Inorganica Chimica Acta 353 (2003) 59 /67

www.elsevier.com/locate/ica

Complex formation of NS N-ethylene bridged bis(N?-benzoyl-O-

ethyl-isourea) and N-benzoylguanidines with late transition metals
Uwe Schroder a,*, Lothar Beyer a, Rainer Richter a, Jorge Angulo-Cornejo b,
Mary Castillo-Montoya b, Maria Lino-Pacheco b
a
Institut fu
r Anorganische Chemie, Universita
t Leipzig, Johannisallee 29, D-04103 Leipzig, Germany
b
Universidad Nacional Mayor de San Marcos, Facultad de Qumica e Ingeniera Qumica, Av. Venezuela s/n, Lima, Peru

Received 6 September 2002; accepted 21 March 2003

Abstract

N S N -ethylene bridged 3-benzoyl-2-ethyl-1-[2-(3-benzoyl-2-ethyl-isoureido)-ethyl]-isourea 1 and 2-benzoylimino-imidazolidine 2

are easily accessible in good yields and act as N ,O donor ligands. After deprotonation 1 and 2 form mononuclear neutral complexes
whose molecular structures have been determined by X-ray structure analysis. The metal ions in the 1:1 complexes of 1 with CuII,
NiII and CoII are coordinated by the two bridging N atoms and the two carbonyl O atoms of one ligand molecule resulting in one
five membered and two six membered chelate rings. The coordination geometry is square planar with cis arrangement of the ligator
atoms. In comparison to the free ligand 1 the lengths of the C /O and C /N bonds involved in coordination are changed
characteristically. The 2:1 complexes of 2 with CuII and NiII are isostructural. One deprotonated imidazolidine N and the carbonyl
O atom of each ligand molecule coordinate the metal ion in a square planar trans arrangement. The X-ray structure analysis of 2
shows, besides an intramolecular imidazolidine-N /H/


/O hydrogen bridge, two intermolecular hydrogen bonds originating from
both imidazolidine N atoms, an N /H/


/N and an N /H/


/O one, leading to the formation of molecular chains in the crystal
structure. 2-Benzoylimino-1,3-diaza-6,9-dioxacycloundecane 3 was synthesized from N -dichloromethylene-benzamide and 1,8-
diamino-3,6-dioxaoctane using the dilution principle. The crystal structure of 3 reveals again, besides an intramolecular N /H/


/O
hydrogen bridge, the formation of molecular chains caused by one intermolecular N /H/


/O hydrogen bridge per molecule. The
bulky structure of the 1,3-diaza-6,9-dioxacycloundecane ring in 3 seems to prevent any complex formation of 3 with late transition
metal ions.
# 2003 Elsevier B.V. All rights reserved.

Keywords: Isoureas; Guanidine derivatives; Complex formation; Molecular structures

1. Introduction coordinate as chelating N ,N ?-donor ligands for early,

middle and late transition metals [5] and often they are
Due to their steric and electronic flexibility and their used as support and ancillary ligands with hard base
capability to act in a variety of possible coordination donors in organometallic chemistry and metal-mediated
modes, substituted guanidines and their anions have organic transformations [6]. Dianionic guanidinates
become interesting as ligands for a wide range of metal exhibit a variety of bi- and tridentate coordination
ions [1]. Thus substituted guanidine moieties can behave geometries [1] and may tend to form supramolecular
as neutral monodentate N -donor unities in complexes of coordination oligomers if additional appropriate N - and
mono- [2] as well as of bi- and tridentate bis- [3] and tris- O -donors are available at the periphery of the ligand
guanidines [4]. Monoanionic guanidinates prefer to molecule [7]. Guanidine moieties are also contained in
biological important compounds like creatine and
creatinine, which have a rich and varied coordination
* Corresponding author. Tel.: /49-341-973-6161; fax: /49-341-
chemistry [8].
973-6199. Whereas the coordination of neutral phos-
E-mail address: [email protected] (U. Schroder). phorylguanidines */bearing a N ,O -donor atom set in
0020-1693/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00322-0
60 U. Schro
der et al. / Inorganica Chimica Acta 353 (2003) 59 /67

