Synthesis, crystal structures, and thermal properties of new zinc(II) thiocyanato coordination compounds

Article abstract of DOI:10.1002/zaac.201000216

Reaction of zinc(II) thiocyanate with pyrazine, pyrimidine, pyridazine, and pyridine leads to the formation of new zinc(II) thiocyanato coordination compounds. In bis(isothiocyanato-N)-bis(μ₂-pyrazine-N,N) zinc(II) (1) and bis(isothiocyanato-N)-bis(μ₂-pyrimidine-N,N) zinc(II) (2) the zinc atoms are coordinated by four nitrogen atoms of the diazine ligands and two nitrogen atoms of the isothiocyanato anions within slightly distorted octahedra. The zinc atoms are connected by the diazine ligands into layers, which are further linked by weak intermolecular S···S interactions in 1 and by weak intermolecular C-H···S hydrogen bonding in 2. In bis(isothiocyanato-N)-bis(pyridazine-N) (3) discrete complexes are found, in which the zinc atoms are coordinated by two nitrogen atoms of the isothiocyanato ligands and two nitrogen atoms of the pyridazine ligands. The crystal structure of bis(isothiocyanato-N)-tetrakis(pyridine-N) (4) is known and consists of discrete complexes, in which the zinc atoms are octahedrally coordinated by two thiocyanato anions and four pyridine molecules. Investigations using simultaneous differential thermoanalysis and thermogravimetry, X-ray powder diffraction and IR spectroscopy prove that on heating, the ligand-rich compounds 1, 2, and 3 decompose without the formation of ligand-deficient intermediate phases. In contrast, compound 4 looses the pyridine ligands in two different steps, leading to the formation of the literature known ligand-deficient compound bis(isothiocyanato-N)-bis(pyridine-N) (5) as an intermediate. The crystal structure of compound 5 consists of tetrahedrally coordinated zinc atoms which are surrounded by two isothiocyanato anions and two pyridine ligands. The structures and the thermal reactivity are discussed and compared with this of related transition metal isothiocyanates with pyrazine, pyrimidine, pyridazine, and pyridine. Copyright

Full text of DOI:10.1002/zaac.201000216

ARTICLE
DOI: 10.1002/zaac.201000216
Synthesis, Crystal Structures, and Thermal Properties of New Zinc(II)
Thiocyanato Coordination Compounds
[a]
[a]
[a]
[a]
Gaurav Bhosekar, Jan Boeckmann, Inke Jeß, and Christian Näther*
Keywords: Coordination chemistry; Zinc; Thiocyanates; Organic-inorganic hybrid composites; Thermochemistry
Abstract. Reaction of zinc(II) thiocyanate with pyrazine, pyrimidine, discrete complexes, in which the zinc atoms are octahedrally coordi-
pyridazine, and pyridine leads to the formation of new zinc(II) thiocya- nated by two thiocyanato anions and four pyridine molecules. Investi-
nato coordination compounds. In bis(isothiocyanato-N)-bis(μ
2
-pyra- gations using simultaneous differential thermoanalysis and thermogra-
zine-N,N) zinc(II) (1) and bis(isothiocyanato-N)-bis(μ -pyrimidine- vimetry, X-ray powder diffraction and IR spectroscopy prove that on
2
N,N) zinc(II) (2) the zinc atoms are coordinated by four nitrogen atoms heating, the ligand-rich compounds 1, 2, and 3 decompose without the
of the diazine ligands and two nitrogen atoms of the isothiocyanato formation of ligand-deficient intermediate phases. In contrast, com-
anions within slightly distorted octahedra. The zinc atoms are con- pound 4 looses the pyridine ligands in two different steps, leading
nected by the diazine ligands into layers, which are further linked by to the formation of the literature known ligand-deficient compound
weak intermolecular S···S interactions in 1 and by weak intermolecular bis(isothiocyanato-N)-bis(pyridine-N) (5) as an intermediate. The crys-
C–H···S hydrogen bonding in 2. In bis(isothiocyanato-N)-bis(pyrida- tal structure of compound 5 consists of tetrahedrally coordinated zinc
zine-N) (3) discrete complexes are found, in which the zinc atoms are atoms which are surrounded by two isothiocyanato anions and two
coordinated by two nitrogen atoms of the isothiocyanato ligands and pyridine ligands. The structures and the thermal reactivity are dis-
two nitrogen atoms of the pyridazine ligands. The crystal structure of cussed and compared with this of related transition metal isothiocya-
bis(isothiocyanato-N)-tetrakis(pyridine-N) (4) is known and consists of nates with pyrazine, pyrimidine, pyridazine, and pyridine.
