466 164 10 6 -18 1t6 90 48* 1 -1 281 21 15 58 16 153 48 79.
s 8 17 221 23s 30 5 10 0 533 520 13 L2 0 24 86r I3 11 218 13 33 5 15 I 412 464 18
5 9 -18 195 105 5 10 I 1030 1043 16 l2 -1t 114 141 46. t3 t2 42t 469 20 5 ls 9 0 Ì4 89*
5 I -lf tll L93 95. 5 10 2 't a9 ¡0¡ I] 12 -10 217 ra0 29 13 t3 145 l6 8l r 5 t5 10 434 41\ ?1
5 9 -16 242 141 35 5 t0 3 878 065 18 t2 -9 108 114 82' 13 14 384 31 2l 5 t5 11 100 61 89.
5 9 -r5 409 341 22 5 t0 4 11L 114 19 l2 -8 326 310 2t 14 -t5 0 94. 4 5 Ì5 T2 362 t89 24
5 9 -I{ 266 t10 29 5 10 5 148 129 14 -1 129 115 48. 14 -14 0 l3 93. 5 t6 t2 0 28 95^
5 9 -13 516 586 15 5 10 6 54I 539 11 12 -6 582 5?8 l5 14 -Ì3 l2 5 90. 5 16 -11 144 44 90.
5 9 -12 3s7 315 20 5 t0 1 531 481 12 12 -5 353 3 69 18 I4 -12 0 1 91. 5 16 -IO 0 82 91.
5 9 -tt 124 -tO6 16 5 10 I 426 448 15 \2 -4 't ø2 1'11 14 t4 11 61. I 5 t6 9 o 55 90.
5 9 -10 313 288 20 5 r0 9 0 8t 79r L2 -3 4 45 464 15 1{ 10 0 5 90r 5 t6 -8 244 2I4 32
5 9 -9 646 616 15 5 10 t0 Ì08 86 65r 12 -2 92t 939 l7 I4 -9 111 85. 5 l5 1 lÌl 53 13.
5 9 -8 2A8 210 20 5 10 lt 0 35 79* t2 -1 151 121 t4 14 -8 212 204 21 5 16 -5 4r2 411 20
5 9 -1 659 642 t4 5 10 12 24 18 ?8¡ l2 0 958 949 18 14 -l 0 8l 84. 5 1.6 5 20r I24 31'
5 9 -6 229 223 24 5 10 13 187 144 35* 12 I 51? 510 13 14 6 5 43 531 14 5 t6 s2l 5tl t6
5 9 -5 448 424 t3 5 10 14 15E 14 g2r 5 12 2 859 903 19 5 14 -5 69 85 Elr 5 16 -3 1s2 20 81.
5 9 -4 2A4 261 18 s 10 15 742 162 83' s 12 3 313 212 20 5 14 -4 316 161 20 5 16 -2 624 62 14
5 9 -3 275 29519 5 10 16 0 5684. 5 12 4 ?81 811 15 s 14 -3 63 41 a2r 5 t6 -t 343 22
59-2 0 34 61. 5 11 -1r 1S4 132 50* s 12 5 221 2t4 27 5 t4 -2 all 88 9 2T 516064Ì 16
59-1 0 39 69¡ 5 11 -16 tt6 203 91. 5 12 6 570 60ð 13 5 14 -1 86 133 80r 5 16 1 316 24 23
590 16t 113 29. 5 11 -15 242 21,A 35 5 12 I 155 188 l8r 5 11 0 985 913 19 5 16 2 655 6t I5
591, 165 1s8 28. 5 11 -14 35A 329 24 5 12 g 283 304 21 5 14 1 176 24 36. 5 t6 3 I91 15 38r
592 0 40 68. 5 11 -13 291 1tO 21 5 12 9 0 113 83i s 14 2 156 ?53 16 5 t6 { 489 493 18
593 496 {99 11 5 11 -12 488 481 16 5 12 10 167 6't 40. 5 14 3 1s4 41 41. 5 t6 5 0 140 8fr
59{ 322 329 11 5 11 -11 {26 43s 18 5 12 11 1{{ s6 82r 5 14 4 {94 489 15 5 16 6 319 348 26
595 1046 1009 t6 5 11 -10 4?9 49't 16 5 72 12 0 69 86¡ 5 11 5 0 4 ¡1. 5 16 1 231 183 34
596 3 60 {13 16 5 11 -9 16? 135 15 5 12 13 0 55 84. 5 14 6 402 438 19 s 16 8 I28 106 68.
591 1094 1064 16 5 11 -8 534 503 13 5 12 14 rs8 141 86r 5 1{ l 0 14 84. 5 16 9 12 196 92.
598 316 302 19 5 11 -'t 114 5L2 14 5 12 rs 0 122 8sr 5 t4 I 160 I 65 45. 5 16 10 Ì12 42 91*
599 1015 1060 18 5 11 -6 499 491 13 5 13 -16 2l? t1 4 42. 5 t4 9 0 69 85. 5 t6 11 206 114 41i
5 9 I0 732 331 19 5 11 -5 405 423 15 5 13 -15 98 6t 92. 5 14 l0 120 19 66. 5 1? -11 2?5 163 31
5 9 11 131 110 15 5 11 -4 413 436 t5 5 13 -14 226 264 38 5 14 11 63 83 8l ¡ 5 1r -10 2?0 319 33
5 9 12 13? 2t? 80* 5 11 -3 242 ]^8r 23 5 13 -13 0 96 90r 5 14 t2 0 21 81, 5 11 -9 242 225 35
5 9 13 488 509 1s 5 11 -2 22L 205 25 5 13 -12 416 369 20 5 14 13 0 68 89. 5 rl -8 333 336 26
5 9 11 16 173 58r 5 11 -1 0 70 74* 5 13 -11 0 L22 88' s 15 -14 13S 2I8 12r 5 ll -l 201 221 40.
5 9 15 216 2A4 25 5 11 0 303 3:.7 19 5 13 -10 522 553 l7 s 15 -13 129 35 93r 5 t1 -6 211 3r0 30
5 9 16 0 97 83. s 11 1 495 489 13 5 13 -9 150 135 17 i s 15 -r2 329 364 21 5 1l -5 75 161 88.
5 9 1l 0 143 84. 5 11 2 161 114 34i 5 13 -0 123 685 1-l s 15 -11 0 31 90i 5 11 -4 295 213 26
5 10 -18 0 151 98¡ 5 tl 3 458 49s 1{ 5 13 -? 151 231 8l' s 15 -r0 453 448 19 5 1l -3 94 130 06r
5 10 -11 241 250 39 5 11 { 50 214 76i 5 13 -6 659 692 14 5 t5 -9 158 49 88. 5 L1 -2 2IL 2t4 31'
5 10 -16 213 161 41^ 5 t1 5 568 515 11 5 13 -5 116 151 s6¡ 5 15 -8 624 629 L5 5 17 -t 91 29 85i
5 10 -15 28L 299 31 5 11 6 513 5.18 13 5 13 -4 514 511 14 5 15 -l t62 r01 88. 5 17 0 93 130
5 l0 -14 0 169 90. 5 11 1 662 648 16 5 13 -3 178 99 34r 5 15 -6 578 603 15 s 17 1 0 105 88r
5 10 -13 261 251 29 5 11 I 620 618 14 5 L3 -2 101 381 16 5L5-592 157 86. 517291 l0 88*
5 10 -r2 159 86 ô1r 5 11 9 130 16{ 1? 5 13 -1 253 184 24 5 15 -4 {50 161 11 5 17 r 144 138 56i
5 10 -11 201 L12 32 5 11 10 584 580 13 5 13 0 140 151 12. 515-399 90 63. 5174242 223 31
s t0 -10 0 52 18* 5 11 11 139 120 L1 5 13 1 356 373 18 5 15 -2 350 310 20 s1?592 14? I9¡
5 l0 -9 0 23 65* 5 11 12 181 {32 15 5 13 2 291 21L 22 51,5-10 6? 83. 51764r2 345 2l
5 10 -8 240 216 25 5 11 13 291 3r1 25 5 13 3 361 354 L8 5 t5 0 0 5r 83r 5 1? 1 24'l 208 34
5 10 -'t 100 221 16* s 11 14 255 265 28 5 13 1 251 2A5 26 5 15 1 119 51 5l' 5I?8456 438 20
5 10 -6 263 264 22 5 L1 15 0 195 83r s 13 5 203 242 3l 5152252 ra1 21 5 t? 9 281 243 31
5L0-5 1e2 418 t3 5 11 16 68 15? 8?* 5 13 6 505 491 15 s 15 3 0 10 82r 5 18 -9 89 11 91*
5 10 -4 214 23L t9 5 12 -16 2r5 16'1 42) 5 13 1 215 2A5 25 5154283 2A5 26 5 18 -8 0 135 93r
510-3 438 4s6 13 5 12 -15 221 131 3e 5 t3 I 487 463 L6 5 15 5 102 3l 84. 5 t8 -? 160 r28 92t
5t0-2 568 586 1.2 5 12 -t4 171 11? 91. 5 13 9 186 115 38i 5 15 6 408 314 2D 5 18 -6 0 232 93r
5 10 -1 148 707 13 5 12 -13 0 r19 08r 5 13 10 488 169 t6 5 15 1 0 1 8l r 5 Ì8 -5 140 tl5 f 5^
5 18 -4 2r6 302 40. 6 1 -9 114 t1t 51* 6 2 7 89 198 69. 6 4 -15 89 12 91. 652523 508 t2
5 13 -3 2SA 23511 6 1 -8 563 55513 6 2 I 202 161 23 6 4 14 0 31 89' 653612 662 12
5 t8 -2 338 30924 6 1 -l 0 J212* 6 2 9 410 382 13 6 4-t3 89 151 86. 6 5 4 312 351 13
5 1.8 -1 L52 259 9r' 6 7 -6 41r 312 13 6 2 10 335 305 16 6 4 -12 rA3 l.t8 39. 6 5 5 893 866 16
5 18 0 {05 398 2t- 6 1 -5 0 164 68* 6 2 Lr 262 258 20 6 4 -1r l5l 330 20 65641I 475 t2
5 18 I 289 36930 6 I -4 164 A325 6 2 12 SL! 496 L2 6 4 -10 395 435 t8 6 s 1 154 166 18
5 18 2 3 98 31222 6 I -3 96 294L1 6 2 13 218 2't9 20 6 4 -9 593 604 Ì4 6 5 I 410 456 t3
5 l8 3 311 360 23 6 L -2 392 434 11 6 2 14 4ø5 486 14 6 4 -8 118 681 14 6 5 9 855 852 l8
5 18 4 349 333 25 6 I -1 171 85 23 6 2 15 l'19 188 33* 6 4 -? 1013 1003 t6 6 5 10 301 295 18
5 18 5 330 341 21 6 t 0 1048 1065 13 6 2 16 400 388 16 6 4 -6 1141 115 9 1s 6 5 11 614 62A 13
5 18 6 151 22098ù 6 1 r 250 245!1 6 2 11 0 141 7l i 6 4 -5 1113 1094 15 6572200 200 30
5 18 'l 314 299 30 6 l- 2 ].40l 7396 !2 6 2 rg 214 291 23 6 4 -4 1115 1101 1 a 6573452 456 15
5 19 -6 0 151 92i 6 I 3 211 214 16 6 3 -20 116 152 90r 6 4 -3 I22l 1225 LJ 6 5 14 131 90 61r
5 19 -5 't6 113 93r 5 I 4 7655 7632 L2 6 3 -19 141 86 82* 6 4 -2 Lr2r tr04 l4 6 5 15 256 204 24
5 19 -4 0 96901 6 I 5 430 43912 6 3-18 65 231 99¡ 6 4 -1 1109 1152 14 6 5 16 0 19 80i
5 19 -3 135 109 60. 6 r 6 !622 1643 13 6 3 -r'l 183 185 18 r 5 4 0 144 ?60 r6 6 5 lf tt3 36 68.
519-2 118 12 16' 6 1 1 409 432 lJ 6 3 -16 349 322 26 641585 566 t3 6 6 -19 148 118 82i
5 19 -1 0 65 91r 6 1 I 1166 1148 15 6 3 -L5 282 295 3r 642506 498 tÌ 6 6-t8 11 25 53.
5 19 0 0 52 91r 6 I 9 13f 103 69¡ 6 3 -14 161 509 18 643621 65T T2 6 6 -t? 181 ?4 98.
5 19 I t 83 4 92* 6 I r0 ?6-t 751 18 5 3 -13 354 340 2t 644281 242 15 6 5 -16 0 38 93.
5 19 2 0 154 93¡ 6 I 11 211 192 24 5 3 -r2 593 5?1 t4 5 4 5 218 2t'l 2). 6 6 -ls 136 12 93.
5 19 3 139 111 71r 6 I ),2 410 429 14 6 3 -11 49? 194 ts 64649 85 61' 6 6 -\4 122 38 92.
5 19 4 84 199 80¡ 6 1 13 103 20 s0. 6 3 -10 s92 612 T3 6 4 I 160 r61 3ì' 5 6 -13 2rO 144 36r
5 19 5 259 249 35 6 I 14 92 209 '15. 6 3 -9 5'10 512 t2 6 4 8 .74 t1s 59i 6 6 -I2 731 151 86r
6 0-20 240 226 42* 5 1 15 137 35 39¡ 6 3 -8 645 648 15 6 4 9 134 25 13. 6 6 t1 306 360 19
6 0 -18 0 222 99. 6 I 16 67 21 13* 6 3 -1 440 432 t3 6 4 r0 345 t6 6 6 -10 0 I58 83'
6 0 -16 0 118 97¡ 6 1 1l 146 92 39ù 6 3 -6 23'l t60 22 64Lr442 42 t4 66-9630 615 14
6 0-11 182 3944¡ 6 I 18 64 3165' 6 3 -s 442 403 12 64t2369 31 Ìf 66-8269 221 23
6 0-r2 201 163 35r 6 2 -20 0 L6r 99. 6 3 -4 26r 222 L8 6 4 13 5r0 41 t3 6 5 -1 lO49 1063 17
6 0-L0 139 416 16 6 2 -r9 134 46 69i 6 3 -3 36? 355 l2 6 4 1{ 391 40 16 6 6 -6 2'13 2L1 2l
6 0 -a 851 8t5 18 6 2 -rA 0 162 98. 6 3 -2 129 ?04 15 6 4 15 441 42 16 6 6 -5 1353 1320 14
6 0 -6 795 829 11 6 2 -1'l 0 2s 96' 6 3 -1 160 95 25 6 4 16 319 31 18 66-4342 308 16
60-4 t0't2 1118 14 6 2 -76 164 105 92i 6 3 0 11{? 1192 13 6 4 tl 35{ 35 19 6 6 -3 1368 1360 r4
60-2 L627 1510 12 6 2 -I5 8f 94 90i 6 3 1 515 495 1t 64182t4 23 3t 66-2241 239 20
600 1709 1693 1.2 6 2 -11 160 t5 80i 6 3 2 968 955 14 6 5 -19 0 143 99. 6 6 -1 1338 1343 14
602 1226 7240 73 6 2 -r3 116 238 88* 6 3 3 586 571 13 6 5 -18 86 111 9lr 660200 2't 4 \1
60{ a23 192 t4 6 2 -t2 213 272 25 6 3 4 1026 1.045 14 6 5 -11 24r 244 38 6 6 I 1020 1033 15
606 205 168 21 6 2 -LL 389 3?6 18 6 3 5 111 't52 t6 6 5-16 85 13 9 91r 662s2 233 10.
608 583 537 14 6 2 -10 502 4A2 14 6 3 6 1001 987 15 6 5 -15 ll9 33'l 23 6 6 3 505 596 14
6 0 10 231 225 21 6 2 -9 500 518 11 6 3 f '708 't 44 11 6 5 -r4 225 213 35 6640 41 68r
6012 595 51512 6 2 -A 821 81018 6 3 I 151 186 18 6 s -r3 495 534 l8 6 6 s 329 325 L6
6 0 t4 373 36116 6 2 -1 476 481L2 6 3 9 455 455 12 6 5 -r2 332 348 23 666242 225 21
6 0 16 301 303 19 6 2 -6 1241 1211 14 6 3 10 857 858 1l 6 5 -11 119 141 17 6 6 I 30 24 'lr^
6 0 18 312 332 20 6 2 -5 144 662 16 6 3 lI 441 {53 l{ 6 s 10 414 {03 1l 66A432 431 14
6 l. -20 13? 232 1r' 6 2 -4 1355 1388 13 6 1 12 499 511 13 6S-9825 810 20 6 6 9 255 229 22
6 1-19 189 26 9A* 6 2 -3 849 869 14 5 3 13 210 213 28 6 5 -8 440 465 I5 6 5 10 l0l 300 19
6 I -18 366 366 28 6 2 -2 1532 1488 12 6 3 74 231 239 25 65-1841 865 l8 6 6 rr 4f6 434 14
6 1 -17 10 9't. 6 2 -l 961 934 1.3 6 3 15 143 141 76¡ 6 5 -6 306 296 19 6612285 261 22
6 r -16 502 533 19 6 2 0 1235 1210 12 6 3 16 r20 23 18. 6 5 -5 434 185 Ìl 6 6 13 519 s51 13
6 I -t5 238 158 3{ 6 2 I 781 ?85 15 6 3 1f 188 I29 32. 6 5 -4 88 2 1I. 6 6 t4 111 122 Al.
6 1 -14 618 594 t6 6 2 2 A54 92814 6 3 18 0 95 00. 6 5 -3 141 r24 33. 6 6 15 541 52T T4
6 1 -13 50 82 85* 6 2 3 566 528 L2 6 4 -19 143 l9 98r 65-24f 111 6 9. 6616203 t21 33
6 t-L2 132 't32 L1 6 2 4 582 561 13 6 4 -18 14s 68 97r 6 s -1 335 319 14 6611393 390 18
6 1-11 0 62a3' 6 2 5 211 18120 6 4-L1 0 62 12* 6 5 0 193 L99 23 6 l-19 0 199 99r
6 1 -10 681 't!2 16 6 2 6 259 251 18 6 4 -16 56 43 78* 6 5 I 563 560 1l 6 7 -18 16? 13 981
6 't -r'l 315 281 3t 6 0 2 10 81 12* 6 10 -12 180 t19 92. 6 11 lt 284 295 21 6135320 288 23
6 1-!6 0 10 9lr 6 0 3 l3s 738 13 6 10 -11 130 t47 88. 6 \t 12 235 223 33 6 t3 6 516 568 15
6 7-15 454 440 2t 6 8 4 119 185 30r 6 t0 -10 251 263 3r 6 tl 13 t54 131 4l r 6 13 I ttg 160 66.
6 -t -14 r28 591. 6 I 5 292 29419 6 r0 -9 37? 121 20 6 11 14 206 133 36' 6138533 538 1-)
6 I -13 544 5'r3 1l 6 I 6 153 115 3?. 6 10 -8 358 341 20 6 12 -16 r|l s 99. 6 13 9 0 140 89.
6 1-r2 t 91 2039* 6 I ? 0 1875* 6 10 7 554 593 14 6 t2 -L5 r24 19 99. 6 13 10 453 4 65 20
6 I -r1 604 605 14 6 A A 249 260 24 6 10 -6 386 399 18 6 12 -14 114 78 98. 6 13 11 0 105 15.
5 7 -10 0 45 81¡ 6 I 9 {21 383 16 6 10 -5 58{ 665 l6 6 t2 -11 141 51 62' 6 13 12 350 319 25
61-9 645 626 t4 6 I 10 I21 r3A 61' 6 10 -4 s09 528 14 5 t2 -r2 93 221 95. 6 13 13 44 19 89.
6 7 -8 0 13 191 5 8 11 489 485 15 6 10 -3 667 594 16 6 12 -lt 153 24 54' 6 14 -14 Ì60 46 83.
61-1 525 54s 13 6 I 12 78 52 81r 6 LO -2 525 542 t3 6 12 -r0 342 366 25 6 14 -13 13 7 84.
6 1 -6 26r 240 23 6 I 13 464 423 16 6 10 -l 1023 912 l1 6 12 -9 t62 164 89. 6 t4 -12 63 162 91.
61-5 319 30418 6 I 14 0 1282* 6 10 0 812 g3i 20 6 12 -8 495 484 tl 6 14 -tt 0 l3 96r
6 I -4 460 463 13 5 8 15 335 331 22 6 l0 I 550 635 16 6 12 I 149 358 22 6 t4 -10 369 344 25
61-3 0 3)'t1. 6 8 Ì6 84 44 58¡ 6 l0 2 533 529 t3 6 t2 -6 660 644 l5 6 14 -9 16 41 92.
6 i -2 554 5{4 12 6 9 -r3 0 137 99. 6 10 I 530 44C ìl 6 14 -8 569 514 1l
6 ? -1 481 449 12 6 9 -17 331 283 31 6 10 4 304 3r1 20 6 12 -4 159 ll8 tl 6 t4 I 0 19 92.
610 438 451 13 6 9 -16 226 153 43r 6 10 s 119 156 34i 6 l-2 -l 465 415 t6 6 14 6 ll4 153 18
611 905 919 16 6 9 -15 410 420 21 6 l0 5 r21 226 80r 6t228I2 818 t5 6 14 -5 125 32 A1.
