Zn(NCS)2-3-cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

Article abstract of DOI:10.1002/zaac.201800428

The reaction of different stoichiometric amounts of Zn(NCS)₂ with 3-cyanopyridine in different solvents leads to the formation of several new coordination compounds, which were structurally characterized and investigated for their thermal behavior. In Zn(NCS)₂(3-cyanopyridine)₄ (1) and Zn(NCS)₂(3-cyanopyridine)₂(H₂O)₂·(3-cyanopyridine)₂ (2) the zinc cations are octahedrally coordinated by two terminally N-bonded thiocyanate anions and four 3-cyanopyridine (1) or two 3-cyanopyridine and two water molecules (2) within slightly distorted octahedra. Zn(NCS)₂(3-cyanopyridine)₂ (3) and Zn(NCS)₂(3-cyanopyridine)₂·(H₂O)_0.5 (3-H₂O) also form discrete complexes but with tetrahedrally coordinated Zn cations. Upon heating compound 1 decomposes without the formation of any intermediate compound. In contrast, compound 2 loses the water molecules in the first step and transforms into compound 1. Surprisingly, upon further heating a second TG step is observed, in which compound 3 is formed as an intermediate, which is not observed if compound 1 is heated directly. The tetrahedral complex 3 melts leading to the formation of an amorphous phase. If the hemihydrate 3-H₂O is heated, it transforms into 3 via melting and crystallization but there are hints that a metastable phase might form as intermediate on water removal.

Full text of DOI:10.1002/zaac.201800428

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201800428
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Zn(NCS)2-3-cyanopyridine Coordination Compounds: Synthesis,
Crystal Structures, and Thermal Properties
Aleksej Jochim,[a] Inke Jess,[a] and Christian Näther*[a]
Dedicated to Prof. Thomas F. Fässler on the Occasion of his 60th Birthday
Abstract. The reaction of different stoichiometric amounts of with tetrahedrally coordinated Zn cations. Upon heating compound 1
Zn(NCS)2 with 3-cyanopyridine in different solvents leads to the for-
mation of several new coordination compounds, which were structur-
decomposes without the formation of any intermediate compound. In
contrast, compound 2 loses the water molecules in the first step and
ally characterized and investigated for their thermal behavior. In transforms into compound 1. Surprisingly, upon further heating a sec-
Zn(NCS)2(3-cyanopyridine)4 (1) and Zn(NCS)2(3-cyanopyridine)2(H2O)2· ond TG step is observed, in which compound 3 is formed as an inter-
(3-cyanopyridine)2 (2) the zinc cations are octahedrally coordinated by mediate, which is not observed if compound 1 is heated directly. The
two terminally N-bonded thiocyanate anions and four 3-cyanopyridine tetrahedral complex 3 melts leading to the formation of an amorphous
(1) or two 3-cyanopyridine and two water molecules (2) within slightly
phase. If the hemihydrate 3-H2O is heated, it transforms into 3 via
distorted octahedra. Zn(NCS)2(3-cyanopyridine)2 (3) and Zn(NCS)2(3- melting and crystallization but there are hints that a metastable phase
cyanopyridine)2·(H2O)0.5 (3-H2O) also form discrete complexes but
might form as intermediate on water removal.
powders are obtained by this route, but to extract structural
information on these intermediates the corresponding
Cd(NCS)2 compounds can be prepared, because they are fre-
quently isotypic.[33] If CoII compounds are thermally decom-
posed, discrete tetrahedral complexes instead of bridging com-
pounds can be obtained, which are frequently isotypic to the
corresponding Zn(NCS)2 analogues.[34] Therefore, the latter
can be used as structure models, which is the reason why we
became interested in Zn(NCS)2 and Cd(NCS)2 coordination
compounds.[35–37] For Co(NCS)2 or Zn(NCS)2 coordination
compounds frequently different polymorphic modifications
can be obtained that in some cases can be selectively prepared
starting from different precursor complexes.[35]
In the course of the overall project we became interested in
Zn(NCS)2 coordination compounds with 3-cyanopyridine as
co-ligand, for which no compounds with Zn(NCS)2 are re-
ported in the Cambridge Structure Database (CSD). There are
very few coordination compounds reported with other transi-
tion metal cations like, e.g. copper that mostly consist of dis-
crete complexes or solvates.[38–40] During our investigations
we obtained a number of new compounds that consist of dis-
crete complexes with octahedrally and tetrahedrally coordi-
nated Zn cations, which were characterized for their thermal
properties and transition behavior. Herein we report on these
investigations.