1,3-position similar to N -benzoylisoureas */with var- 218 ([PhCONC(OEt)NHCHCH2] , 10); 205 (M /2,
ious bivalent and trivalent metal ions, yielding the 18); 193 ([PhCONHC(OEt)NH2] , 40); 105 ([PhCO],
corresponding halo guanidine complexes, was reported 100); 77 (Ph , 33).
[9], up to now only one neutral copper(II) complex of IR (KBr) n (cm1): n(NH) 3233 m; n(CH) 3000 m,
such a monoanionic (benzoyl)guanidinate has been 2982 m, 2936 m, 2890 m; n (C /O) 1612 vs; n(C /N) 1584
characterized by X-ray crystal structure analysis [10b]. vs, 1570 vs; 1484 m; 1443 s; 1384 s; 1371 s; 1330 vs; 1300
Continuing our previous investigations on metal s; 1157 m; 1143 s; 1110 s; 1092 s; 1066 m; 1045 s; 1027 m;
complexes of benzoylisoureas and benzoylguanidines 971 m; 880 s; 760 s; 717 s; 693 m.
[10,11] we synthesized the N S N -ethylene bridged
bis(N ?-benzoyl-O -ethyl-isourea) (1) and two monocyclic
N -benzoylguanidines (2, 3), studied their complex for- 2.1.2. 2-Benzoylimino-imidazolidine 2
mation with copper(II), nickel(II) and cobalt(II) and A bigger amount of 2 was synthesized using a method
characterized the obtained products structurally. described in the literature [13] starting from N -dichlor-
omethylene-benzamide [15] and 1,2-diaminoethane.
Crystals for X-ray diffraction analysis were obtained
2. Experimental from ethanol.
1
H NMR (400 MHz, CDCl3): d 3.48 (s, 4H, /CH2 /);
The following devices were used for measurements: 7.39 (dd, 2H, m -Ph); 7.43 (t, 1H, p -Ph); 8.07 (d, 2H, o-
Boetius melting point apparatus (corrected values), Ph); 8.75 (br, 2H, NH ).
13
Bruker DRX 400 (NMR), V.G. Masslab 12-250 (EI- C NMR (100 MHz, CDCl3): d 42.4 (C H2); 128.6,
MS), V.G. ZAG-HSQ (FAB-MS), Perkin /Elmer Spec- 129.3, 131.7, 138.8 (m ,o,p ,i -Ph); 166.5 (C O); 178.2
trum 2000 (IR), Perkin /Elmer Lambda 900 (UV /Vis), (NC (NHCH2)2).
Johnson-Matthey MSB-MK I (magnetic susceptibility). IR (KBr) n (cm 1): n(NH) 3379 s; n(CH) 3121 m,
The metal contents were determined by standard edta 2942 m, 2894 m, 2820 m; n (C /O) 1614 vs; n(C /N) 1589
titrations of the HClO4/H2SO4 decompositions. vs, 1567 vs; 1529 m; 1486 s; 1445 m; 1404 s; 1346 vs;
1286 m; 1146 m; 1062 s; 886 m; 749 m; 719 s; 694 m; 654
2.1. Synthesis of the bis(N ?-benzoyl-O -ethyl-isourea) m; 513 m.
(1) and the N -benzoylguanidines (2, 3)

2.1.1. 3-Benzoyl-2-ethyl-1-[2-(3-benzoyl-2-ethyl- 2.1.3. 2-Benzoylimino-1,3-diaza-6,9-dioxacycloundecane

isoureido)-ethyl]-isourea 1 3
To a solution of 7.12 g (0.03 mol) N -benzoylthiocar- To a vigorously stirred solution of 10.1 g (0.1 mol)
bamic-O ,S -diethylester [12] in 70 ml ethanol were added triethylamine in 700-ml toluene drop by drop were
0.90 g (0.015 mol) 1,2-diaminoethane in 15 ml ethanol. added 10.1 g (0.05 mol) N -dichloromethylene-benza-
The mixture was refluxed for 2 h. During cooling down mide [15] and 7.4 g (0.05 mol) 1,8-diamino-3,6-dioxaoc-
to room temperature occurred a white precipitation. It tane, each dissolved in 15 ml toluene, simultaneously.
was filtered off and recrystallized from ethanol yielding During the addition a white solid precipitated. The
3.70 g of 1. From the reduced filtrate of the reaction mixture was heated and stirred at 90 8C for 1.5 h and
mixture by keeping at 4 8C overnight were obtained 0.14 than kept stirring at room temperature overnight. After
g (0.75 mmol, 5%) of thick colorless prisms identified as filtration of the mixture the residue was washed with
2 by melting point [13,14] and NMR (see below) and a toluene. The united filtrates were reduced to a minimum
further amount of 1 (0.61 g after recrystallization from followed by digesting of the obtained yellowish /brown-
ethanol). ish grease with 150 ml ethanol. The formed white solid
Tiny white needles. Yield: 4.31 g (70%), m.p. 115/ was filtered off. Further amounts of the product could
117 8C. C22H26N4O4 (410.47 g mol 1): Calc.: C, 64.37; be isolated by reducing the volume of the filtrate and
H, 6.38; N, 13.65; O, 15.59%; Found: C, 63.8; H, 6.42; keeping it at /20 8C. Recrystallization was done from
N, 12.9; O, 15.3%. ethanol, crystals for X-ray diffraction analysis were
1
H NMR (400 MHz, CDCl3): d 1.38 (t, 3H, / obtained from acetonitrile as drop-shaped crystals.
CH2CH3); 3.53 (d, 2H, /NHCH2 /); 4.50 (q, 2H, / Tiny white needles. Yield: 5.8 g (42%), m.p. 148/
OCH2CH3); 7.40 (dd, 2H, m -Ph); 7.47 (t, 1H, p -Ph); 151 8C. C14H19N3O3 (277.32 g mol1): Calc.: C, 60.63;
8.22 (d, 2H, o-Ph); 10.17 (s, 1H, NH). H, 6.91; N, 15.15; O, 17.31%; Found: C, 60.4; H, 7.18;
13
C NMR (100 MHz, CDCl3): d 15.1 (C H3); 41.4 N, 15.0; O, 16.8%.
1
(C H2); 64.6 (/OC H2 /); 128.5, 129.9, 132.3, 138.4 H NMR (200 MHz, CDCl3): d 3.46 (s, br, 2H, /
(m ,o,p ,i -Ph); 163.8 (C O); 178.4 (NC (OEt)N). CH2 /); 3.68 /3.75 (m, 10H, /CH2 /); 7.03 (s, br, 1H,
MS (EI, 70 eV, 60 8C): m /z (fragment ion, rel. int. in NH ); 7.34 /7.44 (m, 3H, m ,p -Ph); 8.21 (d, 2H, o-Ph);
%) 410 (M, 3); 381 (M /Et, 2); 305 (M/PhCO, 2); 10.81 (s, br, 1H, NH).
 U. Schro
der et al. / Inorganica Chimica Acta 353 (2003) 59 /67 61