612 135 7970. 6 9-14 306 2423î 6 10 7 0 t2l 81r 6t213E9 432 19 6 14 -4 188 769 tl
613 106? 10'10 l5 6 9 -Ì3 414 501 27 6 10 I L32 87 68i 6L20lll 124 16 6 14 -3 r05 f5 f2.
514 0 61 'tr. 6 9 -r2 l'12 25L 92r 6 l0 9 159 l't 6 42ù 612t1r5 t05 82. 6 14 2 f90 199 ll
615 1l0f 1121 15 6 9 -lr 4?6 4?6 16 5 r0 r0 1lf 114 3 8. 6122526 521 l4 6 14 1 11r 55 81.
616 136 11 3lr 6 9 -10 250 193 2E 6 10 11 295 21L 24 6t230 85 19. 6 14 0 5r0 518 16
611 l0? 6 1063 l7 6 9 -9 436 425 t1 6 t0 12 0 151 86r 6t24346 360 20 6 14 ì 1ll 58 41.
618 0 113't4. 6 9 -0 145 109 44r 6 IO 73 214 213 21 6t250 130 61. 6 t4 2 296 325 25
619 868 8?7 19 6 9 -1 325 3r4 20 6 10 14 154 126 85i 61260 41 B?. 6 t4 3 84 22 84.
 1 10 102 155 78r 9-6 o 39 11. 6 t0 15 211 249 28 12 1 0 26 84 r 6 14 4 301 290 25
1 11 666 679 I4 9-5 14 121 11r 5 tt t6 I35 246 13. 128 0 t2a 84. 6 14 5 0 35 85r
f 12 120 159 53* 9-4 250 \46 23 6 11 -15 268 25t 3'l t29 I66 66 85 r 6 14 6 62 26 13'
1 13 318 300 27 9-3 111 185 52r 6 11 -14 323 310 30 12 l0 251 243 32 6 14 1 38 95 8E.
1 t4 18 111 81* 9-2 253 225 22 6 11 -t3 352 339 26 12 t1 0 132 09r 5 14 8 60 83 89r
1 t5 120 t63 69* 9-t 4?9 463 t4 6 II -t2 211 325 32 12 t2 2t8 289 30 6 t4 9 0 Ì04 92.
1 16 0 16 84r 90 245 r93 2J 6 11 -11 382 390 23 12 t3 56 233 92r 6 t4 t0 t1 4 22t 49^
1 1? 32 44 62r 91 830 E?2 t9 6 11 -10 250 2\9 32 t2 t4 311 289 24 6 Ì4 l1 I16 100 91.
I -18 0 19 99. 92 117 1? 0 15 6 tl -9 351 355 22 13 -15 213 1Ì 4 46. 6 14 t2 265 3I1 34
I -1? 138 101 99i 93 1129 1144 l-t 6 11 -8 17 236 A6. t3 -14 214 214 36 6 15 -t2 3I9 323 32
8 -16 0 3't 98r 94 5{r 53r 12 6 7L -1 26t 235 21 13 -13 r29 t19 98. 6 15 -11 o 44 91.
0 -15 0 45 95* 95 t224 a207 l'l 6 11 -6 134 166 69. 13 -12 369 384 26 6 15 -10 396 405 25
8 -1{ 0 56 71* 96 393 396 17 6 11 -5 0 l{ 61¡ 13 -11 721 140 93r 6 15 -9 103 12 95r
I -L3 2L5 L62 38r 91 1ls9 1.153 l7 6 11 -4 0 26 øO. 13 -t0 438 416 2T 6 15 -8 309 351 30
I -12 106 57 88* 98 432 4r2 16 6 rt -3 181 198 35. 13 -9 80 155 90. 6 15 -1 o 42 93*
I -11, 338 362 23 99 636 61{ 11 6 11 -2 106 117 6 0. I3 -8 162 451 19 6 15 -6 200 208 4ri
I -10 t27 23 01¡ 9 I0 2A3 252 23 6 1r -1 6rr 602 14 1l -1 L21 61 61. 6 15 1?1 10 80.
8 -9 539 533 1{ 9 l1 449 421 L6 6 tl 0 135 109 16 l3 -6 246 239 32 6 L5 -4 53 59 62r
I -8 194 t35 32 912 135 209 82. 6 11 1 583 626 L5 13 -5 0 82 05r 6 15 -3 r39 36 a6.
I -1 't68 113 1{ 9 13 30 205 81r 6112199 534 t4 13 -4 56 54 3r 6 1s 92 t45 89'
I -6 250 243 24 9 11 0 125 84i 6 11 3 106 643 15 t3 -3 208 t90 { 6 15 -Ì 135 120 13.
8 -5 1055 1079 17 915 t26 99 84r 6 11 4 t50 11T L6 13 -2 42 1a 3. 6 15 0 258 303 30
8 -4 216 18{ 26 9 16 o 't9 86. 6 11 5 683 6€0 1l 13 -1 365 319 0 6 ls I 0 34 90.
8 -t 1150 r16? 16 IO -I7 1t4 t22 99' 6 11 6 658 64{ 14 13 0 442 431 't 6 15 2 198 388 20
I -2 t21 12 't 2. 10 -16 12 44 98* 6 1t 1 411 503 Ì6 13 I 299 310 4 6 15 3 0 I 8?.
I -t 1232 1230 t0 -15 0 ?l 99r 6 lt 8 515 574 15 l3 2 416 411 6 6 15 4 4I1 423 21
8 09538 71¡ 10 -14 0 49 9{r 6119122 431 t 9 13 3 t62 220 82i 6 15 0 16 88r
I 1 t1{0 1138 16 10 -13 t20 16 l8r 6 lt 10 400 319 t9 l3 4 556 55? 15 6 15 6 537 518 t?
15 7042 90i 19 -1 191 114 4?* 7 1 1l 0 lt 79. 921 965 t7 75 -18 0 I02 99r
t5 0 391 140 24 0 -10 771 4 0 61. 7 2 -r9 l9l 41 55¡ -1 594 613 l5 l5 -17 r92 225 99.
15 9 t21 t22 93i 0 -16 0 118 99* 7 2 -18 108 20 99. 0 901 961 17 -16 133 158 99.
15 10 358 379 26 0 -14 266 234 35 1 2-t1 75 131 7?. I 629 616 14 l5 296 32r 31
t6 -11 133 23 81r 0 -L2 341 3A6 25 1 2-t6 0 81 98. 1090 1033 t5 15 -14 0 180 99r
16 -10 2't3 253 35 0 -10 603 544 15 1 2 -15 t25 223 99' 3 105 125 14 l5 -13 341 353 28
l-6 -9095 9't I 0-8 851 ø39 20 1 2 -L4 tI2 213 96. 1 922 94r 17 15 -i.2 6't 156 9lr
16 -a 335 3 93 29 0-6 976 959 18 1 2 -t3 711 295 28 5 57t 5¡6 13 '75 -11 3t8 306 26
16 -1 239 r7'l 31 0 -4 1osl 1049 1? 1 2 -r2 395 1J0 22 6 851 83 8 18 -10 r92 166 41r
16 -6 1{8 {83 2t 0-2 1077 1021 16 I 2 -11 115 382 19 1 251 283 15 -9 0 180 8f*
16 -5 211 201 39* 00 675 630 14 f 2 -10 591 616 15 8 119 160 t4
-t5 -8 81 80 60r
16 -{ 536 530 1? 02 L06 144 12' 12-9362 310 20 9 355 323 tl -1 282 29a 25
l6 -3 310 231 26 04 259 301 2t 12-8866 8?9 15 IO 356 365 18 ?5 -6 165 t5l 39¡
I6 -2 526 s42 18 06 112 154 19 12-1340 341 19 11 0 16L l8' l5 448 458 1s
16 -1 248 107 33 08 450 483 l{ ? 2 -6 8r0 gt4 20 \2 0 105 1A. l5 4 226 t66 26
-708
16 0 485 474 t8 0 10 723 108 15 f2-5644 588 15 13 0 29 80. l5 l 648 16
16 1 0 14{ 9li 0 t2 491 471 13 12-49r3 91t l7 14 161 131 31. l5 -2 o 222 16.
16 2 33L 321 25 0 1{ 454 4?0 15 7 2 -3 555 616 13 1.5 ì49 2l 00. l5 -l 612 619 15
16 3 108 135 91* 0 t6 359 371 Ì9 12-21r4 662 14 16 251 245 26 l5 0 363 346 16
16 4 0 1?9 94i 1 -19 43 50 l9r 12-r452 432 13 -19 160 31 99. 15 I 6t2 60L 12
l6 5 203 L12 42* 1 -18 220 325 f 2 0 366 349 1s -18 0 \2 8?. 2 308 295 18
16 69129 92* 1 -11 149 86 'tr
99i 't 2 1 133 116 l1. -11 190 111 53^ 3 11 I 111 19
16 7 0 181 96i r -16 3?0 383 28 122249 2t3 78 -16 0 59 99. l5 A 401 405 15
16 I 1.54 203 80* I -15 142 53 96* 't 2 3 204 t54 26 -15 259 230 31 f5 5 136 146 15
16 90151 96r I -14 392 394 24 1240 90 12r -14 Ì31 202 42. l5 5 359 352
.103
17
17 -9 0 119 9'1. I -13 153 20 92r 1 2 5 436 429 14 -13 391 432 24 75 1 r13 15
-8 0 186 98* L -t2 356 335 21 't26493 485 13 -L2 422 396 20 75 8 216 188 28
1l -1055 96r I -11 121 16 86. 127495 500 12 -ll 624 618 t5 l5 9 510 485 14
17 -6 149 148 92t 1 -10 245 170 30 1 2 E 504 484 13 -t 0 501 502 t6 15 10 0 88 19.
7'l -5013 94* 1 -9 141 L2 83. 129216 243 23 -9 817 821 16 15 I1 265 241 2s
1'l -{ 136 't4 62ù I -8 1,63 L22 40. 1210104 683 15 -8 695 145 l4 l2 t22 61 68.
17 -3 97 119 94* 1-7 t48 r24 4L. l 2 t1 333 346 t9 842 837 2I I3 0 I 85¡
1l -2 51 31 92. 1-6 311 364 20 1 2 t-2 599 591 11 -6 59? 589 14 ?5 14 145 63 81r
T1 -1 182 190 4 8r 1-5 0 36 ?7* 1213249 228 25 -5 192 162 14 75 0 102 84.
I1 0 171 219 5oi 1-4 025 801 19 12L445! 4?0 16 -4 5?0 587 t4 L6 r28 to't 82.
1-t I 212 246 32 1-3 0 ?4 73i 1 2 t5 14 L1t 82. -3 561 551 l3 16 -18 0 t4 99r
1? 2 316 355 29 1-2 r2?0 131r r5 7 2 16 351 317 19 -2 42r 384 14 16 -11 o 12 99.
17 3 244 2L2 31 1-1 2'18 21't t9 12L]230 20a 29 -t 101 170 l5¡ 't6 -16 210 69 31
1l 4 387 408 25 t0 1454 1455 14 7 3 -19 199 131 9 9. 0 240 28â 22 16 -15 t96 226 99.
1l 5 265 260 34 11 332 313 16 7 I -18 260 2L1 1l 1 Ì58 82 33. 't6 -14 40 127 98r
17 6 {08 417 24 l2 1549 1525 14 7 3 -17 157 184 99r 2 131 33 l0¡ 16 -t 3 493 481 20
1l I 338 330 2A t3 350 313 16 7 3 -16 358 317 29 3 151 14E 32. 16 T2 0 184 93¡
t8 -1 137 I88 81r 14 1145 1437 14 7 3-15 9l 186 99r 4 0 't2 l6 -1.1 694 616 16
t8 -6 215 255 33 Ì5 3t't 269 tE r 3 -t4 321 370 30 5 44s 423 14 16 -10 224 185 35
18 -5 251 209 35 16 1r05 1073 16 ? 3 -13 1¡5 183 93. 6 26). t92 21 16 -9 920 923 22
1.8 -{ 316 291 2ø l7 0 3? ?4. 1 3 -r2 245 214 30 1 511 516 14 16 -8 211
26 206
10 -3 256 262 35 18 531 s23 t2 ? 3 -11 230 210 33 I 4 ô8 454 13 16 -1 1006 1024 20
18 -2 l{1 336 21 19 L24 52 43r I 3 -10 Ì86 l8 4 41r 9 't40 710 15 -6 215 250 24
18 -1 314 288 29 r 10 400 413 15 I 3 -9 159 110 I4. 10 553 58 0 I3 16 -5 830 801 20
18 o 126 291 28 1 11 0 15 ?6* 7 3 -8 10? 95 62. TI 63r 6L4 I4 16 -4 232 r52 21
18 | 210 299 34 1 12 0 5I 76. 't 3 -'l 112 22 51. 5 41 530 14 f6 689 651 r5
18 2 242 226 38 113 83 51 11r 13-6420 460 16 13 539 s42 15 16 160 89 37r
18 3 r6t 252 83i 1 14 14-l 64't5. 7 3 -5 104 89 78i l{ 399 393 18 16 -1 393 3'16 16
18 4 0 19 81. 115 0 50 79r l 3 -4 644 652 15 15 386 2l 16 0 toz 11 16.
18 5 6{ 1-r8 98* 1 15 lL2 r29 51. 't 3 -3 214 211 2r 16 158 220 83 r 16 1 65 48 ?4.
6 2 242 252 24 I -11. 491 488 19 l 9 11 101 59 85* 11 5 526 507 16 I 13 6 51{ 4lt 18
6 i t23 t02 75* I -10 98 35 69* 19I20 90 l3r 11 6 439 500 19 l 13 .T
191 t34 44.
5 4 284 219 20 8-9 618 609 15 7 9 13 0 10 87* 1l 1 348 364 23 l 13 I 3AO 424 25
6 5 382 386 16 8-8 83 116 66. ? 9 14 0 44 89r 11 8 326 321 24 I 13 9 155 81 55r
6 6 534 505 13 8-1 132 753 1.8 7 10 t6 0 't2 99' 11 9 268 224 29 7 13 t0 3ta 290 28
6 7 594 s60 t4 0 -6 t50 129 41r 7 t0 -15 154 84 69. 11 10 114 186 46. l 13 11 98 12 93.
6 I 115 391 16 8-5 841 801 21 ? 10 -14 0 151 99r tl 11 150 43 52. 1 t4 12 2A2 326 4I
6 9 122 693 16 I -4 r4't ?4 81r I 10 -13 68 183 99r 11 L2 220 125 )6 I 14 11 128 l0 99.
6 10 304 290 22 8-3 699 692 11 1 to-t2 0 188 991 11 ll 0 94 90. 1 14 1 4fI 496 25
6 lt 710 746 18 ø-2 251 L43 24 l 10 -11 293 21t 33 t2 -I4 0 2t5 99. ? t4 180 44 99.
6 12 0 117 03r 8-1 674 513 14 l 10 -1.0 141 230 94. 12 -13 153 60 99r 1 14 5s8 560 20
6 73 612 641 16 80 245 248 25 l 10 -9 489 441 18 t2 -t2 306 315 35 7 14 6t 22 91.
6 t4 0 115 86. 81 188 155 33 i 7 10 -8 349 309 24 12 -tl 180 140 99r I 1{ 564 543 18
6 15 439 43? l8 s2 334 336 20 I 10 ? 507 503 18 l2 -10 422 42r 25 ? 14 0 46 9lr
6 16 150 117 85r 83 l5 6 159 39r 7 10 -6 410 428 18 t2 -9 214 215 35 7 14 52J 496 18
1 -18 169 1 86* 84 287 230 22 7 10 -5 538 s35 ).5 ).2 8 502 511 20 I 14 116 10 92'
1 -r? 0 2't6 99* 85 413 401 L6 ? 10 -4 450 399 1? 0 249 96. l 14 285 286 30
1 -16 0 15 99i 86 253 264 26 l 10 -3 594 566 L4 t2 -6 633 586 t5 1 t4 111 23 41.
1 -15 {06 341 8f 644 620 r4 I 10 -2 654 659 15 300 186 21 I 14 98 121 90r
1 -14 0 3? 99* s0 0 11 81r 1 to -I 312 380 20 t2 -4 556 552 tl I 14 146 66 88.
1 -13 347 311 89 5ø2 539 14 l 10 0 369 360 20 t2 -3 206 19t 38. f t4 0 82 90r
1 -12 154 t0 56* 8 10 51 13 83. ? 10 I 166 264 S5* t2 -2 449 501 18 1 14 9t 54 16^
1 -11 235 196 36 8 11 523 535 16 f l0 2 \49 151 83. 12 -1 13 29 88, l 14 126 109 91r
1 -10 15 t4 I8* 8t2 t27 31 64' 7 10 3 140 t04 82r L20 302 208 25 I 14 0 106 92.
'l -9 111 4t 88i 813 371 319 22 f 10 4 136 31. 6 9. 12 1 131 3 12. 1 14 180 259 96.
7 -8 16-7 65 864 I 14 190 53 39r r 10 5 289 3 05 25 722 131 98 53r l 14 25 l8 93.
'l -7 299 286 25 I 15 315 331 25 I 10 6 11 :.18 8 4. 123 t 43 6t12. tt4 40t 401 24
1 -6 159 129 44t 9 t? 265 42 1101365 154 2r 124 \24 150 61. l 14 t3 8 A4 96'
-s 51i 589 13 9 -16 0 13 I t0 I 149 0 99 01. I t4 43t 452 24
1 -4 122 rl2 53. 9 -15 213 29 39 I 10 9 380 351 2I 126 310 269 24 I t5 140 l0 99'
1 -3 803 82t 20 9 -I4 0 t2 99r I 10 10 246 2Ì1 31 \2 1 204 tl9 38. l l5 0 143 99'
1 -2 61 113 19. 9 -13 122 24 84* l t0 11 rl0 349 22 t28 3 85 3t2 22 7 t5 9 0 13 99.
1 -r 1156 1132 1l 9 -rz 32 9 98r ? 10 12 181 193 44. 12 9 236 227 36 r ì5 8 0 14 99.
1 128 55 64. 9 -11 53 t6 80r ? 10 13 268 291 3Ì 12 t0 396 3tt 22 l 15 -l 85 26 99'
1 t2tt 1262 tl 9 -10 0 4 92r f 10 14 0 tl6 90r 12 1Ì 3t4 283 28 l 15 -6 88 98 96'
't 198 100 30 9 -9 85 66 90. 1 \t -Is 212 206 53r 12 t2 391 380 24 r 15 -5 209 l5 4l'
'l 1041 1081 18 9 -8 80 43 13. I I1 -14 132 l-68 99f 13 -13 168 89 65. l 15 o 2r8 99.
1 110 8l 9-l t29 89 66. I It -13 215 2L4 414 13 -12 112 203 64. I t5 54 64 93.
1 953 934 19 9 -6 116 60 85 r 1tI120 104 84. 13 II 144 12 99. I t5 2 2)9 300 32
1 219 195 ?1 95 337 353 22 7 ìt 11 0 150 99. r3 -10 t {l r82 99¡ l t5 1 0 3l 951
 't 2r 150 16 't 9 -4 0 t12 A4. 7 11 -10 16 62 9Ar 13 -9 121 5 ?5. I 15 0 369 366 24
78 198 251 33 1 9 -3 s72 550 14 7 11 -9 t02 13 92. 13 -8 86 91. ? 15 1 0 17 93r
19 535 542 t4 1 9 -2 231 r48 2ø I 11 -8 168 la 91i 13-10 14 91. 1t52365 312 26
7 10 11 110 81i 7 9 -1 943 961 20 7 11 --7 183 188 {6. t3 -6 185 18 48. 7 15 3 108 l4 78r
7 11 234 189 28 'l 9 0 4!0 412 11 I 11 -6 0 104 91i t3 -5 252 20 34 11544A3 418 2l
112 ll1 91 81i 1 9 1 1030 1004 19 l 11 -5 292 311 28 t3 -4 322 30 21 I 15 5 35 81 92i
7 13 t3I 42 8L. 1 9 2 431 46916 l 11 -4 280 324 28 ).3 -3 350 36 24 7 15 6 366 363 21
7 14 0 24 861 1 9 3 945 9?120 l 11 -3 5f I 567 l5 13 -2 414 49 t9 ? 15 I 184 166 91.
? 15 69 91 12* 1 9 4 432 46311 1I1-2 4 90 490 l7 13 -1 35{ 261 23 l 15 a 214 282 31
E -17 0 6f 99. 1 9 5 915 90321 I t1 -1 6t2 621 14 13 0 5r2 5r2 Ì? ? 16 -9 149 145 86.
I -16 0 30 86i 7 9 5 363 40620 7 11 0 699 699 ls 13 r 268 225 30 ? 16 -8 353 350 31
I -15 154 213 99r I 9 I 378 405 t9 l 11 1 583 580 14 13 2 5Ì5 536 ll I t6 -1 I'tI I52 99"
