Synthesis, structures, and magnetic properties of new thiocyanato coordination polymers with 4-(3-phenylpropyl)pyridine as ligand

Article abstract of DOI:10.1002/zaac.201400261

The reaction of different metal salts with 4-(3-phenylpropyl) pyridine (ppp) lead to the formation of compounds of composition M(NCS)₂(ppp)₄ [M = Mn (Mn-1); Fe (Fe-1), Ni (Ni-1); Cd (Cd-1)], M(NCS)₂(ppp)₂(H₂O)₂ [M = Mn (Mn-2); Ni (Ni-2)] and [M(NCS)₂(ppp)₂]n [M = Mn (Mn-3); Ni (Ni-3); Cd (Cd-3)]. On heating compounds M-1 decompose without the formation of any ppp deficient intermediate. In contrast, on heating, Ni-2 transforms into a compound of composition M(NCS)₂(ppp)₂ that does not correspond to Ni-3. Unfortunately, this compound is of low crystallinity and therefore, its structure cannot be determined. The crystal structures of compounds M-1 and M-2 consist of discrete complexes, in which the metal cations are octahedrally coordinated. In compounds M-3 the metal cations are linked by pairs of μ-1,3-bridging anions into chains. IR spectroscopic investigations show, that the value of the asymmetric CN stretching vibration depend on the coordination mode of the anionic ligand as well as on the nature of the metal cation. Magnetic measurements reveal that Ni-3 shows only Curie-Weiss behavior without any magnetic anomaly. A similar behavior is also found for Ni-3. Comparison of the magnetic properties of Ni-3 with those of similar compounds indicates that the magnetic properties are only minor influenced by the Co-ligand.

Full text of DOI:10.1002/zaac.201400261

ARTICLE
DOI: 10.1002/zaac.201400261
Synthesis, Structures, and Magnetic Properties of New Thiocyanato
Coordination Polymers with 4-(3-Phenylpropyl)pyridine as Ligand
Julia Werner,[a] Inke Jess,[a] and Christian Näther*[a]
Keywords: Synthesis; Thiocyanates; Coordination polymers; Crystal Structure; Thermochemistry; Magnetochemistry
Abstract. The reaction of different metal salts with 4-(3-phenyl- cations are octahedrally coordinated. In compounds M-3 the metal cat-
propyl)pyridine (ppp) lead to the formation of compounds of composi- ions are linked by pairs of μ-1,3-bridging anions into chains. IR spec-
tion M(NCS)2(ppp)4 [M = Mn (Mn-1); Fe (Fe-1), Ni (Ni-1); troscopic investigations show, that the value of the asymmetric CN
Cd (Cd-1)], M(NCS)2(ppp)2(H2O)2 [M = Mn (Mn-2); Ni (Ni-2)] and stretching vibration depend on the coordination mode of the anionic
[M(NCS)2(ppp)2]n [M = Mn (Mn-3); Ni (Ni-3); Cd (Cd-3)]. On heat-
ing compounds M-1 decompose without the formation of any ppp de-
ligand as well as on the nature of the metal cation. Magnetic measure-
ments reveal that Ni-3 shows only Curie-Weiss behavior without any
ficient intermediate. In contrast, on heating, Ni-2 transforms into a magnetic anomaly. A similar behavior is also found for Ni-3. Compari-
compound of composition M(NCS)2(ppp)2 that does not correspond to son of the magnetic properties of Ni-3 with those of similar compounds
Ni-3. Unfortunately, this compound is of low crystallinity and there-
fore, its structure cannot be determined. The crystal structures of com-
pounds M-1 and M-2 consist of discrete complexes, in which the metal
indicates that the magnetic properties are only minor influenced by the
Co-ligand.
properties including metamagnetic behavior and a slow relax-
ation of the magnetization.[38–45]
Introduction
Investigations on the syntheses, structures, and properties of
new coordination compounds like e.g. coordination polymers,
metal organic frameworks or inorganic-organic hybrid
compounds are still a growing field in coordination chemis-
try.[1–19] One major advantage of such compounds is the fact,
that based on the nature of the metal cations and the coordina-
tion properties of the ligands their structures can be influenced
to some extent. This allows detailed investigations on their
structure property relationships, which is needed for a more
rational synthesis of compounds with desired physical proper-
ties.
In this context compounds with paramagnetic transition
metal cations that show cooperative magnetic properties are of
interest. This behavior can be observed if the spin centers are
linked by ligands that can mediate strong magnetic exchange.
