Zinc coordination polymers with 1-(3-aminopropyl)-imidazole as bridging bidentate unit

Article abstract of DOI:10.1016/j.ica.2005.10.010

The reaction of Zn(SCN)₂ with one or two equivalents of 1-(3-aminopropyl)-imidazole (api) yields the coordination polymers [Zn(SCN) ₂(api)]_n (1) and [Zn(SCN)₂(api) ₂]_n (2), respectively. Single-crystal X-ray diffraction analysis reveals one-dimensional polymeric chain structures for both compounds. The structure of 1 consists of tetrahedral Zn(SCN)₂(api)₂ units linked by one molecule 1-aminopropyl imidazole in an unsymmetric mode, i.e., each metal center is coordinated by an imidazole nitrogen as well as a nitrogen of the aminopropyl group. The metal ions in 2 display an octahedral coordination geometry with each Zn(SCN)₂(api)₂ unit linked by two molecules of the imidazole, thus, exhibiting two imidazole and two amino groups in the coordination sphere. The polymers were further characterized by IR-, ¹H NMR- and ¹³C NMR-spectroscopy.

Full text of DOI:10.1016/j.ica.2005.10.010

Inorganica Chimica Acta 359 (2006) 327–333
www.elsevier.com/locate/ica
Zinc coordination polymers with 1-(3-aminopropyl)-imidazole
as bridging bidentate unit
*
Ulrich Arnold , Olaf Walter, Manfred Do¨ring
Institute for Technical Chemistry (ITC–CPV), Forschungszentrum Karlsruhe GmbH, P.O. Box 3640, 76021 Karlsruhe, Germany
Received 13 July 2005; received in revised form 6 October 2005; accepted 8 October 2005
Available online 22 November 2005
Abstract
The reaction of Zn(SCN)2 with one or two equivalents of 1-(3-aminopropyl)-imidazole (api) yields the coordination polymers
[Zn(SCN)2(api)]n (1) and [Zn(SCN)2(api)2]n (2), respectively. Single-crystal X-ray diffraction analysis reveals one-dimensional polymeric
chain structures for both compounds. The structure of 1 consists of tetrahedral Zn(SCN)2(api)2 units linked by one molecule 1-amino-
propyl imidazole in an unsymmetric mode, i.e., each metal center is coordinated by an imidazole nitrogen as well as a nitrogen of the
aminopropyl group. The metal ions in 2 display an octahedral coordination geometry with each Zn(SCN)2(api)2 unit linked by two mol-
ecules of the imidazole, thus, exhibiting two imidazole and two amino groups in the coordination sphere. The polymers were further
1
characterized by IR-, H NMR- and 13C NMR-spectroscopy.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Coordination polymer; Zinc; 1-(3-Aminopropyl)-imidazole; Imidazole complex; Thiocyanate
1. Introduction
in separation technology [3], including enantiomer separa-
tion [4]. Furthermore, materials based on metal-organic
frameworks showed interesting (semi)conductive [5], mag-
netic [6], optical [7] as well as catalytic [8] properties with
a broad variety of potential applications in materials sci-
ence and catalysis [9].
Numerous zinc coordination polymers were reported
[10] comprising carboxylate [11] or nitrogen donor ligands
such as 1,2,4-triazole [12], imidazole [13], 1,4-bis(imidazol-
1-ylmethyl)benzene [14], 2,20-bi-1,6-naphthyridine [15], 4,6-
bis(imidazol-1-yl)-1,3,5-triazine-2-one [16], bipyridine [17],
1,2-bis(4-pyridyl)ethylene [18], 2,4-bis(4-pyridyl)-1,3,5-tri-
azine [19] or 1,2-bis(imidazol-1-yl)ethane [20]. During the
course of our studies on the coordination chemistry of 1-
aminoalkyl functionalized imidazoles, we observed that,
with a series of metal salts, coordination networks can be
obtained. Here, we report on the synthesis and character-
ization of zinc coordination polymers bearing 1-(3-amino-
propyl)-imidazole (api) as bidentate bridging building
block.
The design and rational development of well defined
solid state structures with predictable chemical and physi-
cal properties is a highly attractive current challenge with
an enormous potential, e.g., in materials science or cataly-
sis. In this context, the synthesis of coordination polymers
built up by metal centers and polydentate organic ligands is
a very promising approach towards new one-, two- or
three-dimensional crystalline frameworks [1]. A whole ser-
ies of metals and an innumerable variety of multidentate
ligands allow the development of new metal-organic coor-
dination networks with intriguing structures and proper-
ties. Porous coordination polymers have been reported
for resembling zeolites [2], which can extend the series of
well-established zeolitic structures from micro- to meso-
or nanoporosity. These materials offer applications, e.g.,
*
Corresponding author. Tel.: +49 7247 823694; fax: +49 7247 822244.