8 -14 Ì08 15 9lr 1 9 A 24t 22429 l Lt 2 113 l5{ l6 13 3 254 251 32 I 16 -6 310 318 2A
I -13 361 71L 21 1 9 9 232 25132 l 11 3 612 626 14 13 { 579 592 16 ? 16 -5 100 146 98.
a -t2 0 20 95. 7 9 r0 0 t75 85r 7 tl 4 534 624 t4 t3 5 83 2r1 91. I 16 -4 354 346 21
16 -3 25 r13 96r 8 t -3 370 314 t9 8 3 -t6 114 163 81. 46651 653 14 I 5 -4 158 \82 44ù
).6 -2 281 301 l3 ø 7 -2 1283 1361 lt I 3-r5 32 60 99. 4 I 866 841 2l 86-3260 234 2A
16 -1 132 102 95i 0 1 -t 36t 322 t8 8 3 -t{ 107 78 99r 48631 655 15 g 6 -2 0 2'l 83.
160 141 t22 96' 8 1 0 t2S1 t243 t'l I 3-13 201 43 49r 4 9 112 7r3 18 I 5 -1 0 46 83r
16 t 0 11.3 96. 8 1 | 324 23020 I 3-12 193 64 49. 4 10 543 510 15 I 6 0 149 226 84.
16 2 164 13 94* I 1 2 1163 1104 18 8 3-11 136 25 94r 4 11 5?6 580 86L225 zA't 37
16 3 L70 131 96r 8 I 3 115 156 81É I 3-10 285 259 3t 4 12 344 34 4 23 862243 245 2A
15 { 1?4 112 54i 8 1 4 740 744 15 8 3 -9 0 129 93. I 13 364 34 9 2l 8 6 3 584 603 13
16 5 0 105 97r I 1 5 107 24 80* 8 3 -8 506 593 r8 { t4 119 164 81. I 6 4 409 355 1l
16 5 368 363 28 I I 6 182 215 35r 8 3 -l 238 282 33 { 15 196 225 38r I 5 5 185 181 t6
16 'l 185 59 99r 8 1 I 0 t219' I 3 -5 621 690 11 5 -1? l3l r55 99. e663'll 362 2T
!1 -1 0 92 99r I 1 I 196 205 31r 03-5 115 180 1l 5 -16 0 16 99. 061841 891 15
11 -6 135 61 84r 8 1 9 41 3957* 0 3 -{ 908 901 20 5 -15 121 118 89. 8 6 0 246 249 29
17 -5 0 110 99r 8 t 10 231 201 29 03-3 618 660 15 5 -14 128 3{ 99r 869828 819 17
r', -{ 0 119 99¡ I
0
r 11 0 8384i
1 12 148 221 85'
83-2
83-1
861 923 2t 5 -13 130
5 -t2
54 99. 8 6 10
E 6 11 598
0 r2\ 87r
1? -3 244 227 39 585 603 13 66 13 70r 621 15
!1 -2 261 302 30 8 1 13 93 2AA4. 830 951 q61 19 5 -ll 0 54 91. I 6 12 89 I23 86¡
1.7 -l 351 290 26 8 1 11 288 2't3 25 83t 634 616 r{ 5 -10 t38 41 95r I 6 13 380 104 23
17 0 4r5 4t1 25 I 1 15 11 2884. t32 830 81I 2l 5 -9 299 310 30 I 6 14 0 r21 8lr
11 I 260 252 39 I 2 -18 ts8 116 99. 833 117 435 t7 5 -8 0 234 9{r I 7 -16 0 23 99i
1? 2 135 429 24 I 2 -t1 206 158 99* 834 686 680 16 5 -l 414 426 20 I 7 -15 178 90r
17 3 330 285 31 a 2 -L6 0 226 99. 835 156 181 81. s -6 256 301 3l I ? -14 0 11 99i
1? 4 32I 364 32 I 2 -15 148 179 88r 836 411 480 l5 5 -5 569 560 l5 I I -13 198 I 99r
0 -18 69 138 99. I 2 -t4 334 340 33 831 201 t98 32 5 -4 342 163 22 I 1 -12 132 38 llr
0 -16 l0r 221 99r 8 2 -t3 226 269 45' 838 126 89 82. s3605 649 13 I ? -11 0 114 98r
0 -14 234 301 46. 8 2 -r2 40A 466 23 839 151 82 E0* 524r9 {04 18 I l -10 0 90 96r
0 -I2 318 436 26 I 2 -11 330 313 2l I 3 10 0 88 83r 5 -r 638 621 t5 81-9125 323 28
0 -10 551 552 11 I 2 -10 573 5?l 1l I 3 11 20 61 84¡ 50355 346 20 I f -8 0 r29 95.
0 -8 693 ?15 16 g 2 -9 3rO 282 27 I 3 12 160 293 81. 5 I 122 168 I6 8 7 -? 5s? s63 t-)
0 -6 645 674 t5 6 2 -8 498 539 18 I 3 t3 0 106 84r s2335 314 20 81-6t21 14 15.
0 -4 668 573 14 8 2 -1 379 396 2l I 3 14 322 339 24 53737 l5 5 I6 8 7 -5 649 685 l4
0 219 t65 21 I 2 -6 503 510 16 8 3 15 134 t25 85. 5 4 280 25'1 24 I f -4 84 30 87i
0 0 262 202 25 g 2 -5 36Ã 326 20 I 4-11 14{ 209 99* 55581 591 14 I f -3 901 940 l6
0 591. 512 13 I 2 -4 380 340 19 I 4-16 0 191 99i 560 103 84. 81-2202 12 3 6r
0 4 158 810 15 I 2 -3 t34 88 82r I 4-15 198 332 99a 51296 284 24 8 7 -1 1065 113I 27
0 6 689 611 1-t I 2 -2 t43 681* I 4-14 33? 295 33 5 I 144 44 83. I 1 0 81 84 85¡
0 I 615 605 15 8 2 -1 312 281 2r I 1-13 466 163 23 590 t3 84. I 1 I 91t 9'l 4 22
0 10 517 523 15 a 2 0 61 118 80* ø 4-t2 346 392 29 s t0 202 ll3 36. 8720 55 84.
0 T2 437 {28 18 a 2 1 403 418 l? 8 4-II 509 554 20 51190 208 88 r 8 ? 3 180 188 t6
0 1{ 211 291 21 a 2 2 40't 435 r'l I 4-10 465 198 2r 5 12 209 140 36r 8?40 t22 84.
1 -18 216 1?3 43 I 2 3 583 61013 8 4 -9 600 59? 17 5 13 136 244 90. 8 I 5 585 519 14
1 -t1 0 11 99* 8 2 4 629 66øt4 I 4 -8 369 380 23 5 14 12s 155 87. I 1 6 191 246 38r
I -16 111 13? 99. I 2 5 580 583 13 I 4 -l 508 500 17 6 -t1 2tO 226 51. I I I 306 282 24
1 -15 145 13 E6r ø 2 6 684 6911? I 4 -6 269 250 29 6 -16 0 11.7 99r E I 8 131 46 85.
I -14 0 93 99r a 2 7 3t6 25121 I 4 -5 102 18 6 -15 343 3r 9 35 I I 9 130 54 86.
1 -13 92 5 99r I 2 8 725 59916 I 4 -4 9'l 110 84i 6 -14 0 145 99r I I 10 0 l0 88.
I -12 161 59 57r 8 2 9 423 445r8 I 4 -3 204 I09 33 6 -t3 500 500 23 I I tl 124 r29 8lr
1 -11 1r1 16 53r I 2 10 608 591 13 I 4 -2 139 62 8t. 6 -t2 t91 t61 99. 8t12I29 41 89*
1 -10 291 203 30 8 2 11 306 299 23 0 4 -1 209 82 30 6 -11 603 588 18 a1132A1 231 2â
I -9 0 36 91* I 2 t2 400 400 19 040 295 259 22 6 -10 0 202 99. I 7 Ì4 0 I2 90.
1 -8 504 514 17 8 2 13 260 251 28 841 249 28t 26 6 -9 602 645 1l 8 8 -16 145 23 99^
I -1 t 13 1ø 66' 8 2 14 22L 263 74 842 312 396 lE 68332 286 26 I E -r5 155 214 99¡
1 -6 196 83't \1 8 2 15 211 255 21 843 519 522 t4 6 -1 524 4A2 1t I 8 -14 0 22 99.
1 -5 163 171 11r I 3 -18 0 139 99i 844 4 90 501 1s 6-665 208 89. I I -13 364 344 31
1 -4 t22L 1215 18 0 3-tl 0 7399r 845 ?08 ?35 16 6 -5 442 410 t9 I I -12 99 t6 86a
I -11 382 416 29 8 10 -13 0 186 99* I 12 -10 3 95 l9L l0 14 3 133 92 98r 9 1 -6 882 90 9 18
I -10 t12 50 99r I 10 -12 136 148 99* ø12-9 183 t52 99. 14 4 433 441 24 91-5255 223 33
I -9 416 506 21 I 10 -11 310 2?l 35 I 12 -8 {10 317 21 t4 5 0 64 991 9 1 -4 913 934 ll
I -8 0 52 95* 8 10 -10 295 230 3'l s12-1 0 I9 99r 14 6 503 521 9I-3246 222 2S
I -1 5t 6 509 19 I I0 -9 382 355 28 aL2-6 392 349 21 14 7 0 32 99* 9l-261J 1L3 l6
I -6 t6'l 17 91* 8 10 -8 251 290 47 I 12 -5 l.03 99 82r l5 -8 42 198 92. 9 1 -1 0 165 88.
0 -5 1{1 403 20 I 10 -7 3?8 348 26 øt2-4 2J5 21ø 1t* 15 --7 0 40 99. 9 1 0 555 552 16
I -4 r62 39 89r 8 10 -6 269 23I J5 I 12 -3 2'l 14 9li 15 -6 16l 282 99. 9110 r28 89.
I -3 283 251 28 8 10 -5 369 216 25 8t2-2 171 34 94. 15 -5 0 6L 99r 912352 211 22
8 -2 0 100 8?i 8 10 -4 379 245 28 812-1 0 21 95r L5 -4 322 354 35 9 I 3 155 26 66.
I -t 198 171 37r 8 10 -3 197 54 43r I 12 0 0 rr? 96. 15 -l 0 3t 99. 9 1 4 64 04 86.
I 0 165 106 85. 0 10 -2 133 112 91. 812 1 0 38 93. t5 -2 310 3?5 29 9150 r4 8S.
I 1 402 42t ).9 8 10 162 E0 91r 8 t2 2 324 296 21 15 -l 0 48 97r 91649 69 88.
I 144 t77 83r 8 10 0 146 152 75i 8123 293 I12 30 15 0 361 359 29 9 I f 103 99 61r
I 3 596 5?9 14 8 10 | 331 30t 24 8124 416 401 23 t5 | 125 100 99r 9 r I 365 394 23
8 4 93 t{8 84. 8 t0 2 249 256 33 a125 Ì3{ 184 94r 15 2 463 405 23 9ì90 48 90r
8 5 149 148 11 8 l0 3 4r2 4tO 2l BT26 461 413 21 15 3 ).81 120 55' 9 r 10 435 415 20
8 6 6L {4 85. 8 10 4 306 261 26 812 1 204 243 45^ 15 4 244 29L 44. 9 I Ì1 0 24 88.
I 1 55 9 510 t 5 I 10 5 420 450 20 I 12 8 430 43L 24 15 5 189 ll5 99r 9I1246l 454 19
I I 0 32 13. 8 r0 6 25't 2SO 3t ø129 269 232 36 15 6 r44 143 )2À 9 1 t3 ll2 41 90f
0 9 592 584 16 I 10 l 431 318 20 I 12 10 3 96 4 01 25 t6 -6 r03 220 99r 9 2 -16 235 250 54.
t 10 0 39 92' 8 t0 a 220 231 3A' 8 13 -1r r51 '13 99r 76 -5 122 38 99. 9 2 -15 llf Ì88 99¡
I 11 390 399 22 8 10 9 355 360 26 8 t3 -t0 23r L24 50. 16 -4 0 138 99¡ 9 2 -r4 239 295
I 12 0 43 89* 8 10 l0 r59 204 92' 8 13 -9 196 119 99. 16 -3 12r 4r 99. 9 2 -L3 260 239 45.
I 13 301 341 29 8 r0 11 281 289 3r I 13 -8 t66 266 68. L6-20 39 99. 9 2 -12 3r2 3Ì3 31
9 -15 180 75 99r 8 10 Ì2 16't 206 96. 0 13 -? r52 142 10. 16 -1 105 4A 12. 9 2 -11 238 2lJ 45r
9 -14 t89 21 60. 8 11 -14 184 32 99. I 13 -6 3L8 366 34 16 0 2r2 183 49r 9 2 -t0 219 235 38
9 -13 0 I 99* I tl -13 0 31 99¡ 8Ì3-5 216 208 16 I 0 65 99. 9 2 -9 158 240 99.
9 -t2 0 14 99. I 11 -12 176 lt 65i I 13 -4 485 495 22 15 2 334 291 3l 9 2 -8 0 rl5 99r
9 -11 105 14 99. 8 11 -11 92 19 14* 813-3 250 2r2 31 16 3 63 92-1r49 156 80r
9 -10 145 66 11. I r1 -10 t78 68 99* I 13 -2 512 414 20 0 -16 0 211 99. 9 2 -6 0 I 95 *
9 -9 261 234 31 8 11 -9 t8z 252 59. 8 t3 -1 2'l o 188 35 o -14 269 263 45' 9 2 5 159 15 53*
9 -8 183 180 96r I 11 -8 184 119 99r I 13 0 496 505 20 o 12 342 280 l4 9 2 -4 91 228 94.
9 -1 455 413 22 I 11 I 318 356 33 I 13 I r62 210 8l . 0 -10 124 105 ll 92-3242 254 34
9 -6 263 299 35 I tl -6 339 3s1 29 8 13 2 506 sI2 20 0 -8 251 2ro t9 92-2336 341 24
9 -5 641 664 16 I 11 -5 504 {95 21 8 1l 3 96 195 98. 0 6 8t 41 95. 9 2 ì 150 140 23
9 -4 33 9 294 25 8 11 -4 425 461 24 I 13 4 349 369 28 04299 380 29 I 2 0 525 540 l?
9 -3 934 962 t1 0 11 -3 598 599 17 I 13 5 0 19 99. 02533 561 l6 9 2 I 450 499 19
9 {43 410 20 I 11 -2 631 639 16 8 13 6 299 215 32 0 0 619 682 t6 922661 685 t6
9 -1 859 887 18 8 tt -1 501 461 t9 I 13 1 206 1t
45. o 2 123 lt9 I5 92152f 486 16
9 0 322 332 25 8 11 0 513 592 1? I 13 I 117 121 l5 r 0 4 516 589 l6 924696 lt5 L6
9 1 805 ??8 1l 8 tt I 5t6 503 t8 I 13 9 0
-70 99r o6466 448 t9 925238 248 l3
9 2 259 312 30 8 tl 2 415 451 19 I 14 -10 410 381. 3t 08566 518 t6 926654 626 16
9 3 580 562 t5 8 11 3 4r3 380 22 I 14 -9 122 1-t 99r 0 t0 320 321 21 9 2 I 400 422
9 4 2ø5 244 21 8 11 4 29t 344 30 I 14 -8 368 322 32 0 \2 242 195 34 928522 508 ìl
9 5 318 268 25 8 t1 5 t42 222 95r I 14 -? l4 88¡ I -16 1?6 28 99. 929251 294 3l
9 6 30 r02 86¡ I 11 6 36 168 95r 0 14 -6 242 268 45. I -15 0 I 85' 92t0243 294 29
9 1 128 89 6fr I 11 7 0 68 94. I 14 -5 0 29 99. | -14 221 148 54¡ 92trl41 280 93r
9 I t24 69 63' I 1t 8 140 9t 60r 8 14 4 112 Ì09 99. I -13 0 39 99' 9212121 tf3 89.
9 9 0 5l 8Si I lt 9 113 67 93. 8 14 -f l,41 31 9f. 1 -12 153 336 33 92r30 2tt 92^
9 10 l2a 11 91i 8 1l t0 I40 52 93r 8t4-2 0 43 91. I -11 201 3l 99r 9 3 -\5 212 31
9 II 140 129 60^ 8 t1 Ì1 0 2If 96^ I t4 -1 161 33 91. I -10 416 524 24 9 3 -15 134 20 E5*
9 t2 0 19 S3. 8 l2 13 l9 t12 99. 0 14 0 0 125 91 | 1 -9 0 8l 99' I I t4 0 159 99.
8 9 13 1f8 1f9 9Ì. A 12 -L2 348 314 36 I r{ 1 o 4699. 9 I -8 611 130If 9 3-13 r34 E6 99r
0 10 -14 0 t2't 99* I 12 -1Ì 135 166 99. I 14 2 o 262 9A. 9 r -1 164 163 55' 9 3 -r2 259 301 45r
9 3 -11 2¿1 r5238 9 5-16 0 6 99¡ 9 6 10 139 67 91r 9 I 10 166 31 91r 9 11 1 3 8l 357 31
9 3 -10 468 4A923 9 s-15 0 3299. 9 6 1l 3t0 290 28 9 I 11 91 289 98' 9 11 -6 351 359 34
93-9 25J 2444L 9 s-14 0 s099r 9 6 12 121 8s 91i 9 9 13 115 158 99' 9 11 -5 424 402 21
9 3 -8 414 49922 9 5-13 118 11599* 9 l-r5 r41 5l 861 9 9 -12 0 123 99r 9 11 -4 434 4 50 21
93-f 368 38926 9 5-12 t2i 8199¡ 9 1-14 tg't 80 99. 9 9 -1r L21 294 99' 9 11 -3 136 299 s0.
9 3 -6 185 51821 9 5-Ir 216 21946' 9 l-13 0 Ì51 99. 9 9 -10 I75 194 l0' 9 1l -2 388 342 21
93-5 386 44923 9 5-10 137 18499r 9 1-12 0 114 99. 9 9 -9 455 114 2A 9 11 -1 316 309 33
9 3 -1 600 579 16 9 5 -9 315 3A629 9 7 -11 285 315 {3 9 9 -8 181 248 99' 9 1Ì 0 197 242 99*
93-3 420 388 20 9 S -8 82 2t399ù 9 l-10 t55 111 90i 9 9 -l 609 605 21 9 rl 1 238 41i
93-2 509 53215 9 s -? 459 41722 9 7 -9 152 511 26 9 9 -6 325 212 34 9 11 2 0 16 98r
23236 9 I 191 39 99. 9 9 -5 123 '130 11 9 11 98r
9 3 -r 398 38520 9 5 -6 251 -0 3 0 5
930 518 5{817 9 5 -5 {95 53420 9 1 -1 567 5S0 20 9 9 -4 328 360 13 9 11 4 0 3 99.
931 226 2523s 9 5 -{ 243 21236 9 1 -6 61 4098. 9 9 -3 662 69211 9 11 5 0 ? 98r
932 115 40320 9 5 -3 {91 500 19 9 I -5 616 666 a6 9 9 -2 21A 269 3S 9 11 6 19 I 98r
933 0 6491¡ I 5 -2 209 24110' 9 1 -4 99 t681i 9 9 -1 531 5L919 9 11 1 140 20 98r
934 1?1 16145. 9 5 -t 521 496 1? 9 I -3 ?16 74S r8 9 9 0 r'19 22E 95' 9 11 I 0 57 99i
935 83 28 -t3* 9 5 0 22s 165 35 9 'l -2 184 128 49r 9 9 I 326 JoA 29 9 11 9 339 311 31
936 L92 166{11 9 5 1 450 455 19 9 ? -l 598 519 16 9 9 2 2LE 116 40' 9 12 -10 268 192 49.
931 0 2489r 9 5 2 r61 1{0 87i 9 -l 0 221 2L8 38r 9 9 3 236 129 31 9 12 -9 131 17 99.
tl7
930 250 281 33 9 5 3 214 21629 9 1 1 {31 10120 9 9 4 0 81961 9 12 -8 211 99i
939 0 114 91r 9 5 4 tl? 24 6Aù 9 'l 2 211 t9635 9 9 5 0 2592' 9 12 -1 208 16 99r
9 3 10 408 40a22 9 5 5 81 1 16Ê 9 1 3 108 1?694r 9 9 6 0 149{i 9 12 -6 ta2 31 99r
9 3 11 189 19143* 9 5 6 140 125 91r 9 1 4 216 269 30 9 9 1 22A L42 39^ 9 12 -5 0 103 99¡
346 370 25 9 5 7 248 23534 9 -l o 7091¡ 9 9 8 195 1441' 9 12 -4 241 143 {5.
93L2 5
97r 9 12 59 99.
9 3 13 153 114 77r 9 5 8 92 21693* 9 1 6 118 26 93' 9 9 9 170 245 -3 0

