Journal of Supramolecular Chemistry 2 (2002) 415420

Layer and Chain Structures in the Co-Crystals of 18-Crown-6

with Aromatic Thiosemicarbazide Derivatives
Yurii A. Simonov,a Marina S. Fonari,a,* Janusz Lipkowski,b
Edward V. Ganinc and Arkadii A. Yavolovskiid
a
Institute of Applied Physics of the Academy of Sciences of Moldova, Chisinau, Moldova
Institute of Physical Chemistry, Polish Academy of Sciences, ul Kasprzaka 44/52, Warszawa, Poland
c
Odessa State Environmental University of the Ministry of Education and Science of Ukraine, Odessa, Ukraine
d
Bogatsky Physico-Chemical Institute of the National Academy of Science of Ukraine, Odessa, Ukraine
b

AbstractThe crystal structures of 1:2 binary complexes of 18-crown-6 with two thiosemicarbazide derivatives, phenylthiosemicarbazide (PH), (1) and quinoline thiosemicarbazide (QH), (2) are reported. Compound 1 displays a layered structure formed by
the association of PH zigzag chains and crown molecules. In compound 2 centrosymmetric QH dimers alternate with the crown
spacers in the chains. Both structures are sustained by NH. . .O and NH. . .S hydrogen bonds.
# 2003 Elsevier Ltd. All rights reserved.

Introduction
Crown ethers and their complexes have been intensively
studied during the last 30 years.1 The interest stems not
only from the fact that these systems exhibit a wide
variety of structural assemblies but also from the chemical and biological potential of these compounds as
ion exchangers and possible agents for transporting
ionic species in living tissues.
On the other hand, thiosemicarbazides and their derivatives are very suitable complexing agents due to high
exibility of their thiosemicarbazide branch. Metal
complexes and self-assembly of ligands derived from
these systems have been widely reported.2 So far, in
spite of rich exploration, only few examples are known
for the complexes of thiosemicarbazones and thiosemicarbazides and their derivatives with crown ethers (binary complexes of acetone thiosemicarbazone with
12-crown-4,3 complexes of thioamide hydrazide of
2-aminobenzoic acid and thioamide hydrazide of 4-amino1,2,5-thiodiazole-3-carbonic acid with 18-crown-64).
The topology of the networks formed is governed, at
least partially, by the availability of both hydrazine and
thioamide moieties in the same molecule that are capable of self-association of the molecules in a manner
Keywords: Crown based binary complexes; Thiosemicarbazide derivatives; Hydrogen bonding; X-ray crystallography.
*Corresponding author. Tel.: +373-2-738154; fax: +373-2-725887;
e-mail: [email protected]
1472-7862/02/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S1472-7862(03)00051-0

that directs crystal structures in two or even in three

directions. The aim of these studies is to create new
materials for applications such as molecular sieves with
applications to green chemistry.
This paper will outline further studies on hydrogenbonded polymeric networks constructed through the
interaction of crown ether with thiosemicarbazide
ligands possessing a multi-siteconnecting geometry.
Scheme 1 represents the ligands which have been used
successfully for design of 2D and 3D architectures in the
complexes with 18-crown-6 (18C6), hydrazide of 2-aminobenzoic acid (HA), hydrazide of 5-amine-1-benzyl1,2,3-triazole-4-carbonic acid (HB),4,5 thioamide hydrazide of 2-aminobenzoic acid (TB), thioamide hydrazide
of 4-amino-1,2,5-thiodiazole-3-carbonic acid (HT),5
phenylhydrazinecarbothioamide (PH), (2-quinoline-2ylcarbonyl)hydrazinecarbothioamide (QH) (this study).

Experimental
Crystals of 1 and 2 were obtained in nearly quantitative
yield from slow evaporation of the reactants at room
temperature. Intensity data for both complexes were
collected at room temperature for 1 and at 150 K for 2
on a Nonius Kappa CCD diractometer equipped with
graphite monochromatized MoKa radiation using rotation with sample-to-detector distance of 40 mm. Preliminary orientation matrix and unit cell parameters

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Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415420

Table 1. Crystal data and structure renement for compounds 1, 2

Empirical formula
Formula weight
Temperature, K
Space group
a (A)
b (A)
c (A)
b( )
Volume (A3)
Z
Dcalc, (g cm
3)
m, (mm
1)
F(000)
Crystal dimensions,
mm
y range for data
collection, deg.
Limiting indices
Reections collected/unique
Reections with I>2s(I)
Renement method
Data/restraints/parameters
Goodness-of-t on F2
Final R indices [I>2s(I)]
R indices (all data)
Largest di. peak (hole), e/ 3