Therefore, an increasing number of such compounds were re-
cently reported.[14–27] This also includes compounds based on
thio- or selenocyanates, especially in those cases where they
act as bridging ligands.[28–37] In this regard we have reported
on a number of compounds that shows different magnetic
However, thiocyanato compounds with bridging anions are
frequently less stable than those with terminal bonded anions,
which means that the former are frequently more difficult to
prepare in solution. Therefore, we have developed an alterna-
tive route which is based on thermal decomposition of suitable
precursor compounds.[46] In this context it is noted that dif-
ferent strategies for the synthesis of coordination compounds
are reported that are not based on conventional synthesis in
solution.[11,47–50] In the course of this project we have investi-
gated several compounds of composition M(NCS)2(L)2 (M =
MnII, FeII, CoII and NiII and L = monodentate N-donor co-
ligand), in which the metal cations are linked by centrosym-
metric pairs of thiocyanato anions and are separated by the co-
ligands. For the compounds with pyridine antiferromagnetic
behavior is observed with Mn, the compounds with Fe and Ni
show a metamagnetic transition and the Co compound shows
a slow relaxation of the magnetization, which shows that in-
terchain interactions must be of importance.[42,51] To study the
influence of the co-ligand in more detail we decided to prepare
compounds based on 4-(3-phenylpropylpyridine), which is
much larger than pyridine and which should separate the
chains more effectively. Within these investigations we obtain
a large amount of compounds of different composition includ-
ing the desired chain compounds with Mn and Ni. Unfortu-
nately we have not found access to the corresponding Fe com-
pound and that with Co shows a complicated magnetic behav-
ior that cannot be explained without more detailed investi-
gations. Within these investigations we also tried to prepare
corresponding Cd compounds of same composition, which are
* Prof. 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.201400261 or from the au-
thor.
Z. Anorg. Allg. Chem. 2014, 640, (11), 2161–2168
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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J. Werner, I. Jess, C. Näther
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of interest for our project, because they can offer structural
information on the paramagnetic counterparts in those cases,
where the latter cannot be prepared as single crystalline materi-
als.[52,53] Therefore, we are generally interested in their spec-
troscopic and structural properties.
Introduction
Synthetic Investigations
To investigate, which compounds are available, different
stoichiometric ratios of the metal salts and 4-(3-phenylprop-
ylpyridine) (ppp) were stirred in different solvents. The resi-
dues were investigated by elemental analysis, IR spectroscopy,
and X-ray powder diffraction. These investigations reveal that
with manganese and nickel three different compounds of com-
position M(NCS)2(ppp)4 (Mn-1, Ni-1), M(NCS)2(ppp)2(H2O)2
(Mn-2, Ni-2), and [M(NCS)2(ppp)2]n (Mn-3, Ni-3) are ob-
tained. Iron shows only one crystalline phase of composition
Fe(NCS)2(ppp)4 (Fe-1). In contrast, for most stoichiometric ra-
tios between Cd(NCS)2 and ppp only a compound of composi-
tion [Cd(NCS)2(ppp)2]n (Cd-3) could be synthesized but with
a larger excess of the co-ligand a second crystalline phase of
composition Cd(NCS)2(ppp)4 (Cd-1) could be obtained.
XRPD investigations indicate that all compounds M-1 and
M-3 are isotypic, which seems to be also the case for com-
pounds M-2 (Figure 1 and Figure 2). However, Mn-2 is con-
taminated with large amount of Mn-3 (Figure S1, Supporting
Information).
Figure 2. Experimental X-ray powder pattern of Mn-3 (A), Ni-3 (B),
and Cd-3 (C).
are available but comparison of its experimental pattern with
that calculated for Ni-1 proves that they are isotypic (Figure
S14). Moreover, Ni-2 is isotypic to Mn-2 (Figure S15).
Crystal Structures
The compounds Mn-1, Fe-1, and Ni-1 are isotypic and crys-
¯
tallize in the triclinic space group P1 with one formula unit in
the unit cell. The asymmetric unit consists of half a metal cat-
ion, one thiocyanato anion, and two crystallographically inde-
pendent ppp ligands. The metal cations show a slightly dis-
torted octahedrally environment. The metal cations are coordi-
nated by six nitrogen atoms of two terminal N-bonded thiocy-
anato anions and four nitrogen atoms of terminal bonded ppp
ligands into discrete complexes that are located on centers of
inversion (Figure 3). The metal nitrogen distances range be-
tween 2.174(2) and 2.344(2) Å and the angles slightly deviate
from ideal values (Tables S1–S3, Supporting Information).
Figure 1. Experimental X-ray powder pattern of Mn-1 (A), Fe-1 (B),
Ni-1 (C), and Cd-1 (D).
Figure 3. Coordination sphere of Mn-1 as a representative (Ortep plots
of Mn-1, Fe-1, and Ni-1 are shown in Figures S19–S21 in the Support-
ing Information).
From the value of the asymmetric C–N stretching vibration
it can be assumed that in compounds 1 and 2 the thiocyanato
anions are only terminal N-bonded, whereas in compounds 3
they act as a bridging ligand (Figures S2–S10, Supporting In-
formation).