9 4-16 158 22380' 9 5 9 381 351 23 9 1 1 267 16232 9 9 10 0 9? 99' 9 12 -2 280 265 39
9 1-L5 2t9 29399r 9 5 10 116 1-rl 78r 9 'l I o 19 94¡ 9 10 -13 145 170 99' 9 12 -1 159 0l 99¡
I 4-74 263 21041' 9 5 lt 318 3462A 9 ? 9 280 2gA 31 9 10 -12 20? r03 99* 9 12 0 4r8 3 90 25
9 1 -13 334 346 37 9 5 12 259 r8432 9 7 l0 ).27 51 93r 9 tO -Ll 0 1-t5 99r 9 12 I 2t9 214 11.
9 4-L2 326 26835 9 5 13 183 26694* 9 I 11 361 31L 25 9 10 -10 210 133 99r I 12 2 411 11t 23
9 { -1r 249 33539 9 6-15 0 32199r 9 1 !2 109 15 66r I 10 -9 213 145 5?' 9 12 3 296 22ø 34
9 {-10 t29 16999i 9 6-14 0 10899* 9 8-14 o 22ggr 9 10 -8 0 51 99r 9 L2 4 41r 452 23
9 I -9 181 21699r 9 6-13 306 36811 9 8-13 o 29199. 9 t0 -? 0 13991 9 12 5 250 236 40
9 1 -8 r13 1097i 9 6-L2 0 13799. 9 0-12 o 3?99¡ g LO -6 218 1139 9 12 6 444 430 25
91-1 0 16198r 9 6-11 356 3?83{ 9 ¡-ll 702 321 sgr 9 10 -5 0 100 99' 9 12 1 181 t12 99.
9 { -6 0 295r 9 6-10 105 1-r3 99i 9 I -l 0 39 3S 99i 9 10 -4 115 66 601 9 13 -9 28'l 722 44
9 4 -5 0 6093i 9 6 -9 286 22231 9 I -9 o 210 9gr 9 10 -3 284 251 36 9 13 -8 361 315 36
9 4 -4 r23 a916a 9 6 -8 t43 104 99i 9 I -8 o 44 99r 9 10 -2 337 255 30 9 13 -7 1E6 145 99.
94-3 L29 24t69' 9 6 -l 929A. 9 I -'t 2r1 \r4 49. 9 10 -1 303 316 33 9 13 -6 315 380 39
94-2 155 23889r 9 6 -6 1?8 57 95r 9 3 -6 L11 5 59r 9 10 0 712 2ø4 99r 9 13 -5 0 140 99.
9 6 -5 E9 95r 9 E -5 t9? 19 99r 9 lO r 364 391 21 g 13 -4 256 353 46i
9 { -1 364 383 23 9a' 9 13 116 99r
940 365 38323 9 6 -4 0l 5893* 9 I -1 163 99 99. 9 ì0 2 l9O 280 -3 0