13
C NMR (50 MHz, CDCl3): d 42.3, 42.9, 69.5, 70.4, OCH2CH3); 7.36 (dd, 2H, m -Ph); 7.45 (t, 1H, p -
70.6, 73.3 (C H2); 127.8, 129.0 (o ,m -Ph); 131.0 (p -Ph); Ph);.8.11 (d, 2H, o-Ph).
13
139.0 (i-Ph); 161.9 (C O); 177.2 (C N). C NMR (100 MHz, CDCl3): d 15.6 (C H3); 49.8
MS (EI, 70 eV, 60 8C): m /z (fragment ion, rel. int. in (C H2); 64.6 ( /OC H2 /); 128.6, 129.7, 131.9, 136.2
%) 277 (M, 30); 248 (M/Et, 6); 217 (M / (m ,o ,p ,i-Ph); 158.7 (C O); 173.7 (NC (OEt)N).
HO(CH2)2OH, 11); 200 (M/Ph, 15); 188 (M/ FAB-MS (matrix: 3-NBA): m /z 467 (M , rel. int.
(CH2)2O(CH2)2OH, 21); 105 ([PhCO] , 100); 77 (Ph , 100%); 411 (M/2Et/2H, 50).
62). IR (KBr) n (cm1): n (CH) 2982 m, 2932 m, 2907 m,
IR (KBr) n (cm 1): n (NH) 3330 m; n(CH) 2940 m, 2873 m; n (C /O) 1595 vs; n(C /N) 1573 vs, 1505 vs; 1445
2868 m; n(C /O) 1597 vs; n(C /N) 1576 vs, 1538 s; 1487 s; 1422 vs; 1384 s; 1369 s; 1327 vs; 1303 m; 1179 m; 1160
m; 1447 m; 1432 m; 1417 m; 1385 vs; 1358 vs; 1302 m; m; 1149 m; 1117 s; 1078 s; 1066 m; 1029 m; 1007 m; 908
1271 m; 1227 m; 1175 m; 1066 m; 1132 s; 1112 m; 1071 s; m;750 s; 705 s; 592 m.
1024 m; 1013 m; 945 m; 867 m; 810 m; 755 m; 717 s; 683 Vis (CHCl3): l (nm) (log o ) 444.3 (2.93).
m.
2.2.4. CoII complex 1c
2.2. Synthesis of complexes of 1 and 2 Yellow/orange needles. Yield: 0.168 g (51%), m.p.
252 /253 8C. C22H24N4O4Co (467.38 g mol 1): Calc.: C,
56.53; H, 5.18; N, 11.99; O, 13.69; Co, 12.61%; Found:
2.2.1. General procedure
C, 55.95; H, 4.93; N, 12.35; O, 13.9%.
One millimole of 1 (2 mmol of 2, respectively) and 1
FAB-MS (matrix: 3-NBA): m /z 467 (M , rel. int.
mmol of the corresponding metal acetate (copper(II)
32%); 411 (M/2Et/2H, 25); 105 ([PhCO] , 100).
acetate monohydrate, nickel(II) acetate tetrahydrate or
IR (KBr) n (cm1): n (CH) 2980 m, 2931 m, 2906 m,
cobalt(II) acetate tetrahydrate) each dissolved in 10 ml
2872 w; n (C/O) 1589 vs; n(C /N) 1557 vs, 1489 s; 1444
ethanol were mixed together and stirred at 50 8C for 30
s; 1415 vs; 1383 s; 1366 s; 1327 vs; 1302 m; 1179 m; 1159
min followed by further stirring at room temperature
m; 1147 m; 1115 m; 1076 m; 1066 m; 1028 m; 1007 w;
overnight. The precipitations were filtered, washed with
905 m;749 s; 704 s; 684 m; 619 w; 591 w.
ethanol and air-dried. The metal complexes of 1 were
UV /Vis (CHCl3): l (nm) (log o ) 388.8 (3.57); 430.0
purified by dissolving in a minimum of chloroform and
(3.47).