Introduction
The synthesis of new coordination compounds including
polymers, metal organic frameworks, or inorganic-organic hy-
brid compounds is still an important field in coordination
chemistry because many of them have some potential for fu-
ture applications.[1–12] In most cases coordination compounds
are synthesized from solution, but there are also some exam-
ples, in which such compounds were prepared by solid-state
routes, like, e.g. molecular milling or reactions from the
melt.[13–18] Another method that can be used is based on ther-
mal decomposition of suitable precursor compounds, that upon
heating lose their co-ligands stepwise and transform quantita-
tively and irreversibly into new co-ligand deficient phases.
This approach is useful in cases, in which a certain compound
is not available from solution, which is frequently the case for
transition metal thiocyanate coordination polymers containing
metal cations linked by the anionic ligands into 1D or 2D net-
works.
Such compounds are of interest, because several of them
show cooperative magnetic phenomena including a slow relax-
ation of the magnetization, that originates from single chain
magnet behavior.[19–28] One additional advantage of this syn-
thetic route is the fact that frequently different metastable poly-
morphs or isomers can be obtained that are difficult to synthe-
size from solution.[29–32] Unfortunately, only microcrystalline
* Prof. Dr. C. Näther
Results and Discussion
E-Mail: cnaether@ac.uni-kiel.de
[a] Institute of Inorganic Chemistry
Christian-Albrechts-University of Kiel
Max-Eyth-Straße 2
Synthesis
24118 Kiel, Germany
If Zn(NCS)2 is reacted with 3-cyanopyridine in water
or ethanol, three different crystalline phases are obtained,
which according to elemental analysis have the
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201800428 or from the au-
thor.
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composition
Zn(NCS)2(3-cyanopyridine)4
(1), nected into chains that proceed along the c axis (Figure S12
(2), and Table S2, Supporting Information).
Zn(NCS)2(3-cyanopyridine)2(H2O)2·(3-cyanopyridine)2
and Zn(NCS)2(3-cyanopyridine)2 (3). The values for the asym-
metric CN stretching vibration of the thiocyanate amount to
2072, 2087, and 2060 cm–1 for compounds 1, 2, and 3, respec-
tively, which indicates that in all compounds the thiocyanate
anions are terminally coordinated (Figures S1–S3, Supporting
Information). Therefore, compound 1 and 2 should consist of
discrete complexes with octahedrally coordinated Zn cations,
whereas in compound 3 the cations should show a tetrahedral
coordination, which later was proven by single-crystal X-ray
diffraction.
Although single crystals of compounds 1 and 2 could be
easily obtained, the synthesis of crystals of 3 from water leads
to the formation of a new crystalline phase that contains a
small amount of water (3-H2O), for which the CN stretch is
observed at 2080 cm–1 (Figure S4, Supporting Information).
Crystals of compound 3 were later obtained from n-butanol.
Based on the results of the structure determinations powder
patterns were calculated and compared with the experimental
patterns, which proves that all compounds were obtained as
pure phases (Figures S5–S8, Supporting Information). Unfor-
tunately, the synthesis of larger amounts of the hemihydrate 3-
H2O is difficult to achieve and therefore we checked whether
compound 3 could be converted into 3-H2O when the former
is either kept in a water atmosphere or stirred in water. While
no change in the diffraction pattern was detected after storing
3 for 3 d in a water atmosphere, the sample, which was stirred
in water was converted into 2 within 2 h, without any traces
of 3-H2O being observed (Figure S9, Supporting Information).