E-mail address: ulrich.arnold@itc-cpv.fzk.de (U. Arnold).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.10.010

328
U. Arnold et al. / Inorganica Chimica Acta 359 (2006) 327–333
Table 1
2. Experimental
2.1. General procedures
Crystallographic data and refinement details for 1 and 2
1
2
Formula
Mr
C8H11N5S2Zn
306.71
200(2)
0.71073
triclinic
C14H22N8S2Zn
431.89
200(2)
0.71073
triclinic
All reactions were carried out without precautions
against moisture and air. Zn(NO3)2 Æ 6H2O, KSCN and
1-(3-aminopropyl)-imidazole were purchased from Aldrich
and used as received. Zn(SCN)2 was prepared by reacting
Zn(NO3)2 with KSCN in methanol and filtering off the pre-
cipitated KNO3. The thus obtained solutions of Zn(SCN)2
in methanol were used without further isolation and purifi-
cation of the salt. FT-IR spectra were recorded on a
Perkin–Elmer System 2000 instrument using KBr pellets.
NMR data were obtained on a Bruker Avance 250 spec-
T (K)
˚
k(Mo Ka) (A)
Crystal system
Space group
ꢀ
ꢀ
P1 (No. 2)
P1 (No. 2)
˚
a (A)
7.4787(4)
8.1828(5)
12.0259(7)
97.8400(10)
107.5400(10)
109.1500(10)
639.89(6)
2
7.7860(12)
8.8746(12)
13.736(3)
80.881(2)
88.848(2)
87.9620(10)
936.4(3)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
1
1
trometer (250.1 MHz for H, 62.9 MHz for 13C). H and
13C chemical shifts were determined by reference to resid-
ual solvent peaks. Elemental analyses were performed
using a Vario EL III instrument.
Z
2
Dcalc (g cmꢀ3
)
1.592
2.226
312
1.532
1.550
448
l(Mo Ka) (mmꢀ1
F(000)
)
Crystal size (mm)
h Range (ꢁ)
hkl Range
0.4 · 0.2 · 0.4
1.84–28.29
ꢀ9/9, ꢀ10/10,
ꢀ15/15
2.0 · 2.0 · 1.2
2.33–28.27
ꢀ10/10, ꢀ11/11,
ꢀ17/18
2.2. Synthesis of [Zn(SCN)2(api)]n (1)
Reflections collected
Unique reflections (Rint
Data with I P 2r(I)
Parameters refined
6801
6625
Amorphous 1 can be obtained by adding 50 mmol of api
dropwise to a 50 mmol solution of Zn(SCN)2 in 80 ml
MeOH. The polymer precipitates immediately. The solvent
is decanted off and the precipitate is washed with 30 ml
MeOH. After drying in vacuum, 1 is obtained in a yield
of 61%. Crystalline 1 can be prepared by reacting
100 mmol of api with 50 mmol of Zn(SCN)2 in 80 ml
MeOH. After stirring the reaction mixture for 4 h, the sol-
vent is removed in vacuum and the oily residue is allowed
to stand at room temperature. After 4 days colorless crys-
tals of 1 in a yield of 8% are obtained. Further crystalline
fractions yield mixtures of 1 and [Zn(SCN)2(api)2]n (2).
1H NMR (DMF-d7): d 2.18 (m, 2H, CH2); 2.72 (t, 2H,
CH2–NH2); 4.37 (t, 2H, N–CH2); 4.45 (s, br, 2H, NH2);
7.22, 7.63, 8.34 (s, 1H, imidazole CH). 13C–{1H} NMR
(DMF-d7): d 32.7 (CH2); 39.7 (N–CH2); 45.7 (CH2–
NH2); 122.0, 127.5 (imidazole CH); 137.8 (SCN); 139.6
(imidazole CH). Calc. for C8H11N5S2Zn: C, 31.33; H,
3.61; N, 22.83; S, 20.91. Found: C, 31.04; H, 3.44; N,
22.46; S, 20.56%.