941 559 51615 9 6 -3 309 32029 9 I -3 284 384 36 9 10 3 119 4r9 29 9 13 -2 34r 338 34
942 503 53017 9 6 -2 95 23995. 9 I -2 183 lO 50r 9 10 4 3r\ 210 30 9 13 -1 182 96 99.
943 692 69216 9 6 -1 188 539 19 9 8 -1 488 s31 21 9 10 5 288 336 33 9 13 0 248 325 39
944 583 63515 9 6 0 23L 20536 9 I 0 1?4 131 93. 9 10 6 165 24s 98r 9 13 I 0 96 99r
945 132a6 9 6 1 101 734 16 9 I 1 5S5 611 1l 9 10 I 281 301 34 9 13 2 243 195 44r
946 5 95 56116 I 6 2 2L8 19{ 38* 9 I 2 120 3f 94r 9 l0 I 126 22s'15' 9 13 3 t56 43 99r
941 63 0 633 ls 9 6 3 1ø9 825 19 9 8 3 68s 691 1? 9 10 9 214 23s 35 9 13 4 44 92 99.
948 39'l 43122 9 6 1 208 2l 40r 9 8 4 131 95 60. 9 l0 10 134 226 16^ 9 13 5 189 1.00 99r
9{9 4 94 4?9 18 9 6 s 831 81 19 9 0 5 521 s3o 18 9 11 -12 0 126 99' 9 13 6 0 49 99.
9 4 l0 218 23430 9 6 6 240 14 34986 t21 88 69i 9 1l -11 216 24A 61', 9 14 -7 0 20 99r
9 4 11 309 23t21 9 6 1 651 61 16 9 I 't 4?O 510 21 9 11 -10 208 224 99' 9 14 -6 L12 1 99à
9412 L29 14 16ù 9 6 I 0 11 93r988 133 s8 93r 9 11 -9 269 299 41' 9 14 -s 0 33 99r
9 4 13 0 13793* 9 6 9 475 48 20989 195 354 99¡ 9 11 -8 298 330 42 9 14 -4 0 rt2 92.
9 14 -3 0 19 99. 10 2 -10 204 I 99* 10 4 -1 252 2!5 15' lO 6 -r 62e 662 L9 10 9 -11 350 336 42