While for compounds 1, 2, and 3 the reaction time was several
days, time dependent studies were performed, which revealed
that if the metal salt and the ligand are reacted in ratio 1:1,
compound 3-H2O forms in the beginning and transforms on
longer reaction time into 3 (Figure S10, Supporting Infor-
mation). This indicates that 3-H2O is formed by kinetic control
and that for this composition the ansolvate 3 is thermodynami-
cally stable.
Figure 1. View of the coordination sphere of the Zn cation in com-
pound 1 (Zn: white, N: blue, C: black, S: yellow, H: dark grey). An
ORTEP plot of 1 can be found in Figure S11 (Supporting Information).
¯
Compound 2 crystallizes in the triclinic space group P1 and
its asymmetric unit consists of one thiocyanate anion, one
water molecule as well as one coordinating and one non-coor-
dinating 3-cyanopyridine ligand on general positions and one
Zn cation that resides on a center of inversion. The Zn cation
is coordinated by two thiocyanate anions, two 3-cyanopyridine
molecules and two water molecules forming a discrete com-
plex with a slightly distorted coordination octahedron with
2
σθ‹oct› = 1.0 and λoct = 1.001 (Figure 2, Figure S13 and Table
S3, Supporting Information). The coordination sphere of com-
pound 2 is less distorted than that of 1, which might be traced
back to steric influences of the bulky 3-cyanopyridine ligands.
Crystal Structures
Compound 1 crystallizes in the non-centrosymmetric ortho-
rhombic space group Pna21 with one zinc cation, two thiocya-
nate anions, and four 3-cyanopyridine molecules on general
positions (Table S1, Supporting Information). The zinc cations
are coordinated by two N-terminal thiocyanate anions as well
as four 3-cyanopyridine molecules via the pyridine nitrogen
atom forming discrete complexes (Figure 1 and Figure S11,
Supporting Information). As indicated by the values for the
Figure 2. View of the coordination sphere of the Zn cation in com-
pound 2 together with the adjacent non-coordinating 3-cyanopyridine
ligands. Intermolecular hydrogen bonding is shown as dashed lines
(Zn: grey, N: blue, C: black, S: yellow, O: red, H: dark grey). An
ORTEP plot of 2 can be found in Figure S13 (Supporting Information).
2
octahedral angle variance σθ‹oct› and mean octahedral qua-
2
dratic elongation λoct amounting to σθ‹oct› = 9.8 and λoct
=
Each discrete complex is linked to two non-coordinating 3-
1.007 the coordination octahedron is slightly distorted.[41] The cyanopyridine ligands via O–H···NPy as well as C–H···S
bond lengths and angles are similar to those observed for re- hydrogen bonds (Figure 2 and Table S4, Supporting Infor-
lated compounds (Table S1). Short contacts between the cyano mation). These units are further connected into chains along
nitrogen and pyridine hydrogen indicate weak C–H···N the a axis by O–H···S hydrogen bonding, which are further
hydrogen bonding, by which the discrete complexes are con- linked via weak C–H···S and C–H···N hydrogen bonds into
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layers parallel to the ab plane (Figure 3 and Table S4, Support- range from 105.47(9) to 115.26(12)° and from 102.64(7) to
ing Information).
121.44(8)° (Tables S5 and S6, Supporting Information). In 3-
H2O neighboring discrete complexes are connected via C–
H···N hydrogen bonding between the pyridine hydrogen atoms
and the cyano nitrogen atoms into chains along the c axis,
which are linked with adjacent chains via C–H···S hydrogen
bonds into layers parallel to the bc plane (Table S7, Supporting
Information). Additional O–H···S hydrogen bonds to the water
molecules connect the layers into a three-dimensional network
(Figure 5 top).