overlaying with the triple volume of isopropanol.
meff (T /298 K) 2.57 B.M.
Crystals suitable for X-ray structure analyses were
obtained within a few days. Recrystallization from
2.2.5. CuII complex 2a
boiling dimethylformamide yielded crystals of the com-
Violet needles. Yield: 0.356 g (81%), m.p. 295 8C
plexes of 2 in diffractometer quality.
(dec.). C20H20N6O2Cu (439.96 g mol 1): Calc.: C,
54.60; H, 4.58; N, 19.10; O, 7.27; Cu, 14.44%; Found:
2.2.2. CuII complex 1a C, 54.6; H, 5.08; N, 18.8; O, 7.42; Cu, 14.1%.
Violet needles. Yield: 0.207 g (97%), m.p. 231 /232 8C. FAB-MS (matrix: 3-NBA): m /z 441 ([M/H] , rel.
C22H24N4O4Cu (471.99 g mol1): Calc.: C, 55.98; H, int. 5%); 307 (M/PhCONCH2, 58); 251 (M/L,
5.12; N, 11.87; O, 13.56; Cu, 13.46%; Found: C, 55.8; H, 10); 189 ([LH], 55); 136 (3-NBA /OH, 100).
5.36; N, 11.6; O, 13.4; Cu, 13.1%. IR (KBr) n (cm 1): n(NH) 3284 s; n(CH) 3065 m,
FAB-MS (matrix: 3-NBA): m /z 472 (M, rel. int. 2949 m, 2881 m; n(C /O) 1590 s; n (C/N) 1557 vs, 1526
100%). vs; 1498 s; 1488 s; 1475 s; 1440 m; 1396 vs; 1341 m; 1276
IR (KBr) n (cm 1): n (CH) 2979 m, 2928 m, 2907 m, s; 1069 m; 1027 m; 748 m; 706 s; 693 m; 673 m; 551 m.
2869 w; n (C /O) 1597 vs; n(C /N) 1573 vs, 1507 vs; 1445 UV /Vis (solid state): l (nm) 356.1; 559.7.
s; 1415 vs; 1385 s; 1364 s; 1337 m; 1322 vs; 1302 m; 1176
m; 1147 m; 1113 m; 1075 m; 1066 m; 1026 m; 1000 w; 2.2.6. NiII complex 2b
895 m;753 s; 705 s; 686 m; 567 m. Red brown needles. Yield: 0.283 g (65%), m.p. 325 8C
Vis (CHCl3): l (nm) (log o ) 546.6 (2.33). (dec.). C20H20N6O2Ni (435.13 g mol 1): Calc.: C, 55.21;
meff (T /300 K) 1.93 B.M. H, 4.63; N, 19.31; O, 7.35; Ni, 13.49%; Found: C, 55.0;
H, 4.57; N, 19.0; O, 7.79; Ni, 13.0%.
2.2.3. NiII complex 1b FAB-MS (matrix: 3-NBA): m /z 435 (M , rel. int.
Orange needles. Yield: 0.161 g (94%), m.p. 245 / 100%).
246.5 8C. C22H24N4O4Ni (467.16 g mol 1): Calc.: C, IR (KBr) n (cm 1): n(NH) 3261 s; n(CH) 3046 m,
56.56; H, 5.18; N, 11.99; O, 13.70; Ni, 12.56%; Found: 2953 m, 2885 m; n(C /O) 1589 s; n (C/N) 1561 vs, 1534
C, 56.4; H, 5.17; N, 11.4; O, 13.8; Ni, 13.05%. vs; 1499 s; 1487 s; 1475 s; 1440 s; 1399 vs; 1346 m; 1277 s;
1
H NMR (400 MHz, CDCl3): d 1.30 (t, 3H, / 1084 m; 1070 m; 1028 m; 899 m; 747 s; 699 s; 586 m.
CH2CH3); 3.05 (s, 2H, /CH2 /);.4.40 (q, 2H, / UV /Vis (solid state): l (nm) 385.9; 490.9.
62 U. Schro
der et al. / Inorganica Chimica Acta 353 (2003) 59 /67