911-2 224 204 50¡ 10 2 -9 201 57. t0 4 -6 129 154 99i 10 6 0 200 198 52r 10 9 -10 194 99¡
3l
911-1 0 13 99. 10 2 -S 269 t22 11 10 { -5 3to 349 36 l0 6 1 140 ?45 l8 10 9 -9 393 410
9 14 0 362 313 31 10 2 -'l 231 r21 46' tO 4 -4 328 310 33 IO 6 2 l'll' 194 99¡ 10 9 -8 0 208 99*
9 11 1 99 85 99¡ 10 2 -6 180 3r4 99i 10 1 -3 440 463 25 10 6 3 120 144 16 r0 9 -1 418 445 33
9 14 2 446 461 26 10 2 -S 306 288 35 10 4 -2 433 131 24 10 6 4 62 I23 99' 10 9 -6 246 210 54.
9 1{ 3 0 62 99. )-0 2 -4 403 451 2't 10 4 -1 5?5 604 19 10 6 5 481 500 22 10 9 -5 391 404 33
9 11 4 {35 491 28 10 2 -3 205 30236 10 4 0 42s 502 25 10 6 'l6 l2S 144 99r 10 9 -4 I62 22'l 92.
915-3 t16 64 99* 10 2 -2 593 61918 10 4 L 59? 624 t8 l0 6 258 321 40 10 9 -3 13 230 93a
975-2 263 21L 44. l0 2 -l 34 8 351 20 10 4 2 560 53119 l0 6 8 0 4599' 10 9 -2 160 95 99r
9 15 -1 r14 133 99i 10 2 0 681 'to't t6 10 4 3 574 582 19 l0 6 q 44 ll3 99' l0 9 -t 190 55 99'
291 99r 10 2 I 309 32432 10 4 4 38t 402 2'l L0 6 10 0 42 99r 10 9 0 0 68 99.
9 15 0 0
5a 99'
10 0 -t4 0 106 99i 10 2 2 558 ?11 17 10 4 5 {88 {f5 21 10 1 -L2 0 50 99r 10 9 1 119
10 0 -L2 2t6 f499r 10 2 3 170 1E2 99¡ 10 4 6 246 206 40 l0 I -1Ì 360 366 39 10 9 2 65 3 6 6r
10 0 -10 149 399i 10 2 4 55s 555 19 10 1 1 335 337 30 l0 f -10 116 39 14' 10 9 3 193 l.8l 99i
189 99a 10 2 5 289 29231 10 4 I o 90 99. 10 ? -9 406 381 33 10 9 4 161 l5 65i
10 0 -8 0
0 1799r l0 9 5 229 235 4'1.
10 0 -6 429 44426 10 2 6 426 40t24 10 4 9 o 9699* rO f -8
10 0 -4 503 59922 10 2 1 a2 221 98¡ r0 4 10 o 21 82r 10 1 ''l 404 3A9 32 10 9 6 180 r25 58r
100-2 620 65518 l0 2 6 199 184 4l* 10 { 11 184 18 96. 10 1 -6 o l2 99' 10 9 'I 356 344 29
o 99r 1o 1 -5 392 410 32 10 9 13t 99.
10 0 0 14L 12A ).8 10 2 9 152 196 82r 10 5 -13 215 8 0
2'l 99.
10 0 2 601 602 18 1.0 2 10 0 50 96i 10 5 -12 ?9 110 99t 10 1 -4 233 116 48r l0 10 -10 0