Figure 3. Crystal structure of 2 with view along the b axis and onto
the layers. Intermolecular hydrogen bonding is shown as dashed lines
(Zn: grey, N: blue, C: black, S: yellow, O: red, H: dark grey).
Compounds 3 and 3-H2O both crystallize in the monoclinic
space group C2/c with the asymmetric unit of 3 containing one
thiocyanate anion and one 3-cyanopyridine molecule in gene-
ral positions as well as one Zn cation residing on a twofold
rotational axis. The asymmetric unit of 3-H2O consists of two
thiocyanate anions, two 3-cyanopyridine molecules and one Zn
cation in general positions, while one water molecules is lo-
cated on a twofold rotational axis. In both compounds discrete
tetrahedral complexes are formed, in which the Zn cations are
coordinated by two thiocyanate anions as well as two 3-cyano-
pyridine molecules (Figure 4 and Figures S14 and S15, Sup-
porting Information). Although both complexes show similar
dihedral angles between the pyridine ring planes, the 3-cyano
ligands point in different directions in 3 and are on the same
side in 3-H2O.
Figure 5. Crystal structure of 3-H2O (top) and 3 (bottom) with view
along the b axis and intermolecular hydrogen bonding shown as dashed
lines (Zn: grey, N: blue, C: black, S: yellow, H: dark grey).
Similarly to 3-H2O adjacent complexes in 3 are connected
via weak C–H···N hydrogen bonds into chains along the c axis,
which are linked into layers parallel to the bc plane by C–H···S
hydrogen bonds (Figure 5 bottom and Table S8, Supporting
Information). There are some similarities in the crystal struc-
tures of 3-H2O and 3, because comparable pairs of complexes
are found, that are linked by pairs of C–H···S hydrogen bonds.
For these pairs of complexes, some of the pyridine rings are
stacked along the b axis, with the cyano groups stacked onto
each other. This arrangement is repeated in compound 3, which
is not possible in 3-H2O, because of the water molecules (Fig-
ure 5).
Figure 4. View of the coordination sphere of the Zn cation in com-
pound 3 (left) and 3-H2O (right); (Zn: grey, N: blue, C: black, S:
yellow, H: dark grey). ORTEP plots of 3 and 3-H2O can be found in
Figures S14 and S15 (Supporting Information).
While the coordination tetrahedron in 3 is only slightly dis-
torted with a tetrahedral angle variance and mean tetrahedral
2
quadratic elongation of σθ‹tet› = 10.2 and λtet = 1.003, the
2
corresponding values for 3-H2O of σθ‹tet› = 53.8 and λtet
=
Thermoanalytical Investigations
1.013 indicate a stronger distortion.[41] The Zn–N bond lengths
range from 1.925(2) to 2.030(2) Å in 3 and from 1.923(2) to
To examine the thermal properties of the compounds ob-
2.069(2) Å in 3-H2O, whereas the angles in 3 and 3-H2O tained investigations using simultaneous thermogravimetry and
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differential thermal analysis (TG-DTA) were performed (Fig- [Δmcalcd (3) = 54.5% and Δmcalcd (3-H2O) = 53.4%] (Figure 6
ure 6).
and Figures S20 and S21, Supporting Information). The mass
loss of the water molecules cannot be resolved. However for
3-H2O several weak endothermic peaks between 105 and
138 °C are observed in the DTA curve, indicating that the reac-
tion is more complex. Therefore, additional investigations
using differential scanning calorimetry (DSC) and thermomi-
croscopy were conducted. Upon heating the discrete complex
3 at different heating rates, only one strong endothermic signal
is observed in the DSC curve at 139 °C using 10 K·min–1, that
might correspond to melting or decomposition of this com-
pound (Figure 7 top). Thermomicroscopic investigations
clearly prove that melting is observed but additional DSC in-
vestigations show no crystallization upon cooling, indicating
the formation of an amorphous form that practically does not
recrystallize in a second heating run even though a very small
exothermic signal is observed (Figures S22 and S23, Support-
ing Information). As expected, XRPD investigations reveal
that the residue obtained after melting is amorphous against
X-rays (Figure S24, Supporting Information).