¯
The hydrate Mn-2 crystallizes triclinic in space group P1
with two formula units in the unit cell. The asymmetric unit
In further work crystallization experiments were performed consists of two crystallographically independent manganese
at room-temperature, which lead to single crystals of Mn-1, cations, which are located on centers of inversion. Two water
Mn-2, Fe-1, Ni-1 as well as Mn-3, Ni-3 and Cd-3. If the ex- molecules, two thiocyanato anions, and two ppp ligands are
perimental powder pattern of compounds M-1 and M-3 are located in general positions. Each metal cation is coordinated
compared with those calculated from single crystal data it is by two terminally N-bonded thiocyanato anions, two water
proven that they are obtained as phase pure materials (Figures molecules, and two ppp ligands in a slightly distorted octahe-
S11–S18, Supporting Information). For Cd-1 no single crystals dral environment (Figure 4 and Table S4). The metal nitrogen
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Thiocyanato Coordination Polymers with 4-(3-Phenylpropyl)pyridine
distances range between 2.1872(2) and 2.271(2) Å and are tances are between 5.60 (Ni-3) and 5.81 Å (Cd-3) and the
similar to those in compounds 1 (Tables S1–S3, Supporting shortest interchain distance is found in Mn-3 with 11.21 Å
Information).
(Table 1). If these distances are compared with those of the
corresponding pyridine compounds it is proven, that the intra-
chain distances are comparable, whereas the interchain dis-
tances are much larger than those in the pyridine compounds
(Table 1).
Figure 4. Coordination sphere of Mn-2 (An Ortep plot of Mn-2 is
shown in Figure S22 in the Supporting Information).
Compounds Mn-3, Ni-3, and Cd-3 are isotypic and crys-
tallize in the monoclinic space group P21/n with four formula
units in the unit cell. The asymmetric unit consists of two crys-
tallographically independent cations, which are located on cen-
ters of inversion. Two thiocyanato anions and two ppp ligands
are in general positions. The metal cations are coordinated by
two terminal ppp ligands and four μ-1,3-bridging thiocyanato
anions within slightly distorted octahedra and are linked by
pairs of μ-1,3-bridging thiocyanato anions into chains (Fig-
ure 5 and Tables S5–S7).
Figure 6. Crystal structure of Mn-3 as a representative with view
along the crystallographic a axis.
Table 1. The intrachain and interchain M–M distances /Å in Mn-3,
Ni-3, and Cd-3 as well as in the corresponding pyridine (Pyr) com-
pounds retrieved from literature.
Intrachain
Interchain
Reference
Mn-3
Ni-3
Cd-3
5.72
5.60
5.81
11.21
12.15
11.29
8.90
This work
This work
This work
[51]
[Mn(NCS)2(Pyr)2]n 5.77
[Ni(NCS)2(Pyr)2]n
[Cd(NCS)2(Pyr)2]n
5.57
6.01/5.97
8.38
8.62
[54]
[55]
Thermoanalytical Investigations
To investigate if compounds 1 or 2 can be used as precursors
for the preparation of additional compounds by thermal de-
composition, measurements using differential thermoanalysis,
and thermogravimetry (DTA-TG) were performed (Figure 7
and Figures S26–S30, Supporting Information). Because Mn-
2 is always contaminated with Mn-3 it was not investigated
but it can be assumed that it will transform completely into the
latter compound.
On heating only one TG step is observed for compounds 1,
which proves that that all ligands are removed in one step
without formation of any ppp deficient intermediate (Figure 7).
If the hydrate Ni-2 is investigated by DTA-TG measurements
one mass loss is observed starting at about 100 °C that corre-
sponds to the removal of the water molecules and on further
heating the ppp ligands are emitted. From these investigations
it can be assumed that in the first TG step a compound of
composition [Ni(NCS)2(ppp)2]n has formed that must not nec-
essarily be isotypic to Ni-3 as shown previously.[56]
Figure 5. Coordination sphere of Mn-3 as a representative (Ortep plots
of Mn-3, Ni-3, and Cd-3 are shown in Figures S23–S25 in the Sup-
porting Information).
If the TG measurement is repeated and stopped after water
removal and the residue is investigated by XRPD a pattern is
These chains elongate in the direction of the a axis and are obtained that is completely different from that of Ni-3 and
arranged in a way that the N–M–N(ppp) vectors of neigh- which does not contain any reflections of the precursor Ni-2
boring chains are canted (Figure 6). The intrachain M–M dis- (Figure 8). However, the crystallinity of this intermediate com-
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J. Werner, I. Jess, C. Näther
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can be drawn. These correlations are of special importance for
our project especially in those cases where no single crystals
of a given compound are available and structural information
must be retrieved from IR spectroscopic investigations. For
compounds 1 and 3 these values slightly increase from Mn to
Ni with larger differences for compounds 3 (Table 2). This ge-
neral trend is also observed for compounds of similar struc-
tures retrieved from literature (Table 2). Even if they are small,
differences are also found for compounds with different co-
ligands. Finally, it is shown that dependent on the nature of
the metal cation and the co-ligand the vibration are distributed
over a relatively large range, but in any case no overlap be-
tween the terminal and the bridging coordination is observed.