10 0 4 452 12't 23 10 2 ll 168 95 94* 10 5 -11 o 263 99r 10 1 -l 219 243 40 r0 10 -9 11 5l 99i
10 0 6 5l0 530 19 10 3 -14 165 201 83r 10 5 -10 194 139 99r 10 1 -2 0 186 99' 10 10 -8 0 5l 99r
10 0 8 232 216 43* 10 3 -13 2t0 121 6{i 10 5 -9 163 268 96i 10 I -1 198 149 99r 10 10 -6 t59 112 9 9. 143 53' 10 10 -l t16 t80 9-1.
10 0 10 t86 8? 961 10 3 -12 110 314 99r L0 5 -8 0 14r 99i 10 I O O
r0 1 -14 0 268 99i 10 3 -11 0 161 99i 10 5 -7 315 311 38 l0 I 1 0 48 99r 10 10 -s 301 324 42

10 1 -13 2r9 {1 62* 10 3 -10 388 349 32 10 5 -6 205 190 99r lo 1 2 56 lll 99r 10 10 -4 205 266 62.
10 l5
10 I -L2 319 396 36 10 3 -9 207 232 99r t0 5 -5 L'12 298 99. lo I 3 151 215 99' l0 -3 352 349
10 I -11 198 69 99¡ 10 3 -8 385 409 31 10 5 -4 o 145 99. 1o -t 1 4 161 r{ 99' 10 10 -2 0 255 99.
10 1 -10 111 541 29 10 3 -1 l3? 231 82* rO 5 -3 316 266 34 10 5 0 13? 99r 10 10 -1 395 319 30
10 1 -9 126 99r 10 3 -6 365 41{ 31 10 s -2 235 2t 43r ro 1 6 165 13 sl' 10 10 0 243 255
0 .7 ? 157 411 30 l 0 l0 I 283 350 4t
10 Ì -8 626 635 21 10 3 -5 133 138 73. 10 5 -1 26J r1s 31 10 99r r0 t0 265 99.
l0 I -7 211 120 51* 10 3 -4 409 39421 r0 s 0 0 34 99. 10 ? 0 0 24 2 0