C26H42N6O6S2
598.78
293 (2)
P21/c
9.996 (3)
14.585 (5)
11.181 (4)
102.11 (2)
1593.8 (9)
2
1.248
0.214
640
0.150.200.25

C34H44N8O8S2
756.89
150 (2)
P21/c
10.241 (2)
7.777 (2)
23.848 (6)
95.91 (8)
1889.3 (8)
2
1.331
0.201
800
0.200.200.30

2.08 to 27.49

2.76 to 27.48

12<h<12,
0<h<13,

15 <k<18,
0<k <10,

14<l<14

30<l<30
6629/3598
4319/4319
2613
3577
Full-matrix least squares on F2
3598/0/197
4319/0/251
1.050
1.108
R1=0.0471,
R1=0.0455,
wR2=0.1001
wR2=0.0937
R1=0.0667,
R1=0.0730,
wR2=0.1076
wR2=0.0996
0.315 (
0.238)
0.223 (
0.247)

Scheme 1.

were obtained from the peaks of the rst 10 frames,

respectively, and rened using the whole data set.
Frames were integrated and corrected for Lorentz and
polarization eects using DENZO.6 The scaling and
global renement of crystal parameters were performed
by SCALEPACK.6 Reections, which were partly measured on previous and following frames, are used to
scale these frames. The structures were solved by direct
methods and rened using SHELX977 software package. The non-hydrogen atoms of the asymmetric unit
were rened anisotropically (full-matrix least squares
method on F2). C-bound hydrogen atoms were placed in
calculated positions with their isotropic displacement
parameters riding on those of parent atoms, while the
N-bound H-atoms were found from dierential Fourier
maps and rened without any constraints. The X-ray
data and the details of the renement for (1) and (2) are
given in Table 1, the geometric parameters for H-bonds
are given in Table 2.

Table 2. Hydrogen bonds for 1 and 2

D-H...A

d(H...A), Ad(D...A), A (DHA), Symmetry code

for acceptor

1
N(11)H(1N1)...O(4)
N(11)H(2N1)...O(4)
N(12)H(1N2)...O(1)
N(13)H(1N3)...S(11)
2
N(11)H(1N1)...O(1)
N(11)H(2N1)...O(4)
N(12)H(1N2)...O(7)
N(13)H(1N3)...S(11)

2.32(2)
2.34(2)
2.11(2)
2.46(2)

3.075(2)
3.085(2)
2.918(2)
3.273(2)

158(2)
155(2)
163(2)
174(2)

2.24(2)
2.17(2)
2.28(2)
2.52(2)

3.077(2)
2.965(2)
3.081(2)
3.283(2)

158(2)
152(2)
160(2)
150(2)

x,
y+1,
z+1

x,
y+1/2, z
1/2
x,
y+1/2, z
1/2

x+1,
y+2,
z
x, y
1, z

x+1,
y+1,
z

Results and discussion

The 1:2 centrosymmetric binary complex 1 crystallizes
in the monoclinic system, space group P21/c. Figure 1
displays an ORTEP drawing with the atom labels. The
amine group of each PH molecule is perching above and
below the crown moiety and is linked to the macrocycle
via two long and appreciably bent NH. . .O hydrogen
bonds with symmetry related crown oxygens,
N(11). . .O(4) 3.075(2) and N(11). . .O(4)(
x,
y+1,

z+1) 3.085(2) A (angles subtended at the H atoms
158 and 155 , Table 2). The C(26)N(11) bond is

Figure 1. ORTEP view of 1. Thermal ellipsoids are given at 50%

probability level. The symmetry related PH molecule is omitted.

Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415420

practically perpendicular to the crown ether average

plane and nitrogen atom is deviated at 1.90 (1) A from
it. The phenyl ring of the PH molecule is situated
approximately parallel to the macrocycle, with the
dihedral angle between the average planes of the aromatic ring of PH and 6-O atoms of 18C6 being equal
to 2.1(1) . These units are associated into sheets by two
additional hydrogen bonds, NH. . .O and NH. . .S,
originating from both NH groups of hydrazine functionality and utilizing the thioureido S atom or a second crystallographically independent ether O atom as
acceptors.
The
rst
of
these
interactions,
N(12). . .O(1)(x,
y+1/2, z1/2) 2.918(2) A contributes
into stability of (PH)2. . .18C6. . .(PH)2 unit which is
sustained by six N-H. . .O hydrogen bonds. Single
NH. . .S hydrogen bond, N(13). . .S(11)(x,
y+1/2, z
1/2)
3.273(2) A links the PH molecules into zigzag chains
running along c direction in the unit cell (Fig. 2a). In the

417

layer each six PH molecules and two 18C6 are associated into cages closed by aforementioned hydrogen
bonds, each molecule in the layer being shared between
two neighboring cages. The layers are propagated parallel to the (011) plane (Fig. 2b). Two neighboring layers
meet by phenyl substituents that form hydrophobic
surfaces of each layer. The very similar layer organization has been previously found in the 18C6 complex
with HB4,5 where similar cages are found to be interconnected by 16 intermolecular hydrogen bonds of
NH...O(crown) and NH...OC types.
In 1 the sulfur atom contributes only to one NH. . .S
hydrogen bond, responsible for the PH arrangement in
chains in distinction to the free PH8 molecule, where a
chain structure is sustained by two alternating NH. . ..S,
R22(8)9,10 synthons I (Scheme 2) which are very typical
for thiosemicarbazides.