Introduction
the course of such reactions more condensed networks are
formed. This was the origin of further investigations that
should show if paramagnetic transition metal compounds with
terminally bonded small-sized ligands like e.g. thio- or seleno-
cyanates can be transformed into new compounds with bridg-
ing anions that show a modified magnetic behavior [15, 21–
Recently, numerous investigations on the synthesis, struc-
tures and properties of coordination polymers, inorganic-or-
ganic hybrid compounds, or metal organic frameworks have
been reported [1–10]. One important goal in this field com-
prised the preparation of compounds with useful physical prop-
erties. Most of these compounds are prepared in solution,
which frequently leads to mixtures that sometimes have to be
separated by hand. Therefore, a few years ago we started sys-
tematic investigations on the preparation of coordination poly-
mers by thermal decomposition reactions. By this method li-
gand-rich precursor compounds are thermally decomposed,
which frequently leads to the formation of ligand-deficient
compounds in pure form and quantitative yields. We firstly
investigated the synthesis of coordination compounds on the
basis of copper(I) and zinc(II) halides and N-donor ligands
28]. In the meantime we have found several examples for such
a behavior and in the following we also have started investiga-
II
II
tions on the thermal properties of Zn and Cd thiocyanates in
order to prove if a similar thermal reactivity is observed.
A search in the Cambridge Structural Database for zinc(II)
thiocyanates with N-donor ligands leads to about 170 hits [29,
3
0]. In practically all of them the thiocyanato anions are only
terminal bonded and selected examples are given in references
31–38]. In only one of these structures the anions are con-
[
nected by the sulfur atom to the zinc(II) atom but no space
group and coordinates are given [39]. Interestingly, in only
three structures the metal atoms are connected by the thiocya-
nato anion in μ-1,3-coordination [40–42]. Therefore, the ques-
tion raises if bridged zinc(II) thiocyanates can be prepared by
thermal decomposition reactions.
In the beginning, we investigated zinc(II) thiocyanates with
pyridine, pyrazine, pyrimidine, and pyridazine as neutral coli-
gands, for which according to the CCDC only crystal struc-
tures with pyridine were reported. With pyrazine only a struc-
ture of the ligand rich 1:4 compound (1:4 = ratio between
metal and neutral N-donor coligand) bis(isothiocyanato-N)(tet-
rakis(pyrazine-N) zinc(II) was published in 2007 but retracted
[
11–20].
Comparison of the crystal structures of the ligand-rich pre-
cursors and the ligand-deficient intermediates proves that in
*
Dr. C. Näther
Fax: +49-431-8801520
E-Mail: cnaether@ac.uni-kiel.de
[
a] Institut für Anorganische Chemie
Christian-Albrechts-Universität zu Kiel
Max-Eyth-Straße 2
24118 Kiel, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201000216 or from the
author
Z. Anorg. Allg. Chem. 2010, 636, 2595–2601
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2595

G. Bhosekar, J. Boeckmann, I. Jeß, C. Näther
ARTICLE
in 2010 [43]. With pyridine a ligand-rich 1:4 compound of further linked by weak intermolecular S···S interactions be-
composition [Zn(NCS) (pyridine) ] [44] and a ligand-deficient tween the sulfur atoms of the isothiocyanato ligands. The S···S
2
4
1
:2 compound of composition [Zn(NCS) (pyridine) ] [45] is distance amounts to 3.5 Å, which is slightly shorter than the
2 2 n
known and therefore, it can be easily proved if this 1:2 com- sum of the van der Waals radii [50].
pound occurs as an intermediate in the thermal decomposition
reaction of the 1:4 compound. Herein we report on our investi-
gations.