)
3026 (0.0134)
2693
155
3461 (0.0171)
2403
246
Goodness-of-fitꢀ(o3 n F2)
1.055
1.177
˚
(Dp)max,min (e A
)
0.310, ꢀ0.268
R1 = 0.0246,
wR2 = 0.0640
R1 = 0.0288,
0.481, ꢀ1.293
R1 = 0.0472,
wR2 = 0.1317
R1 = 0.0564,
Final R indices [I P 2r(I)]a
R indices (all reflections)
wR2 = 0.0656
wR2 = 0.1416
P
P
P
P
2
2
1=2
a
R1 = (|Fo| ꢀ |Fc|)/ (|Fo|); wR2 ¼ f ½wðF 2o ꢀ F c2Þ ꢁ= ½wðF o2Þ ꢁg
;
2
w ¼ 1=½r2ðF o2Þ þ ðaPÞ þ bPꢁ and P ¼ ðmaxðF o2; 0Þ þ 2F 2c Þ=3.
5.13; N, 25.95; S, 14.85. Found: C, 38.81; H, 5.03; N,
26.10; S, 14.81%.
2.4. X-ray crystallography
X-ray diffraction data were collected on a Siemens
SMART 1000 CCD diffractometer at 200 K. The struc-
tures were solved by direct methods and refined by full-
matrix least-squares based on F2 using all measured unique
reflections. Non-hydrogen atoms were given anisotropic
displacement parameters, hydrogen atoms were localized
and refined isotropically. The calculations were performed
using SHELXS-97 and SHELXL-97 [21]. Graphical representa-
tions were drawn with WINRAY [22]. Crystal data, data col-
lection and refinement parameters for 1 and 2 are
summarized in Table 1.
2.3. Synthesis of [Zn(SCN)2(api)2]n (2)
Crystalline 2 can be prepared by adding an excess of
150 mmol of api to a 50 mmol solution of Zn(SCN)2 in
80 ml MeOH. After stirring the reaction mixture for 2 h,
the solvent is removed in vacuum until an oily, slightly
brownish residue is obtained. After 1 week at room temper-
ature colorless crystals of 2 are obtained, which are allowed
to grow during a period of 3 months to give the polymer in
3. Results and discussion
1
a yield of 49%. H NMR (DMF-d7): d 2.04 (m, 2H, CH2);
3.1. Synthesis
2.68 (t, 2H, CH2–NH2); 3.40 (s, br, 2H, NH2); 4.27 (t, 2H,
N–CH2); 7.12, 7.47, 8.09 (s, 1H, imidazole CH). 13C–{1H}
NMR (DMF-d7): d 33.5 (CH2); 39.1 (N–CH2); 44.9 (CH2–
NH2); 120.8, 127.8 (imidazole CH); 136.6 (br, SCN); 138.6
(imidazole CH). Calc. for C14H22N8S2Zn: C, 38.94; H,
Amorphous 1 can easily be obtained by reacting
Zn(SCN)2 with one equivalent of api. The compound
precipitates immediately upon addition of imidazole to

U. Arnold et al. / Inorganica Chimica Acta 359 (2006) 327–333
329
solutions of the metal salt in methanol. Reaction of
Zn(SCN)2 with two equivalents of api under the same reac-
tion conditions gives an oily mixture of 1 and 2, which crys-
tallizes within a few days yielding at first crystals of 1
followed by mixtures of 1 and 2. Pure 2 can be synthesized
by reacting Zn(SCN)2 with three equivalents of imidazole
and crystallization of 2 from the reaction mixture. Com-
pounds 1 and 2 are insoluble in water and organic solvents
such as EtOH, acetonitrile, CH2Cl2, THF, toluene or hex-
ane. Polymer 1 is partially soluble in acetone whereas poly-
mer 2 dissolves readily in this solvent. Both compounds
show good solubility in DMSO and DMF.
from d = 1.86 for the free ligand to d = 4.45 for 1 and
d = 3.40 for 2. Complexation of api is further indicated
in the H NMR spectra of 1 and 2 by the low-field shift
1
of imidazole CH resonances (Dd of up to 0.7) relative to
the free ligand. 13C NMR data of coordinated api are
not remarkably shifted compared to free api and fall within
the usual range.13C-resonances due to the thiocyanate
ligands are observed at d = 137.8 (1) and d = 136.6 (2).
Apart from the expected slight shift of resonances, NMR
data of 1 and 2 in DMSO solution are the same as those
obtained from DMF solutions. Attempts to characterize
the structures of 1 and 2 by HPLC coupled with ESI-MS
from solutions of the compounds in mixtures of DMF
and methanol and also, in the case of 2, mixtures of ace-
tone and methanol, failed and only low molecular mass
3.2. Spectroscopic characterization
The characteristic solid state IR data of api and the
coordination polymers 1 and 2 are summarized in Table
2. Coordination of the amino group to zinc is indicated
by the shift of the symmetric and asymmetric NH2 stretch-
ing vibrations from 3420 cmꢀ1 for the free ligand to
3229 cmꢀ1 for 1. The band of api shows a shoulder towards
lower wavenumbers, the band of 1 towards higher wave-
numbers. Two sharp bands at 3308 and 3249 cmꢀ1 were
observed for 2. All compounds show bands between 3100
and 3160 cmꢀ1, which can be attributed to the C–H stretch-
ing vibrations of imidazole ring. The C–H stretches of the
aminoalkyl group were observed between 2880 and
2970 cmꢀ1. The spectra of 1 and 2 are dominated by very
strong and sharp bands at 2082 and 2065 cmꢀ1, which
can be assigned to the SCN ligand. The NH2 deformation
vibration of api should display an absorption in the 1650–
1560 cmꢀ1 region shifting towards lower wavenumbers
upon complexation. However, it is difficult to determine
this absorption with certainty, due to superposition with
stretching vibrations of imidazole ring, which already
appear in this area [23]. Spectra below 1500 cmꢀ1, espe-
cially data for polymer 2, are complex and dominated by
imidazole ring stretching, bending and deformation vibra-
tions. The bands of polymer 1 in this area correspond to
those of free api and are shifted up to 40 cmꢀ1 compared
to the free ligand.
Table 3
˚
Selected bond lengths (A) and angles (ꢁ) for compounds 1 and 2
1
2
Zn(1)–N(4)
Zn(1)–N(5)
Zn(1)–N(1)
Zn(1)–N(3B)
N(4)–C(7)
N(5)–C(8)
S(1)–C(7)
1.9559(17)
1.9721(17)
1.9862(14)
2.0193(15)
1.162(2)
1.156(2)
1.6204(18)
1.6232(19)
Zn(1)–N(1)
Zn(1)–N(3Z)
Zn(1)–N(6Z)
Zn(1)–N(4)
Zn(1)–N(7)
Zn(1)–N(8)
N(7)–C(13)
N(8)–C(14)
S(1)–C(13)
S(2)–C(14)
2.158(3)
2.159(3)
2.167(3)
2.172(3)
2.217(3)
2.240(4)
1.171(5)
1.153(5)
1.640(4)
1.630(4)
S(2)–C(8)
N(4)–Zn(1)–N(5)
N(4)–Zn(1)–N(1)
N(5)–Zn(1)–N(1)
N(4)–Zn(1)–N(3B)
N(5)–Zn(1)–N(3B)
N(1)–Zn(1)–N(3B)
C(7)–N(4)–Zn(1)
C(8)–N(5)–Zn(1)
N(4)–C(7)–S(1)
106.12(7)
N(1)–Zn(1)–N(3Z)
N(1)–Zn(1)–N(6Z)
N(3Z)–Zn(1)–N(4)
N(6Z)–Zn(1)–N(4)
N(1)–Zn(1)–N(7)
N(3Z)–Zn(1)–N(7)
N(6Z)–Zn(1)–N(7)
N(4)–Zn(1)–N(7)
N(1)–Zn(1)–N(8)
N(3Z)–Zn(1)–N(8)
N(6Z)–Zn(1)–N(8)
N(4)–Zn(1)–N(8)
N(3Z)–Zn(1)–N(6Z)
N(1)–Zn(1)–N(4)
N(7)–Zn(1)–N(8)
C(13)–N(7)–Zn(1)
C(14)–N(8)–Zn(1)
N(7)–C(13)–S(1)
N(8)–C(14)–S(2)
88.22(13)
91.44(12)
91.02(13)
89.32(12)
89.22(12)
93.08(13)
86.73(13)
90.33(13)
90.21(12)
87.05(13)
93.14(13)
90.25(13)
179.61(13)
179.10(14)
179.41(14)
137.5(3)
109.30(7)
109.50(7)
111.69(7)
109.49(7)
110.63(6)
162.93(17)
161.41(17)
178.41(18)
179.39(19)
N(5)–C(8)–S(2)
The 1H and 13C NMR spectra of 1 and 2 in DMF solu-
tion are very similar. The resonances for both compounds,
except the signals for the NH2 protons, were observed at
almost the same d values. The broad NH2 signal is shifted
137.4(3)
178.1(4)
178.5(4)
Table 2
Selected IR data for api, 1 and 2
Compound
Characteristic bands in Mid-IR (cmꢀ1
)
3500–3200
3200–3000
3109 (m, sh)
3124 (m)
3000–2800
2100–2000
1700–1500
api
3420 (vs, sh)a
2940 (m, sh)
2949 (w, sh)
1586 (s, sh), 1512 (m)
1
3229 (m, sh)
2082 (vs)
2065 (vs)
1582 (w, sh), 1534(m)
1527 (m)
2
3308 (s)
3249 (m)
3157 (m), 3138 (w)
3120 (m)
2966 (w), 2938 (m)
2883 (w)
1612 (w), 1590 (m)
1528 (s), 1516 (m)
a
vs = very strong, s = strong, m = medium, w = weak, sh = shoulder.

330
U. Arnold et al. / Inorganica Chimica Acta 359 (2006) 327–333
fragments were detected. The simplicity of the NMR spec-
tra indicates uniform or at least very similar species with
almost the same structural characteristics. Furthermore,
NMR data of 1 and 2 show no evidence of uncoordinated
aminopropyl and imidazole groups. These results suggest
the presence of oligomeric chain structures that arrange
in ring structures.
[Zn(SCN)2(4-tert-butyl-1,2,4-triazole)2] [24] or [Zn(SCN)2-
(ethylenediamine)] [25]. The Zn–N(amino) distances are
longer than the Zn–N(imidazole) or Zn–N(triazole)
distances and this can also be observed in complexes with
chelating histidine ligands, e.g., [Zn(histidinemethylester)2]-
(BPh4)2 [26], where the Zn–N(imidazole) bonds (1.947(1)
˚
and 1.991(1) A) can be directly compared to the Zn–
˚
N(amine) bonds (2.047(1) and 2.012(1) A). The SCN
3.3. Crystal structure analysis
ligands in 1 show very small distortions from linearity
(178.41(18)ꢁ and 179.39(19)ꢁ) and bind to the metal in a
non-linear mode with Zn–N–CS angles around 162ꢁ. The
SCN ligands in triazole and ethylene diamine derivative
are almost linear and the Zn–N–CS angles are between
178.2(7)ꢁ and 168.7(8)ꢁ.
Selected bond distances and angles of compounds 1 and
2 are listed in Table 3. Figs. 1 and 2 show WINRAY views of 1
and 2 with the atomic labeling schemes. Both compounds
consist of Zn(SCN)2 units linked by api thus building up
one-dimensional polymeric chain structures. In polymer
1, the metal centers are connected by one molecule api in
a non-symmetric mode, i.e., each Zn(SCN)2 unit shows a
tetrahedral coordination environment with an imidazole
and an amino group in the coordination sphere. The tetra-
hedron is only slightly distorted with a maximum deviation
of 3.35ꢁ from ideal geometry. The Zn–N distances are in
In polymer 2, the Zn(SCN)2 units are linked by two mol-
ecules api thus displaying an octahedral geometry with two
imidazole and two amino groups in the coordination
sphere. The NCS, imidazole and amine donors are in trans
position, respectively. Despite the steric requirement of the
api ligand and the steric constraint of the polymer chain,
distortion of the coordination polyhedron is small. The
valence angles in the octahedron differ from 90ꢁ by a max-
imum of 3.27ꢁ. The Zn–N(api) distances are almost equal
˚
the range between 1.956(2) and 2.019(2) A with the Zn–
NCS bonds (1.956(2) and 1.972(2) A) being shorter than
the Zn–N(imidazole) bond (1.986(1) A) and the Zn–
N(aminopropyl) bond (2.019(2) A). This is in accordance
˚
˚
˚
with an average bond length of 2.164 A and the distances
˚
˚
Zn–NCS are around 2.228 A. This is in contrast to polymer
with other tetrahedral zinc thiocyanato complexes such as
1 where the Zn–N(imidazole) distances differ from the Zn–
H31
H32
C6
N3
H31B
H32B
N3B
C4
C5
C1
Zn1A
N2
N1
C2
Zn1
C3
N4
N5
C7
C8
S1
S2
Fig. 1. One-dimensional polymeric chain structure of 1. All hydrogen atoms except those of the amino groups have been omitted for clarity.