Figure 6. TG-curves at 1 K·min–1 for compounds 1, 2, 3-H2O, and 3.
Upon heating compound 1 only one poorly resolved mass
step is observed, in which all of the 3-cyanopyridine molecules
are emitted leading to the formation of Zn(NCS)2 (Δmcalcd
=
69.6%). Obviously, compound 3 cannot be obtained as an in-
termediate, even at very low heating rates (Figure S16, Sup-
porting Information).
In contrast, the aqua complex 2 shows two well resolved
mass steps that are each accompanied by endothermic events
in the DTA curve (Figure 6 and Figure S17, Supporting Infor-
mation). The experimental mass loss in the first step of 7.72%
is in good agreement with that calculated for the removal of
the two water molecules (Δmcalcd = 5.68%). If the residue ob-
tained after water removal is investigated by XRPD, a phase
pure sample of 1 is obtained (Figure S18, Supporting Infor-
mation). This is surprising, because the formation of a solvate
of compound 3 would be expected but obviously the octahe-
dral coordination is retained and the coordination sphere is
completed by the two 3-cyanopyridine solvate molecules.
Moreover, upon further heating a second mass loss is observed,
that is in nice agreement with that calculated for the emission
of two 3-cyanopyridine molecules (Δmcalcd = 32.8%), indicat-
ing the formation of a compound with the composition
Zn(NCS)2(3-cyanopyridine)2. If the residue formed in this step
is identified by XRPD, it is proven that the tetrahedral complex
3 has formed, which interestingly does not form if compound
1 is heated directly in a DTA-TG experiment (Figure S18, Sup-
porting Information). Therefore, compound 1 was annealed at
Figure 7. DSC curves at different heating rates for 3 (top) and 3-H2O
(bottom).
In contrast to 3, the DSC curves of the hemihydrate 3-H2O
90 °C for one day, which also leads to the formation of pure 3 look more complicated. Heating rate dependent measurements
(Figure S19, Supporting Information).
show that at 5, 10, and 20 K·min–1 one endothermic event, that
The TG curves for 3-H2O and 3 look very similar and the is followed by an exothermic signal and on further heating a
overall mass loss until 350 °C in in rough agreement with that second endothermic peak is observed (Figure 7 bottom). A
expected for the removal of all 3-cyanopyridine ligands closer look reveals that a very weak endothermic signal is ob-
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served before the strong endothermic event and XRPD investi- metastable intermediate can also be prepared by annealing the
gations proves, that some of 3-H2O has been transformed into hemihydrate, 3-H2O was stored at 90 °C for one day, which
3 (Figure S25, Supporting Information). leads to a crystalline phase that is similar to that of the interme-
The first strong endothermic signal observed in the DSC diate obtained after the first endothermic event and looks more
measurement of 3-H2O can be traced back to melting of this pure (Figure S28). Unfortunately, indexing of this pattern fails.
compound, followed by crystallization of 3, that melts upon However, even though the XRPD pattern of this intermediate
further heating, because the temperature observed in the last shows some similarities to that of the hemihydrate 3-H2O, one
endothermic event corresponds to that of the melting point of cannot expect that this reaction is topotactic. This was also
3 (see also Figure S22). In this case water removal and melting proven by single crystal measurements at different tempera-
would occur at the same temperature. Alternatively the first tures, in which no changes were observed until 90 °C. On
strong endothermic event can correspond to the water removal, higher temperatures the diffraction pattern disappeared com-
leading to the formation of a metastable phase that upon fur- pletely and looks like that for a powder.
ther heating exothermically transforms into 3. Thermomicro-
scopic investigations indicate that the hemihydrate 3-H2O
Conclusions
starts to melt at about 104 °C and that crystals form from the
melt, that disappear upon further heating (Figure 8). Moreover,
XRPD investigations of the phase that has formed after the
exothermic event clearly prove that compound 3 has formed
(Figure S26, Supporting Information). However, it is noted that
for different batches of 3-H2O varying DSC curves were mea-
sured. In one of the measurements three endothermic events
are observed, of which the first one corresponds to the water
removal of 3-H2O and the last one to the melting of 3, whereas
the middle one was never observed before. Heating and cool-
ing cycles reveal that all of these events are irreversible (Figure
S27, Supporting Information).