Results and Discussion
Crystal Structures
The 1:2 compound bis(isothiocyanato-N)-bis(μ -pyrazine-
2
N,N') zinc(II) (1) crystallizes in the monoclinic space group
C2/m with two formula units in the unit cell and is isotypic
to its manganese [46], iron [47], cobalt [48], and nickel [49]
analogues reported recently. The zinc atoms are located on po-
sition 2/m, the isothiocyanato ligands on a mirror plane and
the pyrazine ligand on a center of inversion (Figure 1). Each
zinc atom is coordinated by four nitrogen atoms of the pyra-
zine ligands and two nitrogen atoms of the isothiocyanato li-
gands within a slightly distorted octahedral arrangement (Fig-
Figure 2. Crystal structure of compound 1 with view onto the layers
ure 1 and Table 1). The isothiocyanato ligands are trans-
(
black = metal, dark-grey = nitrogen, grey = carbon, light-grey = sul-
oriented and are only terminally bonded.
fur, white = hydrogen).
The 1:2 compound bis(isothiocyanato-N)-bis(μ -pyrimidine-
2
N,N') zinc(II) (2) crystallizes in the orthorhombic space group
Cmca with four formula units in the unit cell and is isotypic
to its manganese [51], iron [51], cobalt [46, 52] and nickel
[
22] analogues reported recently. The zinc atom is located on
position 2/m, the isothiocyanato ligand on a mirror plane and
the pyrimidine ligand on a twofold rotation axis (Figure 3).
The zinc atom is coordinated by four nitrogen atoms of the
pyrimidine ligands and two nitrogen atoms of the isothiocya-
nato ligands within slightly distorted octahedral arrangement
(
Figure 3 and Table 2). As in compound 1, the isothiocyanato
ligands are trans-configured and act only as terminal ligands
through the nitrogen atoms.
Figure 1. Crystal structure of compound 1 with labelling and displace-
ment ellipsoids drawn at the 50 % probability level. Symmetry trans-
formations used to generate equivalent atoms: A: –x, –y+1, –z; B: x,
–y+1, z; C: –x, y, –z; D: –x+1/2, –y+3/2, –z.
Table 1. Selected bond lengths /Å and angles /° for 1.
Zn(1)–N(1)
2.060(3)
2.2486(17)
180.0
89.43(7)
90.57(7)
88.59(9)
91.41(9)
Zn(1)–N(11)
N(1)–Zn(1)–N(1)A
N(1)–Zn(1)–N(11)
N(1)–Zn(1)–N(11)
N(11)–Zn(1)–N(11)C
N(11)–Zn(1)–N(11)B
Symmetry codes: A: –x, –y+1, –z; B: x, –y+1, z; C: –x, y, –z; D:
–x+1/2, –y+3/2, –z.
Figure 3. Crystal structure of compound 2 with labelling and displace-
ment ellipsoids drawn at the 50 % probability level. Symmetry trans-
formations used to generate equivalent atoms: A: –x+1, –y+1, –z; B:
The zinc atoms are connected by the pyrazine ligands in μ-
N,N' coordination into layers, which are stacked in the direc-
tion of the crystallographic c axis (Figure 2). These layers are x, –y+1, –z; C: –x+1, y, z; D: –x+3/2, y, –z+1/2.