C4
N2
C1
C3
C5
C2
C6
H31
N1
H31Z
N3Z
N3
H32
H32Z
N7
Zn1A
Zn1
S1
C13
H61Z
H61
N8
N6Z
C14
S2
H62Z
N4
H61
Fig. 2. One-dimensional polymeric chain structure of 2. All hydrogen atoms except those of the amino groups have been omitted for clarity.

U. Arnold et al. / Inorganica Chimica Acta 359 (2006) 327–333
331
N(amino) distances and where the Zn–NCS distances are
shorter than the Zn–N(api) distances. The values are in
accordance with other coordination polymers bearing octa-
hedral Zn(SCN)2 units such as those with 1,2,4-triazole [12]
or 2,20-bi-1,6-naphthyridine [15] as bridging organic build-
ing blocks. Like in polymer 1 the SCN ligands are almost
linear (178.1(4)ꢁ and 178.5(4)ꢁ) and coordinate to the Zn
center in a non-linear mode. However, the angles Zn–N–
CS (137.4(3)ꢁ and 137.5(3)ꢁ) are much smaller compared
to polymer 1. These angles are usually in the range between
150ꢁ and 180ꢁ [27] but exceptions with very small Zn–N–
CS angles such as the octahedral zinc thiocyanato complex
with the tetradentate 1,4,8,11-tetraazacyclotetradecane
ligand (Zn–N–CS angles of 132.0(10)ꢁ and 137.8(9)ꢁ) are
described [28].
The packing structures of 1 and 2 are predominantly
determined by hydrogen bonding (Figs. 3 and 4). Adjacent
polymeric chains are assembled via interchain N–Hꢂ ꢂ ꢂS
hydrogen bonds between amino and thiocyanate groups.
˚
The Hꢂ ꢂ ꢂS distances in 1 (Fig. 3) are around 2.57 A with
angles N3–H31–S1 and N3–H32–S2 of 157.1(14)ꢁ and
166.9(15)ꢁ, respectively. The corresponding angles around
the sulfur atoms are 83.8(14)ꢁ (C7–S1–H31) and
109.1(15)ꢁ (C8–S2–H32). Polymer 2 (Fig. 4) displays two
different types of interchain N–Hꢂ ꢂ ꢂS bonds. The distances
˚
H62ꢂ ꢂ ꢂS1 (2.53(3) A) are significantly shorter than the dis-
N3Z
N3D
H31Z
H31D
S1A
S1B
C7AF
C7BF
C7B
C7A
S1BF
S1AF
H31
H31F
N3
H32
N3ZF
H32F
C8A
C8B
S2A
S2BG
S2B
S2AG
C8BG
C8AG
H32G
H32G
N3ZG
N3G
Fig. 3. View of a section of the metal–ligand network in 1 showing the interchain N–Hꢂ ꢂ ꢂS hydrogen bonds (dashed lines).
N6ZF
H61F
H62F
C13F
S1ZF
S1ZF
H62F
H61F
C13F
N6ZF
N3AF
H31F
H32F
C14F
S2AF
S2B
C14B
H31Z
H32Z
N3Z
Fig. 4. View of a section of the metal–ligand network in 2 showing the interchain N–Hꢂ ꢂ ꢂS hydrogen bonds (dashed lines).

332
U. Arnold et al. / Inorganica Chimica Acta 359 (2006) 327–333
˚
Lehn (Eds.), Comprehensive Supramolecular Chemistry, Pergamon,
Oxford, 1996;
(j) J.-M. Lehn, Supramolecular Chemistry: Concepts and Perspec-
tives, VCH, Weinheim, 1995.
tances H31ꢂ ꢂ ꢂS2 (2.68(3) A). The corresponding angles of
the former (N6–H62–S1: 151.2(14)ꢁ, C13–S1–H62:
116.6(14)ꢁ) are somewhat smaller than those of the latter
(N3–H31–S2: 166.4(15)ꢁ, C14–S2–H31: 120.0(15)ꢁ). The
polymeric chains are assembled into planes via hydrogen
bonding, giving rise to a layered packing structure.
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Additional crystallographic data have been deposited at
the Cambridge Crystallographic Data Centre, CCDC ref-
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conts/retrieving.html (or from CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; e-mail:
deposit@ccdc.cam.ac.uk).
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Financial support from the Bundesministerium fur Bil-
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dung und Forschung (BMBF), Germany and the Bakelite
AG, Duisburg is gratefully acknowledged.
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