Four new compounds based on Zn(NCS)2 and 3-cyanopyr-
idine are reported, of which two show an octahedral and two
a tetrahedral coordination. Upon heating the octahedral precur-
sor compounds, a transformation into a tetrahedral discrete
complex is observed, which in one case strongly depends on
the actual heating rate and thus, on the kinetics of the reac-
tions. Upon further heating the tetrahedral complex shows
melting: this is rarely observed for coordination compounds,
because they usually decompose before melting. On solidifica-
tion of the melt an amorphous phase is obtained. However,
this complex can also be obtained by water removal from a
hemihydrate that also consists of tetrahedral complexes. This
reaction is more complex, because it proceeds via melting and
crystallization of the final complex that melts on further heat-
ing. There are strong indications that a metastable phase is
formed on water removal but we cannot definitely differentiate
whether the first melting originates from melting of the hemi-
hydrate or the metastable ansolvate formed by water removal.
Experimental Section
Synthesis: ZnSO4·H2O was obtained from Merck, and
Ba(NCS)2·3H2O as well as 3-cyanopyridine were obtained from Alfa
Aesar. All chemicals were used without further purification.
Zn(NCS)2 was prepared by the reaction of equimolar amounts of
ZnSO4·H2O and Ba(NCS)2·3H2O in water. The resulting colorless pre-
cipitate of BaSO4 was filtered off and the filtrate was concentrated to
complete dryness resulting in a colorless residue of Zn(NCS)2. If not
noted otherwise all crystalline powders were prepared by stirring the
reactants in solution at room temperature. The residues were filtered
off and dried in air.
Synthesis of 1: A mixture of Zn(NCS)2 (90.8 mg, 0.50 mmol) and 3-
cyanopyridine (312.3 mg, 3.00 mmol) was stirred in 1.0 mL of ethanol
for 2 d. Yield: 230 mg (77%). Single crystals were obtained by layer-
ing a solution of Zn(NCS)2 (45.4 mg, 0.25 mmol) in 1.0 mL water with
2.0 mL ethyl ether and carefully adding 3-cyanopyridine (156.2 mg,
1.50 mmol) in 1.0 mL ethyl ether. After one day colorless crystals were
obtained. C26H16N10ZnS2 (597.99 g·mol–1): calcd. C 52.22, H 2.70, N
23.42, S 10.72%; found C 54.19, H 2.55, N 24.60, S 11.14%.
Figure 8. Microscopic images of 3-H2O upon heating, from which the
transformation into 3 via melting and crystallization becomes obvious.
XRPD investigation of these residues shows, that after the
first event a pattern is observed, that is different from that of
3-H2O, even if strong similarities are observed, indicating the
formation of a new phase (Figure S28, Supporting Infor-
mation). After the second endothermic event some of this new
form was transformed into compound 3, but the overall crystal-
Synthesis of 2: Zn(NCS)2 (90.8 mg, 0.50 mmol) and 3-cyanopyridine
(208.2 mg, 2.00 mmol) were stirred in 1.0 mL water for five days upon
linity of this sample is poor (Figure S28). To prove if this which a colorless precipitate was obtained. Yield: 242 mg (76%). Sin-
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Table 1. Selected crystal data and details of the structure refinements for 1, 2, 3-H2O, and 3.