2
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New Zinc(II) Thiocyanato Coordination Compounds
Table 2. Selected bond lengths /Å and angles /° for 2.
from the isothiocyanato anions and two nitrogen atoms from
the pyridazine ligand (Figure 5 and Table 3). Because the two
nitrogen atoms are neighbored, no extended structures can be
formed.
Zn(1)–N(1)
2.2929(12)
2.0331(18)
88.72(6)
89.83(5)
90.17(5)
91.28(6)
180.0
Zn(1)–N(2)
N(1)–Zn(1)–N(1)C
N(2)–Zn(1)–N(1)A
N(2)–Zn(1)–N(1)
N(1)A–Zn(1)–N(1)C
N(2)–Zn(1)–N(2)A
Table 3. Selected bond lengths /Å and angles /° for 3.
Zn(1)–N(1)
Zn(1)–N(3)
2.0267(16)
1.932(2)
Symmetry codes: A: –x+1, –y+1, –z; B: x, –y+1, –z; C: –x+1, y, z;
D: –x+3/2, y, –z+1/2.
N(3)–Zn(1)–N(3A)
NN(3)–Zn(1)–N(1)
N(3A)–Zn(1)–N(1)
N(1A)–Zn(1)–N(1)
119.23(18)
105.64(8)
111.93(9)
101.08(9)
The zinc atoms are connected by the pyrimidine ligands in Symmetry codes: A: –x+1, y, –z+½.
μ-N,N' coordination into layers, which are located in the a/c
plane (Figure 4).
In the crystal structure the complexes are connected by weak
intermolecular C–H···N and C–H···S interactions into layers
that are located in the a/c plane (Figure 6).
Figure 4. Crystal structure of compound 2 with view in the direction
of the b axis (black = metal, dark-grey = nitrogen, grey = carbon, light- Figure 6. Crystal structure of compound 3 with view along the crystal-
grey = sulfur, white = hydrogen).
lographic b axis. Intermolecular C–H···S and C–H···N interactions are
shown as dashed lines (black = metal, dark-grey = nitrogen, grey =
carbon, light-grey = sulfur, white = hydrogen).
Compound 3 crystallizes in the monoclinic space group C2/c
with four formula units in the unit cell. The isothiocyanato
anions and the pyridazine ligands occupy general positions,
whereas the zinc atoms are located on twofold rotation axis
Thermoanalytical Investigations
(
Figure 5). In contrast to compounds 1 and 2, in 3 the zinc
atoms are only tetrahedrally coordinated by two nitrogen atoms
On heating, compounds 1, 2, and 3 in a thermobalance de-
composition starts at about 200 °C for 1 and at about 150 °C
for 2 and 3 (Figure S5–S7 in the Supporting Information). For
all compounds a continuous mass loss is observed without the
occurrence of distinct steps. From the experimental mass loss
it is obvious that the complete ligands are removed in one step
and that also the decomposition of the isothiocyanato anion
cannot be distinguished. Therefore, no ligand deficient inter-
mediates can be observed in the thermal decomposition reac-
tion of compounds 1–3.
If the 1:4 compound 4 is heated two different mass steps are
observed, that are accompanied with endothermic events in the
DTA curve at 96 °C and 183 °C (Figure 7). From the DTG
curve it is obvious that the two steps are well resolved and the
experimental mass loss in the first step of 31.5 % is in perfect
agreement with the removal of half of the pyridine ligands
Figure 5. Crystal structure of compound 3 with labelling and displace-
ment ellipsoids drawn at the 50 % probability level. Symmetry trans-
formation used to generate equivalent atoms: A : –x+1, y, –z+1/2.
Z. Anorg. Allg. Chem. 2010, 2595–2601
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G. Bhosekar, J. Boeckmann, I. Jeß, C. Näther
ARTICLE
(
Δmcalcd. = –31.4 %). Therefore, it can be assumed that in the
Additional investigations show that compound 4 is not very
first step a ligand-deficient 1:2 compound of composition stable at room temperature and decomposes within two hours.