10 1 -6 617 665 20 10 3 -3 0 1399i 10 5 I 191 t6 91. to 1 9 3A3 391 2A l0 10 l 264 43

r01-5 0 67 99r 10 3 -2 285 2A534 10 5 2 o 116 99r r0 8 12 0 9 99' l0 10 4 24'l 220
10 1 -4 190 499 23 10 3 -1 6'l 28971 10 5 3 143 210 98. l0 8 -11 169 52 99' 10 l0 5 158 2t 0 99i
101-3 158 20 98* 10 3 0 121 8097r r0 5 4 285 246 34 1o I -10 156 8 99' 10 10 6 149 2TI 99.
10L-2 321 36031 10 3 1 1r0 144 9?r 10 5 5 310 399 21 10 I -9 110 90 99r l0 11 I 320 296 45
10 I -1 0 2097¡ 10 3 2 219 ls4 32 10 s 6 255 241 3A rO I -0 128 19 99' Ì0 lÌ f 345 28I 41
10 I 0 2i-3 9144. r0 3 3 0 1f5 99. 10 5 ? J15 42\ 21 10 I -1 234 190 54r 10 lr -6 3410 323 40
10 I 1 0 8696i 10 3 4 381 42a26 r0 5 I 240 2L9 40 l0 I -6 36 12 99' 10 Il -s 205 99*
t0 7 2 140 182 ?4* l0 3 5 137 140 97¡ 10 5 9 3s5 391 2S 1,0 I -5 3S8 {1? 33 10 11 -4 t69 24r 99.
l0 1 3 13f 5995¡ r0 3 5 466 445 22 10 5 l0 2OO ¡.94 4lr 10 I -4 154 50 l5' 10 lt -3 0 194 99.
10 1 { 249 26640 10 3 1 266 255 37 10 6 -13 1t 109 99r 10 I -3 4't3 529 26 10 11 -2 0 t38 99¡
10 I 5 0 46 97* 10 3 I 455 495 23 10 6 -r2 0 49 99i 10 I -2 l9s 26 99' 10 r1 -1 101 91*
10 6 {49 4A623 10 3 9 2tL 25{ 46i 10 6 -11 0 15 99* 10 I -r 480 538 25 10 11 0 161 13 08,

t0 I ? 0 73 99r 10 3 r0 386 362 25 10 6 -10 120 11 99r 10 I O 35 74 85' t0 11 1 86 11 99a

10 I 0 581 567 19 10 3 11 15 0 215 l5r r0 6 -9 156 112 99. l0 8 I s18 561 22 10 11 2 199 34 99i
l0 1 9 136 39 9-r* 10 4 14 51 rto 99* 10 6 -8 32 62 99r lO A 2 202 84 49* l0 11 3 0 194 99r
10 1 10 533 54s 27 10 4 -13 0 98 99. 10 6 'l 132 218 99i lO ø 3 494 463 22 10 I1 4 110 102
10 I 11 113 80 98r 10 4 -72 0 70 99¡ 10 6 -6 82 114 99i 10 I 4 9l ?6 99' 10 11 5 0 2ø3 99.
10 2 -t4 r4f 131 99. 10 4 -11 185 t5 68. 10 6 -5 291 366 40 10 8 5 381 3¡l 2l r0 12 6 2r1 r82 624
10 2 -r3 0 11r 99r 10 4 -10 166 24 99r 10 6 -4 226 261 4gr IO I 6 157 29 99' lO 12 5 138 104 96^
10212 0 84 qq* 10 4 -9 0 58 99¡ 10 6 -3 511 552 21 10 I 1 132 261 99' l0 12 -4 2t1 219 48.
10 2 -lt 0 104 99i 10 { 6254. 10 6 1 193 24j 99i 10 I I 66 ?3 cc' ì0 12 -3 I46 140 95.
ro t2 -2 318 384 34 11 2 210 313 99¡ 11 5 2 121 110 99. 11 8 4 184 22 99r rz 3 3 22 r82 99.
t0 t2 -1 249 249 50i 1t 2 0 213 99r 11 5 I 24t 222 SO. II 9 -l 155 185 99' 12 3 2 0 25t 99¡
10 12 0 {11 425 3l 11 2 1E0 43. tt 5 0 160 161 99* 11 9 6 0 87 99' 12 3 -t 234 220 5¿.
I 43 lt 2t2 99a 11 5 346 36334 11 9 -5 169 41 99' 12 3 0 299 3lt 4l
10 12 218 266 2 111 1
t0 t2 2 343 442 3f 11 2 18 30 99r 11 5 2 226 251 51r rr 9 -4 0 10 99' Ì2 I I 255 209 54.
10 12 3 148 2t3 92r rl 2 0 102 99. l1 5 3 424 41526 1Ì 9 -3 0 5299' 12 3 2 361 348 38
10 13 -3 0 100 99. 11 2 0 9599. 11 5 4 0 221 99r ll 9 -2 256 5 5l' 12 3 f 224 268 99.
10 t3 -2 151 161 86. 11 3 -l 0 141 99. 11 5 s 204 406 99. 11 9 -1 200 I43 99' Ì2 4 6 252 269 99^
10 13 -l t9? 11 631 11 3 l0 249 248 59¡ 11 5 6 o 20199r Ìl 9 0 0 2699'12 4 5 l5l 369 45
lt o -12 0 99 99^ 11 3 -9 202 119 99. 11 5 l 356 3A2 32 ll 9 1 ÌÌ8 25r 99' \2 4 4 119 240 99.
11 0 -10 198 246 99^ tr 3 I 0 224 99* rr 6 -10 t9o s9 99. ll 9 2 196 82 99' 12 4 -3 223 346 99.
 *
il
o
CD ttt I I I I I I I lÞÈ
Ò r r r I I I I r rPP

o PúNOO-þ
ðóo {Þaõ ó ñióbo ooNo o PP oPo uPa o oôN

o ÀNÀNUPN O NÑUÀÀ¡¡
e¡joj{úP¡ooP€ts6P Jo{NN hJ{6JN
€ñdþo
É ÀÑ5N€ UUÀEó
Ø ãgñj@¡õ¡õo@uúc{þuEoo
ô ; i i i¡ir¿. i
'
È
þPHFP

qøøuÀ ÀÀÀuouuuuo
o ttll
I I I I I I I I I PP I I I I I I I
È ü À ù À { ò ri¡ ô þ ¡ P o È ñ ù ¡ ú ô ¡ ó

UNUNNÑNUtsUUONO
õ{À Pñ
áuoo tslJ5ÀúÞ€¡¡
o
UøO¡N
a;6;€€@;oJoÀuñpp ¡!{ÞNÀNe66 ôõ5óo6oP6
o €6€9þ NoNoN þ9€uþ
6þa6€€ÞÉ€õ€Þþô€ @þþ{o o!6eu
o i;.ii¡ilrr*4.

óè!!! !!!J{ ô66660ô6ô

ttrlrlll lllllll¡llllllllrl
orupoÉiruÀuô PNoòø6!èE

PN Ñ
ñÀÀÈÞauo!€
oõoþEg¡õu€õ€€óo E6þ6€
;;i'

NNNNN

rtrr llllrlll llllllll llrl llll

Åü ér r - uo p oÈñoi 6ô¡@À uñPo P No

!qJq e
ÉÉoðoôdùu@NouùN oñoô¡

uõ66u
ø€oo6€aþu
@óú ó þ þ €þ 6úG6o € @ o 6N 6N N € €6@ 5 ñ c þ
;;; ¡ ¡ i ¡; r
'. '

lr