Therefore, in this case the coordination mode of the anionic
ligand can easily be determined.
Table 2. Values of the asymmetric CN stretching vibration in cm–1 for
compounds M-1 and M-3, as well of similar compounds with same
structure retrieved from literature (Pyr = pyridine).[51,56]
Compound
Cd
Mn
Fe
Ni
Figure 7. TG curves for Mn-1, Fe-1, Ni-1, Cd-1, and Ni-2.
M(NCS)2(ppp)4
M(NCS)2(ppp)2
M(NCS)2(Pyr)4
M(NCS)2(Pyr)2
M(NCS)2(Ethyl-Pyr)4 2037
M(NCS)2(Ethyl-Pyr)2 2105
2064
2091
2050
2097
2060
2087
2060
2090
2044
2092
2063
–
2066
2093
2050
–
2081
2109
2082
2110
2069
2113
pound is very poor with broad reflection profiles and all
attempts to index its powder pattern failed. However, the
asymmetric C–N stretching vibration is observed at
2170 cm–1 and 2112 cm–1 in the IR spectra and therefore, it
can be assumed that also bridging thiocyanato anions are pres-
ent.
Magnetic Investigations
The magnetic properties of the paramagnetic compounds
M-1 were investigated by susceptibility measurements be-
tween room-temperature and 2 K. For the discrete complexes
1 and 2 only paramagnetic behavior without any magnetic
anomaly is expected because the thiocyanato anions are only
terminal bonded. In agreement the temperature dependence of
the susceptibility follows the Curie (Mn-1 and Ni-1) or Curie-
Weiss (Fe-1) law, with significant antiferromagnetic interac-
tions for Fe-1 (Table 3 and Figures S31–S33, Supporting Infor-
mation). The experimental magnetic moment for Mn-1 is in
good agreement with that calculated for a MnII ion in high-
spin configuration, whereas the values for Fe-1 and Ni-1 are a
slightly higher (Table 3).
Table 3. Selected experimental data of the magnetic measurements of
Mn-1, Fe-1, Ni-1, and Ni-3.
Figure 8. Experimental X-ray powder pattern of the residue obtained
in a TG measurement of Ni-2 after water removal (A), of Ni-2 (B) and
calculated XRPD pattern for Ni-3 (C).
Mn-1
Fe-1
Ni-1
Ni-3
Θ /K
0.6
–21.5
4.30
5.86
4.89
1.6
8.0
C /cm–3·K·mol–1
μeff /μB
4.43
5.95
5.92
1.13
3.00
2.82
1.21
3.12
2.82
IR Spectroscopic Investigations
μeff(HS) /μB
It is well known that the coordination mode of the thiocyan-
ato anion can be estimated from the value of the CN stretching
For Ni-3, in which the metal cations are linked by μ-1,3-
vibration. In the case of terminally N-bonded thio- bridging anionic ligands also only Curie-Weiss behavior is ob-
cyanato anions this vibration is observed at about 2050 cm–1, served (Figure S34, Supporting Information). The experimen-
whereas for the μ-1,3 bridging mode it is located around tal magnetic moment of 3.12 μB is in good agreement with
2100 cm–1.[57–59] However, it can be expected that the actual that calculated for NiII in a high-spin configuration. The Weiss
values depend on the nature of the metal cation and the organic constant of 8.0 K indicates dominant ferromagnetic interac-
co-ligand and therefore, in some cases no definite conclusions tions, which are also observed in similar compounds of this
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Thiocyanato Coordination Polymers with 4-(3-Phenylpropyl)pyridine
Table 4. Selected magnetic data for compounds of composition [Ni(NCS)2(L)2]n (L = co-ligand). Please note the compound with 4-ethylpyridine
exists in two polymorphic modifications.