Zn(SCN) (pyridine) (5) is formed that decomposes on further To prove the identity of all intermediates experiments using
heating.
2
2
time-dependent X-ray powder diffraction were performed (Fig-
ure 9). This experiment clearly shows that within about 1 h at
room temperature a transformation only into the ligand-defi-
cient 1:2 compound 5 is observed.
Figure 9. Time dependent XRPD patterns of compound 4 measured at
room temperature.
Spectroscopy
All compounds were additionally investigated by IR and Ra-
man spectroscopy because the coordination mode of the isothi-
ocyanato anion can easily be determined from their vibrational
Figure 7. DTG, TG, and DTA curves for compound 4. Heating rate = spectra (see Figures S7–S10 in the Supporting Information).
–
1
4
°C·min ; given are the mass changes /% and the peak temperatures
P
Due to the transformation of compound 4 into compound 5
even at room temperature, for 4 only a Raman spectrum could
be measured in glass capillaries.
T
/°C.
To prove this assumption a second TG experiment was per-
In general the three normal vibrational modes of the linear
isothiocyanato anion include the pseudo-asymmetric stretching
vibration ν [ν(CN)], the bending mode ν [δ(NCS)] and the
formed, in which the residue formed after the first mass loss
was isolated. The result of an elemental analysis of this residue
is in good agreement with that calculated for a 1:2 compound
1
2
pseudo-symmetric stretching vibration ν [ν(CS)]. All three
3
(
see Experimental Section). Moreover, if the residue is investi-
bands can be used to diagnose the coordination mode of the
isothiocyanato anion but the most interesting band is the very
gated by X-ray powder diffraction it is proven that the 1:2
compound bis(isothiocyanato-N)-bis(pyridine-N) zinc(II) (5) is
formed, that consists of discrete complexes, in which the
zinc(II) atom is coordinated by two N-bonding isothiocyanato
anions and two pyridine ligands within a slightly distorted tet-
rahedron (Figure 8) [45].
strong C–N stretching vibration ν , which is shifted only by a
1
few wavenumbers in terminal N-bonded isothiocyanato com-
pounds relative to that in the reference compound potassium
–
1
thiocyanate (ν = 2053 cm ) [53, 54]. In contrast, in μ -N,S
1
2
bridging isothiocyanato compounds ν1 occurs above
2
100 cm–1 and in μ -N bridging isothiocyanato compounds ν
2
1
–1
is found near or just below 2000 cm . In compounds 1–3, and
5
values of 2065, 2055, 2084/2099, and 2071/2097 cm–1 are
found for ν , which is in agreement with the presence of N-
1
bonded isothiocyanato anions (see Supporting Information)
(Table 4).
1
Table 4. Stretching vibration ν [ν(CN)] in the infrared (4000–
–1
–
1
4
00 cm ) and Raman spectra (3500–100 cm ) for the thiocyanato an-
ions in compounds 1–5.
Compound IR bands /cm–1
Raman bands /cm–1
1
2
3
4
5
2065
2062
2055
2062, 2054
2093
2099, 2084
–
2097, 2071
2069
2084, 2068
Figure 8. Experimental XRPD patterns of the residues obtained after
the first heating step in the thermal decomposition reaction of 4 (top)
and XRPD pattern for the 1:2 compound 5 calculated from single crys-
tal data.