2.3. X-ray structure determinations whether an auxiliary base (AcO , HCO3, OH ,

MeO) was used or not in several solvents. Steric
All measurements were carried out on a Siemens CCD and/or electronic influences of the long oxaalkylene
SMART diffractometer equipped with a graphite mono- chain in 3 could be the reason for this.
chromator utilizing Mo Ka radiation (l/0.71073 A ).
All data were collected at /55 8C. Lorentz-polarization 3.2. Molecular structures
corrections and absorption corrections by SADABS
were applied to the intensity data. All structures were
solved by direct methods. The non-hydrogen atoms were 3.2.1. 3-Benzoyl-2-ethyl-1-[2-(3-benzoyl-2-ethyl-
refined anisotropically [16]. The positions of the hydro- isoureido)-ethyl]-isourea 1 and its complexes 1a, 1b and
gen atoms were taken from difference syntheses and 1c
refined isotropically for all structures except 1a for The ligand 1 forms a centrosymmetric molecule (Fig.
which the hydrogen positions were calculated and not 1) which is mainly planar [t (O1C2N1C1) /9.8(6)8,
refined. t (N2C1N1C2) /2.0(6)8] with no contacts between
The structure determination of 2 is a more accurate both halves of the molecule. The angle between the
redetermination of an already known structure [17]. phenyl ring C3 /C8 and the fragment O1C2N1 is 2.0(5)8.
Details of crystal data and structural determinations The molecule has intramolecular hydrogen bonds N2 /
and an angle
H2/


/O1 with an N/


/O distance of 2.634 A
are given in Table 1. Tables 2/4 show selected bond
distances and angles. N /H/


/O of 135.28. The bond lengths in the central part
of the molecule show p-electron delocalization with a
shorter N1 /C1 bond (1.321 A ) and a longer N1 /C2
bond (1.357 A).
3. Results and discussion
The complex formation of 1 with copper, nickel and
3.1. Syntheses cobalt gives the chelates 1a, 1b and 1c (Figs. 2 and 3).
The nickel and the cobalt complex are isostructural
Bis(N ?-benzoyl-O -ethyl-isoureas) are obtainable by whereas the copper complex crystallizes with two
condensation of two equivalents of N -benzoylthiocar- independent molecules in the asymmetric unit. In all
bamic-O ,S -diethylester [12] with one equivalent of a three complexes the metal atom is coordinated by two O
primary diamine [11a]. However, in the case of 1,2- atoms and two N atoms. The coordination is nearly
diaminoethane */in difference to the synthesis of bis(N ?- square-planar with coordination angles MO1N2/
benzoyl-O -ethyl-isoureas) containing longer bridging MO3N4 of 1.8(3) and 3.0(3)8 for 1a, 1.3(1)8 for 1b and
alkyl chains [11a] */a tendency to cyclization forming 1.8(2)8 for 1c. The phenyl rings form angles with the
2-benzoylimino-imidazolidine 2 up to an extent of 5% adjacent chelate rings of 4.0 /12.78 (1a), 4.2 and 10.88
was observed (this work, see Scheme 1). In good yields 2 (1b) and 4.4 and 10.48 (1c). The complex formation
can be synthesized easily from N -dichloromethylene- changes the lengths of the central C /O and C /N bonds
benzamide and 1,2-diaminoethane [13]. Whereas the by lengthening the O1 /C2 and N1 /C1 bonds and
structure of 2 has been investigated in the context of the shortening the N1 /C2 and N2 /C1 bonds.
development of anion receptors based on acylguanidi-
nium groups [17], up to now its metal complex forma- 3.2.2. 2-Benzoylimino-imidazolidine 2 and its complexes
tion behavior has not been studied. 2-Benzoylimino-1,3- 2a and 2b
diaza-6,9-dioxacycloundecane 3 was synthesized from The structure of ligand 2 (Fig. 4) deviates clearly from
N -dichloromethylene-benzamide and 1,8-diamino-3,6- planarity. The imidazolidine fragment is nearly planar
dioxaoctane using the dilution principle in order to but the phenyl ring C5 /C10 forms an angle of 35.6(1)8
minimize the formation of oligo- and polymeric side with the central part of the molecule O1C1N1C2N3.
products. Thus 3 was obtained in a yield of 42%. The molecule has an intramolecular hydrogen bridge
By reaction of 1 and 2 with the acetates of CuII, NiII N3 /H3/


/O1 with an N/


/O distance of 2.667 A and an
and CoII in ethanolic solution the corresponding neutral angle N /H/


/O of 120.68.
chelate complexes were obtained, using the acetate as Besides there are two intermolecular hydrogen bonds
deprotonator for the ligands. The complexes precipitate originating from the N atoms of the imidazolidine
from the reaction mixture and can be isolated easily by fragment and leading to the formation of molecular
filtration. The Ni and Cu complexes of 1 are soluble in chains in the crystal structure: N2 /H2/


/N1[/x , /y/
boiling dimethylformamide, whereas the complexes of 2 2, /z/1] (N/


/N 2.974 A , N /H/


/N 174.78) and N3 /
were recrystallized from chloroform/iso-propanol. De- H3/


/O1[/x , /y/1, /z/1] (N/


/O 2.957 A , N /H/


/
spite 3 has the same donor atom set in a quite similar O 128.78).
arrangement like 2, all our attempts to get metal (NiII, Again there is a p-electron delocalization with a
PtII, CuII, ZnII, AgI) complexes of 3 failed, regardless somewhat longer N1 /C1 bond (1.359 A ) and a some-
Table 1
Crystallographic and structural determination data