Co-ligand
Θ /K
Hc /kOe
TN /K
Interchain distance /Å
Reference
ppp
Pyridine
4-Ethylpyridine I
4-ethylpyridine II
8.0
14.8
4.6
3.9
–
6
–
–
–
3.9
–
11.253 Å
8.380 Å
8.308 Å
8.281 Å
This work
[54]
[56]
–
[56]
family. We also tried to measure Mn-3 obtained from solution ior and ferromagnetic interactions. This is in agreement with
but we always obtained poor magnetic curves that indicates the results obtained for similar compounds and indicates that
the presence of a contamination. If the material is investigated there is no simple correlation between the shortest interchain
by XRPD measurements directly after the magnetic measure- Ni–Ni distances and the strength of this interaction.
ments always a mixture of Mn-3 and the hydrate Mn-2 is pres-
ent, which shows that Mn-3 is extremely hygroscopic. Several
Experimental Section
different batches were measured but all magnetic curves
looks similar. A similar behavior is observed e.g. for
[Mn(NCS)2(2-methylpyrazine)2]n, which shows antiferromag-
netic ordering on cooling.[60] However, even this compound is
hygroscopic, always contaminated with a very small amount
and thus, it susceptibility curve shows a strong increases after
the antiferromagnetic maximum. In contrast, Mn-3 is always
contaminated with large amounts of the hydrate Mn-2 and
therefore, the paramagnetic impurity seems to dominate.
Therefore, one cannot decide if it Mn-3 will also show antifer-
romagnetic ordering, which would be typical for this class of
compounds.
Concerning the magnetic properties of Ni-3 it is noted that
in all compounds of composition [Ni(NCS)2(L)2]n, in which
the Nickel cations are connected by pairs of μ-1,3-bridging
thiocyanato anions always ferromagnetic interactions with
either Curie-Weiss behavior or metamagnetism is observed
(Table 4). If these magnetic data are compared with that of Ni-
3 there is no simple correlation between the shortest interchain
distances and the Weiss constant or the nature of the magnetic
Syntheses: MnSO4·H2O, NiSO4·6H2O and CdSO4·8/3H2O, KNCS,
FeCl2·4H2O were obtained from Merck, Ba(NCS)2·3H2O and 4-(3-
phenylpropyl)pyridine were obtained from Alfa Aesar. Solvents were
used without further purification. Crystalline powders of all com-
pounds were prepared by stirring the reactants in the respective sol-
vents at room temperature. The residues were filtered off and washed
with the used solvent and dried in air. The purity of all compounds
was checked by X-ray powder diffraction and elemental analysis (Fig-
ures S11–S18, Supporting Information).
Cd(NCS)2: Ba(NCS)2·3H2O (3.1 g, 10 mmol) and CdSO4·8/3H2O
(2.6 g, 10 mmol) were stirred in water (100 mL). The white precipitate
of BaSO4 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 and ele-
mental analysis.
Mn(NCS)2: Ba(NCS)2·3H2O (17.9 g, 58.4 mmol) and MnSO4·6H2O
(9.9 g, 58.4 mmol) were stirred in water (400 mL). The white precipi-
tate of BaSO4 was filtered off and the water evaporated using a rotary
evaporator. The homogeneity of the product was investigated by
behavior observed (Table 4). Therefore, the packing of the X-ray powder diffraction and elemental analysis.
chains in the crystal seems to be more important.
Ni(NCS)2: Ba(NCS)2·3H2O (17.5 g, 57 mmol) and NiSO4·6H2O
(15.0 g, 57 mmol) were stirred in water (400 mL). The white precipi-
tate of BaSO4 was filtered off and the water evaporated using a rotary
evaporator. The homogeneity of the product was investigated by
X-ray powder diffraction and elemental analysis.
Conclusions
Several new coordination compounds based on transition
metal thiocyanates with 4-(3-Phenylpropyl)-pyridine as co-li-
gand were synthesized. It was shown that the discrete com-
plexes with terminal coordinated thiocyanato anions can easily
be prepared for the paramagnetic compounds, whereas those,
in which the metal cations are linked by the anionic ligands,
are difficult to synthesize. This shows that the former com-
pounds are energetically favored, which can be traced back to
the low chalcophilicity of the paramagnetic compounds. It is
noted that the opposite is the case for compounds based on
CdII, which prefer coordination to sulfur. IR spectroscopic in-
vestigations reveal, that a continuous shift of the asymmetric
stretching vibration is observed for the different metal cations
and that in this case one can easily differ between a terminal
and a bridging coordination. Unfortunately, only one com-
pound with a bridging coordination of the anionic ligands can
Synthesis of Mn-1: Single crystals suitable for single-crystal X-ray
diffraction were obtained by the reaction of Mn(NCS)2 (0.25 mmol,
44.3 mg) and 4-(3-phenylpropyl)pyridine (0.50 mmol, 96.3 μL) in H2O
(1.5 mL). Colorless block-shaped crystals were obtained after two
weeks. A white crystalline powder on a larger scale were obtained by
stirring Mn(NCS)2 (171.1 mg, 1.00 mmol), and 4-(3-phenylpropyl)-
pyridine (770.6 μL, 4.00 mmol) in ethanol (5 mL) for 3 d. Yield:
97.1%. C58H60MnN6S2 (960.22): calcd. C 72.55, H 6.30, N 8.75; S
6.68%, found C 71.93, H 6.32, N 8.77, S 6.62%. IR (ATR): ν˜max
=
3023 (w), 2942 (w), 2859 (w), 2060 (s), 1609 (m), 1419 (m), 1422
(m), 1222 (w), 1011 (m), 839 (m), 748 (s), 702 (s), 603 (m), 570 (m),
512 (s) cm–1.
Synthesis of Fe-1: Single crystals suitable for single-crystal X-ray dif-
fraction were obtained by the reaction of FeCl2·4H2O (0.25 mmol,
49.7 mg), KNCS (0.5 mmol, 48.6 mg) and 4-(3-phenylpropyl)pyridine
be prepared phase pure (Ni-3) that shows Curie-Weiss behav- (0.5 mmol, 93.3 μL) in water (1.5 mL). Orange colored crystals were
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J. Werner, I. Jess, C. Näther
ARTICLE
obtained after one month. A yellow crystalline powder on a larger
Synthesis of Cd-3: Cd(NCS)2 (0.30 mmol, 68.6 mg) and 4-(3-phen-
scale were obtained by stirring FeCl2·4H2O (198.8 mg, 1.00 mmol), ylpropyl)pyridine (0.15 mmol, 28.9 μL) were dissolved in ethanol
KNCS (194.4 mg, 2.00 mmol) and 4-(3-phenylpropyl)pyridine (1.5 mL) and heated at 80 °C for 3 d. The resulting solution was cooled
(770.6 μL, 4.00 mmol) in ethanol (5 mL) and H2O (2 mL) and EtOH down and single crystals suitable for single-crystal X-ray diffraction
(3 mL) for 3 d. Yield: 90.1%. C58H60CoN6S2 (964.22 g·mol–1): calcd.
C 72.25, H 6.27, N 8.72; S 6.65%, found C 71.72, H 6.21, N 9.15, S
were obtained. A colorless crystalline powder was synthesized by stir-
ring Cd(NCS)2 (229 mg, 1.00 mmol) and 4-(3-phenylpropyl)pyridine
6.75%. IR (ATR): ν˜max = 3024 (w), 2942 (w), 2859 (w), 2063 (s), (192.6 μL, 1.00 mmol) in ethanol (5 mL) for 7 d. Yield: 75.8%.
2015 (m), 1609 (m), 1496 (m), 1419 (m), 1222 (m), 1011 (m), 841
C58H60CdN6S2 (1017.69 g·mol–1): calcd. C 57.83, H 4.85, N 8.99, S
10.29%, found C 57.42, H 4.70, N 8.97, S 10.51%. IR (ATR): ν˜max
= 3018 (w), 2942 (w), 2858 (w), 2091 (s), 1612 (m), 1494 (w), 1425
(m), 1226 (w), 1015 (m), 799 (m), 749 (s), 699 (s), 597 (m), 493 (m)
(m), 749 (s), 702 (s), 603 (m), 570 (m), 513 (s) cm–1.
Synthesis of Ni-1: Single crystals suitable for single-crystal X-ray dif-
fraction were synthesized by Ni(NCS)2 (0.25 mmol, 43.7 mg) and 4- cm–1.
(3-phenylpropyl)pyridine (0.5 mmol, 93.3 μL) in acetonitrile (1.5 mL).
After few weeks, blue crystals were obtained. A blue colored crystal-
Elemental Analysis: CHNS analysis was performed with an EURO
line powder on a larger scale was obtained by stirring Ni(NCS)2 EA elemental analyzer, fabricated by EURO VECTOR Instruments
(87.4 mg, 0.50 mmol), and 4-(3-phenylpropyl)pyridine (385 μL, and Software.
2.00 mmol) in ethanol (4 mL) for 6 d. Yield: 93.8%. C58H60N6NiS2
(963.98 g·mol–1): calcd. C 72.27, H 6.27, N 8.72, S 6.65%; found C
72.33, H 6.34, N 9.12, S 6.17%. IR (ATR): ν˜max = 3023 (w), 2942
Differential Thermal Analysis and Thermogravimetry: The DTA-
TG measurements were performed in a dynamic nitrogen atmosphere
(w), 2859 (w), 2081 (s), 1612 (m), 1496 (m), 1419 (s), 1423 (s), 1211 (purity: 5.0) in Al2O3 crucibles with a STA-409CD thermobalance
(m), 1014 (m), 824 (m), 750 (s), 703 (s), 570 (m), 515 (s) cm–1.
from Netzsch. All measurements were performed with a flow rate of
75 mL·min–1 and were corrected for buoyancy and current effects. The
instrument was calibrated using standard reference materials.