1
2
3-H2O
3
Formula
C26H16N10ZnS2
597.98
orthorhombic
Pna21
20.3753(3)
10.2971(3)
13.0044(4)
90
C26H20N10ZnO2S2
634.01
C28H18N12Zn2OS4
797.52
monoclinic
C2/c
26.3508(8)
7.8374(2)
21.1469(7)
90
128.475(2)
90
3419.06(19)
200(2)
4
1.549
1.690
26.004
12557
3319
2991
213
0.0192
0.0284
0.0755
–
C14H8N6ZnS2
389.75
monoclinic
C2/c
15.6866(7)
7.3157(3)
16.0845(7)
90
114.680(3)
90
1677.22(13)
200(2)
4
1.544
1.719
25.995
7877
1646
1528
105
0.0280
0.0243
0.0672
–
MW /g·mol–1
Crystal system
Space group
a /Å
triclinic
¯
P1
8.1100(4)
8.3595(4)
11.5153(6)
85.843(4)
76.988(4)
71.326(4)
720.60(7)
200(2)
1
1.461
1.040
26.004
9488
2823
2629
187
0.0259
0.0238
0.0635
–
b /Å
c /Å
a /°
β /°
90
90
γ /°
V /Å3
2728.41(12)
200(2)
4
1.456
1.089
26.003
23911
5348
5104
352
0.0251
0.0247
0.0629
–0.006(4)
1.060
T /K
Z
Dcalc /g·cm–3
μ /mm–1
θmax /°
Measured refl.
Unique refl.
Refl. Fo Ͼ 4σ(Fo)
Parameter
Rint
R1 [F0 Ͼ 4σF0)]
wR2 [all data]
Flack x parameter
GOF
1.066
0.221/ –0.230
1.058
0.308/ –0.316
1.080
0.445/ –0.389
Δρmax/min /e·Å–3
0.252/ –0.289
gle crystals for 2 were obtained by the same procedure as those for 1, Crystallographic data (excluding structure factors) for the structures in
but with a different amount of 3-cyanopyridine (104.1 mg, 1.00 mmol) this paper have been deposited with the Cambridge Crystallographic
used. C26H20N10O2ZnS2 (634.02 g·mol–1): calcd. C 49.25, H 3.18, N Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
22.09, S 10.12%; found C 50.79, H 3.01, N 23.02, S 10.23%.
of the data can be obtained free of charge on quoting the depository
numbers CCDC-1870423 (1), CCDC-1870420 (2), CCDC-1870422
(3-H2O), and CCDC-1870421 (3) (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
Synthesis of 3-H2O: Single crystals were obtained in a similar way
as those of 1 and 2 with less 3-cyanopyridine (52.1 mg, 0.50 mmol)
used. A powder could be synthesized by stirring a mixture of
Zn(NCS)2 (90.8 mg, 0.50 mmol) and 3-cyanopyridine (52.1 mg,
0.50 mmol) in water for 1 h. Yield: 31 mg (16%). The precipitated
colorless powder was filtered of and dried at 70 °C for 1 h.
C14H9N6O0.5ZnS2 (398.78 g·mol–1): calcd. C 42.17, H 2.27, N 21.07,
S 16.08%; found C 43.24, H 2.09, N 21.97, S 16.63%.
X-ray Powder Diffraction (XRPD): The measurements were per-
formed using Cu-Kα1 radiation (λ = 1.540598 Å) with a Stoe Trans-
mission Powder Diffraction System (STADI P) that is equipped with
a MYTHEN 1 K detector and a Johansson-type Ge(111) monochroma-
tor.
Synthesis of 3: Compound 3 was obtained by the reaction of
Zn(NCS)2 (90.8 mg, 0.50 mmol) with 3-cyanopyridine (52.1 mg,
0.50 mmol) in 1.0 mL ethanol or water after 2 d. Yield: 94 mg (48%).