For molecules with a center of symmetry the complementari-
ness of the Raman and infrared spectra implies only one infra-
2
598
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New Zinc(II) Thiocyanato Coordination Compounds
red active [ν (CN)] and one Raman active [νsym(CN)] band, structures of the ligand-rich precursors is only possible to some
as
as it should be the case for compounds 1, 2, and 4. For com- extent.
pounds 3 and 5 [ν (CN)] and [νsym(CN)] should be infrared
Finally, it must be mentioned that because of the structural
as
and Raman active. For compounds 1, 4, and 5 the experimental similarities between compounds 4 and 5, in which always dis-
measurements are in agreement with this rule. For compound crete complexes are formed it could be expected that even for
2
two bands are observed in the Raman spectra, but only one the compound with pyridazine a ligand-rich discrete 1:4 com-
broad band in the infrared spectra. In contrast, for compound plex must exist. However, we performed several experiments
3
two bands are observed in the infrared spectra and only one to prepare this compound but it has not formed even if a large
broadened band in the Raman spectra. Repeated measurements excess of pyridazine was used or the reaction was performed
of different batches for these compounds support this observa- in pure ligand. In any case only the 1:2 compound 3 was ob-
tion and we have really no explanation for it.
tained.
Conclusions
Experimental Section
In this contribution four zinc(II) thiocyanates were prepared
and investigated for their thermal properties. It was found that
the 1:2 compounds 1–3 decompose in one step without the
formation of ligand-deficient intermediates. This is a bit sur-
prising because recently we investigated the corresponding
compounds with the transition metals manganese, iron, cobalt,
and nickel, which in the case of e.g. pyrazine as coligand
shows the same topology of the coordination network [15, 49].
Syntheses
Zn(NCS)
2
: Ba(NCS)
2 2 4 2
·3H O (3.0755 g, 10 mmol) and ZnSO ·H O
(
1.61434 g) were stirred in water (100 mL). The colorless precipitate
4
of BaSO was filtered off and the water was removed from the filtrate
by heating. The final product was dried by 80 °C. The homogeneity
of the product was investigated by X-ray powder diffraction.
2
Compounds 1–3: Zn(NCS) (181.5 mg) and pyrazine, pyrimidine, or
If these compounds are heated a transformation into ligand- pyridazine (160.2 mg) were stirred in acetonitrile (2 mL) for 1 d. The
deficient 1:1 compounds is observed, in which the metal atoms precipitates were filtered off and washed with ethyl ether. On slow
are bridged by the isothiocyanato anions and the octahedral evaporation of the acetonitrile from the filtrate crystals are obtained,
which are suitable for single-crystal X-ray diffraction. The purity was
checked by XRPD (see Figure S1–S3 in the Supporting Information)
and elemental analysis. C10H N S Zn (341.71): calcd. C 35.15, H 2.36,
8 6 2
N 24.59 %; found C 35.23, H 2.38, N 24.49 % (1); C 35.05, H 2.29,
N 24.43 % (2); C 35.28, H 2.21, N 24.42 % (3).
coordination is retained. In compounds 1 and 2 also octahedral
coordination is present and it could be assumed that zinc is as
chalcophilic as the elements manganese, iron, cobalt, and
nickel in order that also intermediates with bridging isothiocy-
anato anions are formed, which is not the case here. In this
context it must also be mentioned that similar 1:2 compounds
Compound 4: The literature known compound 4 was prepared accord-
can also be prepared with e.g. zinc halides and pyrazine that ing to a different procedure by the reaction of ZnCl (136.3 mg) KNCS
2
shows the same topology of the coordination network as com- (194.4 mg) and pyridine (1 mL) in water (2 mL). The colorless precip-
pound 1 [18]. If e.g. the chloro compound is heated, a structure itate was filtered off and washed with pyridine. The purity was checked
by XRPD (see Figure S4 in the Supporting Information).
is formed, in which the zinc atoms are octahedrally coordi-
12 10 4 2
C H N S Zn (337.73): calcd. C 42.42, H 2.97, N 16.49, S 18.88 %;
nated and connected into chains by the chlorine atoms, which
are further linked by the pyrazine ligands into layers [18].
For the ligand-rich 1:4 compound 4 a ligand-deficient 1:2
intermediate 5 is observed on thermal decomposition, but the
structure of this compound is different from that what we ex-
found C 42.45, H 3.15, N 16.78, S 19.12 %.