Figure 2. (a). Zigzag chain of PH molecules in 1. (b). Layer in 1. Red: oxygen, blue: nitrogen, yellow: sulfur.

418

Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415420

Scheme 2.

Figure 3. ORTEP view of 2. Thermal ellipsoids are given at 50%

probability level. The symmetry related QH molecule is omitted.

Figure 4. Chain in 2.

2 crystallizes in the monoclinic system, space group P21/c.

An ORTEP drawing with numbering scheme is shown
in Fig. 3. Similar to 1, primary amine group of QH
yields two weak and essentially bent NH. . .O hydrogen
bonds, N(11). . .O(4) 2.965(2), N(11). . .O(1)(
x+1,

y+2,
z) 3.077(2) A (angles subtended at the H atoms
158 and 152, Table 2), one more subsidiary NH. . .O
interaction exists with the translated macrocycle,
N(12). . .O(7)(x, y
1,
z) 3.283(2) A. Two QH molecules are combined into a centrosymmetric dimer via
two NH. . .S hydrogen bonds, N(13). . .S(11)(
x+1,

y+1,
z) 3.283(2) A, R22(10) graph set,11 II (Scheme
2). This H-bonded 10-membered ring is essentially corrugated with the deviations (from planar) of the contributing atoms falling in the range from 0.456(3) A for
C(26) to
0.432(3) A for N(12) and the dihedral angle
between the average planes of the planar quinoline system and R22(10) synthon itself equal 20.0(1) . The QH
dimers and crown molecules alternate in the chains
along b direction in the unit cell (Fig. 4). Fig. 5 displays
the chain packing in 2.
The aforementioned R22(10)11 synthon was previously
found in the associated in chains TB molecules in the
complex with 18C6. However, the amine group available
in TB in the neighboring to the thiosemicarbazide functionality position facilitates the further unication of
TB centrosymmetric dimers into chains via NH. . .S and
NH. . .O hydrogen bonds. In this case sulfur atom is
involved in two lying approximately at the straight line
NH. . .S hydrogen bonds, III, Scheme 2. The combination of TB chains and rows of crown ethers aords

Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415420

419

Figure 5. Packing of chains in 2.

Figure 6. Layer in the complex 18C6.(TB)2.

the layer structure, which is depicted in Fig. 6. The

comparison of these two packing modes reveals some
unexpected similarities. First, the unit cell dimensions
are very close for these two compounds, for 18C6.(TB)2:
a=10.437(2), b=7.942(3), c=19.958(7) A, b=90.89(2),
for 2 see Table 1. Space group P21/c is the same in both
cases. The chains that combine crown molecules and QH
(or TB) dimers are running along b direction in the unit

cell in both structures (Figs 5 and 6). Only van der Waals
interactions bind chains in 2. In 18C6.(TB)2 the layers
built of the similar chains and bound by H-bonding
interactions, are propagated in the same plane as the
chains in 2. So, one may say that the quinoline system
of two QH molecules that belong to the neighboring
chains corresponds in size to the H-bonded TB molecules. In the case of 2 the further development of chain

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Y. A. Simonov et al. / Journal of Supramolecular Chemistry 2 (2002) 415420

structure into the layered one is impeded by the absence

of the neighboring proton donor group in QH and it
prevents the transformation of II to III.

Supporting information
Tables of crystal data, atomic coordinates and thermal
parameters, full bond distances and angles, and structure factors may be obtained on request from the
authors. Crystallographic les in CIF format are also
available from the authors and from the Cambridge
Crystallographic Data Centre, on quoting the full journal citation and the deposition numbers CCDC 192819
and CCDC 192820 for compounds 1 and 2, respectively.
Acknowledgements
Support of this research from MRDA-CRDF (grant
MP2-3021) is gratefully acknowledged.
References and notes
1. (a) Pedersen, C. T.; Frensdor, H. K. Angew. Chem., Int.
Ed. Engl. 1972, 11, 16. (b) Lehn, J. M. Acc. Chem. Res. 1978,
11, 49. (c) Cram, D. J.; Cram, J. M. Acc. Chem. Res. 1978, 11,
8.
2. Allen, F. N.; Kennard, O. Chemical Design Automation
News 1993, 8 (1), 31 The search of thiosemicarbazide derivatives gave more than 200 hits for these molecules coordinated
to the metals and free ligands..
3. Henschel, D.; Blaschette, A.; Jones, P. G. Acta Cryst. 1997,
C53, 1875.
4. Fonari, M. S.; Simonov, Yu. A.; Kravtsov, V. Ch.; Lipkowski, J.; Ganin, E. V.; Yavolovskii, A. A. J. Mol. Str. 2003,
647, 129. CIF les are available from the authors and from the
Cambridge Crystallographic Data Centre, on the deposition
numbers CCDC 182691 and CCDC 175853 for the TB and
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kowski, J.; Ganin, E. V.; Yavolovskii, A. A. Russian Kristallograya 2002, 47, 93 CIF les are available from the
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160250 for the HA and HB crown complexes, respectively.
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1237. (b) Ferrari, M. B.; Bonardi, A.; Fava, G. G.; Pelizzi, C.;
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