Synthesis of Cd-1: A colorless crystalline powder was prepared by
stirring Cd(NCS)2 (114.3 mg, 0.50 mmol), and 4-(3-phenylpropyl)pyr-
idine (577.8 μL, 3.00 mmol) in acetonitrile (5 mL) for 7 d. Yield:
89.2%. C58H60CdN6S2 (1017.69 g·mol–1): calcd. C 68.45, H 5.94, N
8.26, S 6.30%; found C 68.38, H 6.20, N 8.36, S 5.94%. IR (ATR):
Single-Crystal Structure Analysis: The investigations were per-
formed with the imaging plate diffraction system (IPDS-1 for Mn-1,
Fe-1, Ni-1, Mn-2 and IPDS-2 for Mn-3, Ni-3, Cd-3) with Mo-Kα-
ν˜max = 3024 (w), 2942 (w), 2861 (w), 2064 (s), 1609 (m), 1496 (m), radiation from STOE & CIE. The structure solution was performed
1422 (m), 1222 (m), 1014 (m), 839 (m), 749 (s), 702 (s), 602 (m), 788 with direct methods using SHELXS-97, and structure refinements were
(s), 571 (m), 513 (s) cm–1.
performed against F2 using SHELXL-97.[61] All non-hydrogen atoms
were refined with anisotropic displacement parameters. The hydrogen
Synthesis of Mn-2: Mn(NCS)2 (0.25 mmol, 42.8 mg) and 4-(3-phen- atoms were positioned with idealized geometry and were refined iso-
ylpropyl)pyridine (0.50 mmol, 96.3 μL) were dissolved in acetonitrile
tropic with Uiso(H) = 1.2·Ueq(C) using a riding model. Selected crystal
(1.5 mL). The solvent was reduced by slow evaporation and after sev-
data and details of the structure refinements are listed in Table 5.
eral months a few single crystals were obtained. IR (ATR): ν˜max
3424 (b), 3354 (w), 30198 (w), 3024 (w), 2944 (w), 2855 (w), 2095 Crystallographic data (excluding structure factors) for the structures in
(s), 1612 (s), 1558 (m), 1494 (m), 1452 (m), 1423 (m), 1225 (m), 1065 this paper have been deposited with the Cambridge Crystallographic
=
(m), 1015 (m), 822 (m), 754 (s), 697 (s), 602 (m), 516 (s), 496 (s), Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
454 (s) cm–1.
Copies of the data can be obtained free of charge on quoting the de-
pository numbers CCDC-1015241 (Mn-1), CCDC-1015239 (Fe-1),
CCDC-1015242 (Ni-1), CCDC-1015240 (Mn-2), CCDC-1015237
Synthesis of Mn-3: A solution of Mn(NCS)2 (0.50 mmol, 85.6 mg)
and 4-(3-phenylpropyl)pyridine (0.25 mmol, 48.2 μL) in acetonitrile (Mn-3), CCDC-1015238 (Ni-3), and CCDC-1015236 (Cd-3)
(1.5 mL) was heated at 80 °C for 3 d and cooled down. The resulting
solution was reduced by slow evaporation. On slow evaporation of the
solvent of the clear solution single crystals suitable for single-crystal
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk).
X-ray diffraction was obtained. A beige crystalline powder was ob- X-ray Powder Diffraction (XRPD): XRPD experiments were per-
tained. IR (ATR): ν˜max = 3061 (w), 2942 (w), 2857 (w), 2087 (s), formed with a Stoe Transmission Powder Diffraction System (STADI
1613 (m), 1558 (m), 1494 (m), 1423 (m), 1228 (m), 1069 (m), P) with Cu-Kα-radiation (λ = 1.5406 Å) that is equipped with a linear
1014 (m), 836 (m), 800 (m), 749 (s), 699 (s), 597 (m), 573 (m), position-sensitive detector (Delta 2θ = 6.5–7° simultaneous; scan range
493 (s) cm–1.
overall = 2–130°) from STOE & CIE and an Image Plate Detector
(scan range overall = 0–127°) and a PANalytical X’Pert Pro MPD
Synthesis of Ni-3: Ni(NCS)2 (0.50 mmol, 87.4 mg) and 4-(3-phen- reflection powder diffraction system with Cu-Kα radiation (λ =
ylpropyl)pyridine (0.25 mmol, 48.2 μL) were dissolved in ethanol
(1.5 mL) and heated at 80 °C for 3 d. The resulting solution was cooled
down and single crystals suitable for single-crystal X-ray diffraction
were obtained. A light green colored crystalline powder was synthe-
sized by stirring Ni(NCS)2 (174.9 mg, 1.00 mmol) and 4-(3-phen-
ylpropyl)pyridine (192.6 μL, 1.00 mmol) in ethanol (5 mL) for 7 d.
154.0598 pm) equipped with a PIXcel semiconductor detector from
PANanlytical.
Magnetic Measurements: All magnetic measurements were per-
formed using a Physical Property Measuring System (PPMS) from
Quantum Design, which is equipped with a 9 T magnet. The data were
Yield: 80.2%. C30H30N4NiS2 (569.42 g·mol–1): calcd. C 63.28, H 5.31, corrected for Core diamagnetism using Pascal constants.