1 1a 1b 1c 2 2a 2b 3

Molecular formula C22H26N4O4 C22H24N4O4Cu C22H24N4O4Ni C22H24N4O4Co C10H11N3O C20H20N6O2Cu C20H20N6O2Ni C14H19N3O3
Formula weight 410.47 471.99 467.16 467.38 189.22 439.96 435.13 277.32
(g mol 1)
Crystal habit, color colorless prisms violet prisms orange prisms orange plates colorless prisms violet prisms red /brown prisms colorless drop-

U. Schro
shaped
Crystal system monoclinic monoclinic monoclinic monoclinic monoclinic monoclinic monoclinic monoclinic
Space group P 21/n P 21/n P 21/n P 21/n P 21/n P 21/n P 21/n P 21/c

der et al. / Inorganica Chimica Acta 353 (2003) 59 /67

a (A) 6.435(1) 24.515(3) 12.923(1) 12.963(1) 5.053(1) 4.726(1) 4.757(1) 11.007(1)
b (A) 14.117(2) 7.433(1) 13.750(1) 13.820(1) 9.879(1) 19.588(2) 19.633(2) 10.858(1)
c (A) 11.426(1) 26.550(4) 13.128(1) 13.122(1) 18.441(2) 10.077(1) 10.018(1) 12.066(1)
b (8) 96.686(2) 117.445(2) 116.021(2) 116.046(2) 91.375(1) 102.224(2) 103.881(2) 90.969(2)
V (A 3) 1030.9(2) 4293.6(10) 2096.1(4) 2112.0(4) 920.4(1) 911.8(1) 908.3(2) 1441.8(3)
Z 2 8 4 4 4 2 2 4
Dcalc (g cm 3) 1.322 1.460 1.480 1.470 1.366 1.603 1.591 1.278
F (0 0 0) 436 1960 976 972 400 454 452 592
Crystal size (mm) 0.31/0.16/0.07 0.53/0.15 /0.07 0.41 /0.28 /0.26 0.21/0.21 /0.05 0.39 /0.31 /0.25 0.26/0.16/0.08 0.44/0.23/0.10 0.43/0.19/0.16
Linear absorption 0.093 1.054 0.963 0.850 0.093 1.229 1.100 0.091
Coefficient m
(mm1)
2u Range (8) 4.6 /45.0 3.7 /45.0 4.5 /58.0 4.5 /58.0 4.4 /58.0 4.2 /58.0 4.2 /58.0 5.0 /58.0
Measured reflec- 4381 17 068 13 530 13 906 5896 6091 6066 9371
tions
Unique reflections 1345 5591 5069 5171 2212 2249 2213 3492
Observed reflec- 965 4122 3992 3495 1668 1773 1959 2101
tions [I /2s (I )]
Refined parameters 189 564 376 376 171 173 173 257
wR2 0.2582 for 1345 0.2135 for 5591 un- 0.0852 for 5069 un- 0.0927 for 5171 un- 0.1192 for 2212 0.0813 for 2249 un- 0.0763 for 2213 un- 0.1290 for 3492
unique reflections ique reflections ique reflections ique reflections unique reflections ique reflections ique reflections unique reflections
R1 0.0853 for 965 ob- 0.0682 for 4122 ob- 0.0333 for 3992 ob- 0.0389 for 3495 ob- 0.0423 for 1668 0.0290 for 1773 ob- 0.0277 for 1959 ob- 0.0477 for 2101
served reflections served reflections served reflections served reflections observed reflec- served reflections served reflections observed reflec-
tions tions
Goodness-of-fit on 1.172 1.120 1.010 0.940 1.041 1.017 1.037 0.998
F2
Greatest difference 0.45 and /0.34 1.65 and /0.95 0.35 and /0.33 0.38 and /0.52 0.21 and /0.25 0.30 and /0.27 0.30 and /0.28 0.31 and /0.22
peak and hole
3)
(e A

63
64 U. Schro
der et al. / Inorganica Chimica Acta 353 (2003) 59 /67

Table 2 Table 4
) and angles (8) for 1, 1a, 1b and 1c
Selected distances (A ) and angles (8) for 3
Selected distances (A