Elemental Analysis
pected in the beginning because the octahedral coordination is CHNS analysis was performed with an EURO EA elemental analyzer,
transformed into a tetrahedral coordination, in which the iso- fabricated by EURO VECTOR Instruments and Software.
thiocyanato anions are always N-bonded. We also investigated
similar compounds of composition M(NCS) (pyridine) (M =
2
4
Spectroscopy
Mn, Fe, Co, and Ni) that also consist of discrete complexes,
in which the metal atoms are coordinated by two N-bonded
isothiocyanato anions and four pyridine ligands and which are
Fourier transform IR spectra were recorded with a Genesis series FTIR
spectrometer from ATI Mattson in KBr pellets. Raman-spectra were
isotypic to compound 4 [55–59]. If these compounds are recorded with a Bruker ISF66 FRA106 between 3500–100 cm–1 in a
heated, also 1:2 intermediates can be isolated, but in contrast closed glass tube.
to compound 5 the octahedral coordination is retained and the
metal atoms are bridged by the isothiocyanato anions into
Differential Thermal Analysis and Thermogravimetry
chains [60–62]. Obviously, in the case of zinc the tetrahedral
coordination with N-bonded isothiocyanato anions is more sta-
ble than the octahedral coordination with μ-1,3 bridging ani-
ons. These observations clearly show that the situation is
The DTA-TG measurements were performed in nitrogen atmosphere
(
2 3
purity: 5.0) in Al O crucibles using a STA-409CD thermobalance
from Netzsch. All measurements were performed with a flow rate of
sometimes more complex and the prediction of the existence 75 mL·min–1 and were corrected for buoyancy and current effects. The
and structures of ligand-deficient intermediates based on the instrument was calibrated using standard reference materials.
Z. Anorg. Allg. Chem. 2010, 2595–2601
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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2599

G. Bhosekar, J. Boeckmann, I. Jeß, C. Näther
ARTICLE
Single-Crystal Structure Analysis
Holstein. We thank Professor Dr. Wolfgang Bensch for access to his
experimental facility.
All investigation was performed with an imaging plate diffraction sys-
α
tem (IPDS-1) with Mo-K -radiation from STOE & CIE. The structure
solution was performed with direct methods using SHELXS-97 [63],
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and structure refinements were performed against F using SHELXL-
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2
3
[
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formula
C
10
341.71
H
8
N
6
S
2
Zn
C
10
341.71
H
8
N
6
S
2
Zn
C
10 8 6 2
H N S Zn
36, 770.
–
1
MW /g·mol
341.71
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crystal system
space group
a /Å
b /Å
c /Å
monoclinic
C2/m
orthorhombic monoclinic
Cmca
9.6383(7)
15.6599(13)
8.4943(8)
90.0
C2/c
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10.2096(10)
10.4294(8)
7.1818(8)
118.94(1)
669.2(1)
293
14.7258(12)
5.5843(3)
17.3102(15)
96.89(1)
1413.2(2)
170
β /°
3
V /Å
1282.1(2)
170
T /K
Z
2
4
4
–
3
D
calc /g·cm
1.696
1.770
1.606
–
1
μ /mm
2.114
2.234
2.027
θ
max / deg
28.00
27.95
27.98
measured refl.
3244
7021
7734
R
int
0.0559
849
0.0741
815
0.0347
1694
unique reflns.
refl.[F > 4σ(F
parameters
[F > 4σ(F
[all data]
o
o
)] 812
772
52
1433
51
88
R
1
wR
o
o
)]
0.0382
0.1039
1.099
0.0293
0.0756
1.027
0.0327
0.0938
1.006
2
GOF
Δρmax/min/e·Å–3
0.65/ –0.68
0.45/–1.27
0.37/–0.50
[
[
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Received: May 20, 2010
Published Online: August 25, 2010
Z. Anorg. Allg. Chem. 2010, 2595–2601
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2601