N 9.84, S 11.26%, found C 63.27, H 5.40, N 9.67, S 11.22%. IR
(ATR): ν˜max = 3017 (w), 2942 (w), 2858 (w), 2109 (s), 1615 (m), 1422
IR Spectroscopy: IR spectroscopic investigations were performed
(m), 1226 (m), 1018 (w), 804 (m), 750 (s), 699 (s), 598 (m), 514 (m) with an ATI Mattson Genesis Series FTIR Spectrometer, control soft-
cm–1.
ware: WINFIRST, from ATI Mattson.
2166
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© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 2161–2168

Thiocyanato Coordination Polymers with 4-(3-Phenylpropyl)pyridine
Table 5. Selected crystal data and details on the structure determinations for compounds M-1, M-2, and M-3.
Mn-1
Fe-1
Ni-1
Mn-2
Mn-3
Ni-3
Cd-3
Formula
C58H60MnN6S2 C58H60FeN6S2 C58H60N6NiS2 C30H34MnN4O2S2 C30H30MnN4S2 C30H30N4NiS2 C30H30CdN4S2
MW /g·mol–1
Crystal system
Space group
Z
960.18
961.09
963.95
601.67
565.64
monoclinic
P21/c
569.41
monoclinic
P21/n
4
623.10
monoclinic
P21/n
4
triclinic
triclinic
triclinic
triclinic
¯
¯
¯
¯
P1
P1
P1
P1
1
1
1
2
4
Dcalc /mg·m–3
1.237
0.381
–
1.257
0.423
0.8083,
1.263
0.509
–
1.300
0.598
0.8401, 0.9423
1.309
0.631
0.6921, 0.9089
1.343
0.863
–
1.399
0.904
–
μ /mm–1
Min/max. transm.
0.9544
a /Å
b /Å
c /Å
α /°
9.4775(8)
11.4676(10)
13.2370(9)
72.275(9)
82.587(9)
70.243(9)
1289.14(18)
200(2)
9.4304(7)
11.3925(9)
13.1629(10)
72.311(9)
82.717(9)
70.497(9)
1269.50(17)
200(2)
9.4730(6)
11.3573(9)
13.1127(10)
72.416(9)
83.004(8)
70.540(8)
1267.67(16)
200(2)
8.0118(6)
12.3995(10)
15.8623(11)
79.652(9)
82.825(9)
90.096(9)
1537.6(2)
293(2)
11.4485(3)
15.9460(4)
15.7759(5)
90
94.624(2)
90
11.2010(5)
16.0326(6)
15.7935(7)
90
96.715(4)
90
11.6228(3)
16.1656(6)
15.7701(4)
90
93.387(2)
90
β /°
γ /°
V /Å3
T /K
2870.64(14)
200(2)
2816.8(2)
293(2)
2957.86(15)
293(2)
θmax /°
Measured refl.
Rint
Unique reflns.
Refl.[Fo Ͼ 4σ(Fo)] 2873
2.50 to 25.00
8547
0.0875
2.52 to 27.00 2.51 to 25.00 2.31 to 26.01
2.12 to 28.00
44573
0.0789
6898
1.82 to 25.00 2.12 to 27.97
14916
0.0512
5320
8049
0.0740
4372
12061
0.0484
5876
19820
0.0679
4951
41660
0.0414
42407
5191
4402
4021
3017
4582
5919
3535
Parameters
R1 [Fo Ͼ 4σ(Fo)]
wR2 [all data]
GOF
304
305
301
359
337
337
337
0.0490
0.1243
0.950
0.0400
0.1008
0.953
0.256 and
–0.450
0.0424
0.0885
0.936
0.235 and
–0.288
0.0417
0.1076
1.001
0.0389
0.0933
1.089
0.0569
0.1178
1.141
0.511 and
–0.308
0.0428
0.0923
1.101
0.366 and
–0.535
Δρ(max/min) /e·Å–3 0.256 and
0.253 and –0.479 0.331 and
–0.350
–0.402
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Supporting Information (see footnote on the first page of this article):
Calculated XRPD patterns, Ortep plots of compounds Mn-1, Fe-1,
Ni-1, Cd-1, Mn-2 and Ni-2. TG curves for Mn-1, Fe-1, Ni-1, Cd-1.
Experimental and calculated XRPD patterns for compounds Mn-1,
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Acknowledgements
This project was supported by the Deutsche Forschungsgemeinschaft
(DFG) (Project No. NA 720/5–1) and the State of Schleswig-Holstein.
We thank Professor Dr. Wolfgang Bensch for access to his experimen-
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Received: May 27, 2014
Published Online: July 25, 2014
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Z. Anorg. Allg. Chem. 2014, 2161–2168