1 1aa 1ba 1ca Bond lengths

O1 /C1 1.255(2) O2/C4 1.424(2)
Bond lengths O2 /C5 1.410(2) O3/C6 1.424(3)
M/O1 1.907(4) 1.845(1) 1.857(1) O3 /C7 1.427(3) N1/C1 1.336(2)
M/O3 1.911(4) 1.841(1) 1.850(2) N1 /C2 1.351(2) N2/C2 1.346(2)
M/N2 1.907(4) 1.837(1) 1.839(2) N2 /C3 1.458(2) N3/C2 1.332(2)
M/N4 1.894(5) 1.834(1) 1.841(2) N3 /C8 1.449(2) C3/C4 1.517(3)
O1/C2 1.258(4) 1.275(6) 1.280(2) 1.286(2) C5/C6 1.514(3) C7/C8 1.500(3)
O2/C1 1.329(4) 1.351(6) 1.345(2) 1.359(2)
Bond angles
O2/C9 1.463(4) 1.454(6) 1.454(2) 1.464(2)
C1/N1/C2 120.8(1) O1/C1/N1 127.6(2)
N1 /C1 1.321(5) 1.358(7) 1.350(2) 1.346(3)
N1 /C2/N2 124.1(2) N1/C2/N3 116.7(2)
N1 /C2 1.357(5) 1.318(7) 1.318(2) 1.317(2)
N2 /C1 1.326(5) 1.301(7) 1.306(2) 1.320(3)
N2 /C11 1.454(5) 1.469(7) 1.471(2) 1.475(3)
C11/C12 1.508(8) 1.516(7) 1.511(3) 1.521(3)
Bond angles
fragments are nearly planar and the phenyl rings C5 /
O1/M/N2 92.4(2) 93.7(1) 93.0(1)
O3/M/N4 92.0(2) 93.4(1) 92.9(1) C10 form angles of 23.3(2)8 (2a) and 26.3(2)8 (2b) with
M/O1 /C2 124.8(3) 125.6(1) 126.1(1) the central parts O1N1C1. One of the intermolecular
C1/N1/C2 120.8(3) 121.7(5) 120.4(2) 121.2(2) hydrogen bridges N2 /H2/


/N1[/x/1, /y , /z/1] is
M/N2 /C1 124.4(4) 124.6(1) 125.1(2) preserved (2a: N/


/N 3.208 A , N /H/


/N 167.98; 2b: N/


/
N1 /C1/N2 126.6(3) 127.3(5) 127.6(2) 126.9(2) , N /H/


/N 172.08).
O1/C2/N1 125.4(3) 129.0(5) 128.2(2) 127.7(2)
N 3.158 A
The complex formation results, as expected, in a
a
Mean values of the equivalent bonds and angles. lengthening of the O1 /C1 and N1 /C2 bonds and a
shortening of N1 /C1 bonds. The bond lengths in the
Table 3
imidazolidine ring are also changed by complex forma-
) and angles (8) for 2, 2a and 2b
Selected distances (A tion. The bonds N3 /C2 become shorter and the bonds
N2 /C2 become longer and there is a clear difference
2 2a 2b between these bonds which are equal in the ligand. The
Bond lengths same is true for the bonds N2 /C3 and N3 /C4 which
M/O1 1.936(1) 1.845(1) have equal lengths in the ligand and different lengths in
M/N3 1.908(1) 1.861(1) the complexes.
O1/C1 1.242(2) 1.271(2) 1.279(2)
N1 /C1 1.359(2) 1.334(2) 1.322(2)
N1 /C2 1.342(2) 1.367(2) 1.367(2)
N2 /C2 1.333(2) 1.354(2) 1.351(2)
3.2.3. 2-Benzoylimino-1,3-diaza-6,9-dioxacycloundecane
N2 /C3 1.448(2) 1.437(2) 1.439(2)
N3 /C2 1.330(2) 1.316(2) 1.314(2) 3
N3 /C4 1.450(2) 1.472(2) 1.473(2) The structure of 3 (Fig. 6) resembles the structure of 2
C3/C4 1.533(2) 1.528(2) 1.531(2) but there are also noteworthy differences. The long
Bond angles oxaalkylene chain leads to a clear deviation from
O1/M/N3 88.7(1) 90.5(1) planarity although the angle between the phenyl ring
M/O1 /C1 127.9(1) 128.4(1)
C9 /C14 and the fragment O1N1C1 is only 11.0(2)8.
C1/N1/C2 118.2(1) 118.1(1) 117.5(1)
M/N3 /C2 126.3(1) 126.0(1) There is an intramolecular hydrogen bond N2 /H2/


/
O1/C1/N1 127.1(1) 128.8(1) 128.8(1) O1 with an N/


/O distance of 2.616 A and an angle N/
N1 /C2/N2 121.2(1) 117.9(2) 118.4(1) H/


/O of 138.18. Owing to steric reasons and contrary to
N1 /C2/N3 129.1(1) 129.1(2) 128.2(1) the structure of 2 there is only one intermolecular
hydrogen bridge N3 /H3/


/O1[x , /y/1/2, z/12] (N/


/
O 2.825 A , N/H/


/O 162.68) which leads to formation
of a chain.
what shorter N1 /C2 bond (1.342 A ). The bonds C2 /N2 The bond lengths in 3 resemble the bond lengths of 2
and C2 /N3 are of equal length. with exception of the bonds N1 /C1 and N1 /C2 which
The complex formation of 2 with copper and nickel change their relation of length from 1.359: 1.342 A in 2
gives the isostructural bischelates 2a and 2b (Fig. 5). The to 1.336: 1.351 A in 3.
metal atoms are coordinated by two O atoms and two N The bulky structure of 3 shows that spatial require-
atoms. The molecules have an inversion center and the ments of the oxaalkylene chain make the formation of
coordination is square-planar. Again the imidazolidine complexes very improbable.
U. Schro
der et al. / Inorganica Chimica Acta 353 (2003) 59 /67 65

Scheme 1.

Fig. 1. Molecular structure of 1.

66 U. Schro
der et al. / Inorganica Chimica Acta 353 (2003) 59 /67

Fig. 2. Molecular structure of 1a.

Fig. 5. Molecular structure of 2a (M/Cu) and 2b (M /Ni).

Fig. 3. Molecular structure of 1b (M/Ni) and 1c (M/Co).

Fig. 4. Molecular structure of 2. Fig. 6. Molecular structure of 3.

 U. Schro
der et al. / Inorganica Chimica Acta 353 (2003) 59 /67 67

4. Supplementary material (c) M.P. Coles, P.B. Hitchcock, J. Chem. Soc., Dalton Trans.
(2001) 1169;
(d) S.M. Mullins, A.P. Duncan, R.G. Bergmann, J. Arnold,
Further details on the structure determinations are Inorg. Chem. 40 (2001) 6952.
available on request from the Cambridge Crystallo- [6] (a) Y. Zhou, G.P.A. Yap, D.S. Richeson, Organometallics 17
graphic Data Centre, 12 Union Road, Cambridge, CB2 (1998) 4387;
1EZ, UK, quoting the deposition numbers: CCDC (b) T.-G. Ong, D. Wood, G.P.A. Yap, D.S. Richeson, Organo-
207130-207137 (1, 1a, 1b, 1c, 2, 2a, 2b, 3). metallics 21 (2002) 1;
(c) G.R. Giesbrecht, G.D. Whitener, J. Arnold, J. Chem. Soc.,
Dalton Trans. (2001) 923.
[7] (a) I.M. Muller, R. Robson, Angew. Chem. 112 (2000) 4527;
Acknowledgements (b) I.M. Muller, R. Robson, F. Separovic, Angew. Chem. 113
(2001) 4519.
The authors thank the DAAD (J.A.-C., M.C.-M.) [8] M. Mitewa, Coord. Chem. Rev. 140 (1995) 1.
[9] W.O. Lin, C.N. Guimares, M.C. De Souza, J.B.N. Da Costa,
and the DFG (M.L.-P.) for financial support.
H.G. Alt, Phosphorus Sulfur Silicon 92 (1994) 1.
[10] (a) J. Angulo-Cornejo, M. Lino-Pacheco, R. Richter, L. Hennig,
K.-H. Hallmeier, L. Beyer, Inorg. Chim. Acta 305 (2000) 38;
References (b) L. Beyer, R. Richter, R. Wolf, J. Zaumseil, M. Lino-Pacheco,
J. Angulo-Cornejo, Inorg. Chem. Commun. 2 (1999) 184.
[1] P.J. Bailey, S. Pace, Coord. Chem. Rev. 214 (2001) 91. [11] (a) R. Richter, U. Schroder, L. Beyer, J. Angulo-Cornejo, M.
[2] P.J. Bailey, K.J. Grant, S. Pace, S. Parsons, L.J. Stewart, J. Chem. Lino-Pacheco, Z. Anorg. Allg. Chem. 627 (2001) 1877;
Soc., Dalton Trans. (1997) 4263. (b) J. Angulo Cornejo, F. Anaya Melendez, L. Beyer, R. Richter,
[3] (a) S. Pohl, M. Harmjanz, J. Schneider, W. Saak, G. Henkel, J. J. Sieler, Z. Anorg. Allg. Chem. 624 (1998) 892.
Chem. Soc., Dalton Trans. (2000) 3473; [12] B.W. Nash, R.A. Newberry, R. Pickles, W.K. Warburton, J.
(b) S. Pohl, M. Harmjanz, J. Schneider, W. Saak, G. Henkel, Chem. Soc. C (1969) 2794.
Inorg. Chim. Acta 311 (2000) 106. [13] J. Burkhardt, K. Hamann, Chem. Ber. 100 (1967) 2569.
[4] (a) H. Wittmann, A. Schorm, J. Sundermeyer, Z. Anorg. Allg. [14] M. Augustin, M. Richter, S. Salas, J. Prakt. Chem. 322 (1980)
Chem. 626 (2000) 1583; 55.
(b) V. Raab, J. Kipke, O. Burghaus, J. Sundermeyer, Inorg. [15] R. Neidlein, W. Haussmann, Chem. Ber. 99 (1966) 239.
Chem. 40 (2001) 6964. [16] G.M. Sheldrick, SHELX-97, A Program System for the Solution
[5] (a) P.J. Bailey, K.J. Grant, L.A. Mitchell, S. Pace, A. Parkin, S. and Refinement of X-ray Crystal Structures, University of
Parsons, J. Chem. Soc., Dalton Trans. (2000) 1887; Gottingen, Germany, 1997.
(b) S.R. Foley, G.P.A. Yap, D.S. Richeson, Chem. Commun. [17] R.P. Dixon, S.J. Geib, A.D. Hamilton, J. Am. Chem. Soc. 114
(2000) 1515; (1992) 365.