Single crystals were grown from butanol using the same amounts of
Zn(NCS)2 and 3-cyanopyridine. After one day colorless crystals suit-
able for X-ray structure determination were obtained. C14H8N6ZnS2
(389.77 g·mol–1): calcd. C 43.14, H 2.07, N 21.56, S 16.45%; found
C 43.75, H 1.95, N 22.41, S 17.13%.
IR Spectroscopy: The IR spectra were measured with an ATI Mattson
Genesis Series FTIR Spectrometer, control software: WINFIRST, from
ATI Mattson.
Elemental Analysis: CHNS analysis was performed with a EURO EA
elemental analyzer, fabricated by EURO VECTOR Instruments.
Thermogravimetry and Differential Thermal Analysis (TG-DTA):
DTA-TG measurements were performed in a dynamic nitrogen atmo-
sphere in Al2O3 crucibles with a STA-PT 1000 thermobalance from
Linseis. The instrument was calibrated using standard reference mate-
Single-crystal Structure Analysis: Data collection was performed
with an imaging plate diffraction system (IPDS-2) from STOE & CIE
using Mo-Kα radiation. The structure solution was performed with
SHELXS-97[42] and structure refinements were performed against F2
using SHELXL-2014.[43] A numerical absorption correction was ap-
plied using programs X-RED and X-SHAPE of the program package
X-Area.[44] All non-hydrogen atoms were refined with anisotropic dis-
placement parameters. The C–H hydrogen atoms were positioned with
idealized geometry and were refined isotropically with Uiso(H) = 1.2
Ueq(C) using a riding model. The absolute structure of 1 was deter-
rials. All measurements were performed with
75 mL·min–1 and were corrected for buoyancy.
a flow rate of
Differential Scanning Calorimetry (DSC): The DSC measurements
were performed with a DSC 1 Star System with STARe Excellence
Software from Mettler-Toledo AG. The instrument was calibrated
using standard reference materials.
mined and is in agreement with the selected setting [Flack-x parameter: Supporting Information (see footnote on the first page of this article):
–0.006(4)]. Selected crystal data and details of the structure refine-
ments can be found in Table 1.
XRPD patterns, ORTEP plots, IR spectra, DTA-TG curves DSC curves
and structure drawings.
Z. Anorg. Allg. Chem. 2019, 212–218
www.zaac.wiley-vch.de 217
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
[21] S. Wöhlert, T. Fic, Z. Tomkowicz, S. G. Ebbinghaus, M. Rams,
Acknowledgements
W. Haase, C. Näther, Inorg. Chem. 2013, 52, 12947–12957.
[22] M. Rams, M. Böhme, V. Kataev, Y. Krupskaya, B. Büchner, W.
Plass, T. Neumann, Z. Tomkowicz, C. Näther, Phys. Chem. Chem.
Phys. 2017, 19, 24534–24544.
[23] M. Rams, Z. Tomkowicz, M. Böhme, W. Plass, S. Suckert, J.
Werner, I. Jess, C. Näther, Phys. Chem. Chem. Phys. 2017, 19,
3232–3243.
This project was supported by the Deutsche Forschungsgemeinschaft
(Project No. NA 720/5–2) and the State of Schleswig-Holstein. We
thank Prof. Dr. Wolfgang Bensch for access to his experimental facili-
ties.
[24] M. Mousavi, V. Bereau, C. Duhayon, P. Guionneau, J.-P. Sutter,
Chem. Commun. 2012, 48, 10028–10030.
[25] J. Palion-Gazda, B. Machura, F. Lloret, M. Julve, Cryst. Growth
Des. 2015, 15, 2380–2388.
Keywords: Zinc thiocyanate; 3-Cyanopyridine; Crystal struc-
ture; IR spectroscopy; Thermal properties
[26] R. González, A. Acosta, R. Chiozzone, C. Kremer, D. Armentano,
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Received: October 1, 2018
Published online: November 22, 2018
Z. Anorg. Allg. Chem. 2019, 212–218
www.zaac.wiley-vch.de 218
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim