Synthesis, Structures, and Properties of Transition Metal Thiocyanato Coordination Compounds with 4-(4-Chlorobenzyl)pyridine as Ligand

Article abstract of DOI:10.1002/zaac.201400341

Reactions of transition metal thiocyanates with 4-(4-chlorobenzyl)pyridine (Clbp) lead to the formation of compounds of composition M(NCS)₂(4-(4-chlorobenzyl)pyridine)₄ (Mn-1, Fe-1/I, Fe-1/II, Ni-1, and Cd-1) and M(NCS)₂(4-(4-chlorobenzyl)pyridine)₂ (Mn-2, Ni-2, and Cd-2). In the crystal structures of compounds M-1 the metal cations are octahedrally coordinated by two terminal N-bonded thiocyanato anions and four Clbp ligands, whereas in compounds M-2 the metal cations are linked by μ-1, 3-bridging anionic ligands. IR spectroscopic investigations show that the value of the asymmetric C-N stretching vibration depends on the coordination mode of the thiocyanato ligand and the nature of the metal cations. The thermal properties were investigated by simultaneous differential thermoanalysis and thermogravimetry as well as temperature dependent X-ray powder diffraction. On heating compound Ni-1 looses half of the Clbp ligands and transforms into Ni-2. Clbp deficient intermediates were also detected on thermal decomposition of Mn-1 and Fe-1/I but the samples are of low crystallinity and therefore, their structures cannot be determined. Magnetic investigations reveal that Ni-2 shows only Curie-Weiss paramagnetism without any magnetic anomaly.

Full text of DOI:10.1002/zaac.201400341

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ARTICLE
DOI: 10.1002/zaac.201400341
Synthesis, Structures, and Properties of Transition Metal Thiocyanato
Coordination Compounds with 4-(4-Chlorobenzyl)pyridine as Ligand
Julia Werner,[a] Tristan Neumann,[a] and Christian Näther*[a]
Dedicated to Professor Martin Jansen on the Occasion of His 70th Birthday
Keywords: Crystal structure; Thiocyanato coordination polymers; Thermochemistry; IR spectroscopy; Magnetochemistry
Abstract. Reactions of transition metal thiocyanates with 4-(4-chlo-
robenzyl)pyridine (Clbp) lead to the formation of compounds of com-
thiocyanato ligand and the nature of the metal cations. The thermal
properties were investigated by simultaneous differential thermoanaly-
position M(NCS)2(4-(4-chlorobenzyl)pyridine)4 (Mn-1, Fe-1/I, Fe-1/ sis and thermogravimetry as well as temperature dependent X-ray
II, Ni-1, and Cd-1) and M(NCS)2(4-(4-chlorobenzyl)pyridine)2 (Mn- powder diffraction. On heating compound Ni-1 looses half of the Clbp
2, Ni-2, and Cd-2). In the crystal structures of compounds M-1 the ligands and transforms into Ni-2. Clbp deficient intermediates were
metal cations are octahedrally coordinated by two terminal N-bonded also detected on thermal decomposition of Mn-1 and Fe-1/I but the
thiocyanato anions and four Clbp ligands, whereas in compounds M- samples are of low crystallinity and therefore, their structures cannot
2 the metal cations are linked by μ-1,3-bridging anionic ligands. IR
be determined. Magnetic investigations reveal that Ni-2 show only Cu-
spectroscopic investigations show that the value of the asymmetric rie-Weiss paramagnetism without any magnetic anomaly.
C–N stretching vibration depends on the coordination mode of the
project we are especially interested in compounds, in which
the central metal atoms are coordinated only by monodentate
ligands and are linked by pairs of thio- or selenocyanato anions
into chains, which are not further connected into layers by the
Introduction
Investigations on the synthesis, structure, and properties of
new coordination compounds are still an active field in coordi-
nation chemistry. The major goal in this area includes the de-
co-ligands. Unfortunately, the compounds with bridging li-
velopment of strategies for a more rational synthesis of com-
gands are sometimes difficult to prepare in solution and there-
pounds with definite structures and desired physical proper-
fore, we use an alternative solid state route, in which suitable
ties.[1–11] This also includes investigations on compounds that
precursor compounds with terminal bonded anionic ligands are
show cooperative magnetic phenomena and therefore, a large
thermally decomposed.[45–47] The synthesis of coordination
number of compounds based on small ligands like e.g. azides,
compounds via typical solid state methods is not uncommon
and also other strategies were reported.[48–51] However, one
disadvantage of thermal decomposition reactions is the fact
that only crystalline powders and sometimes different modifi-
cations are obtained and therefore, structural information is
difficult to retrieve.[52] In some cases the coordination mode
of the anionic ligands might be determined by IR spec-
troscopy.[53,54] Moreover, structural information can also be
extracted by preparing the corresponding compounds with cad-
oxalates and others were recently reported.[12–18] In this con-
text also coordination compounds based on thio- or selenocya-
nates are of interest and some representative examples are
given in the reference list.[19–34]
In our own research, we are also interested in the magnetic
properties of thio- and selenocyanato coordination polymers,
with focus on compounds, in which the central metal atoms
are linked by μ-1,3-bridging anionic ligands.[35] In the course
of this project we have investigated several of such com-
pounds, predominantly based on MnII, FeII, CoII, and NiII that mium or zinc, because in several cases they are isotypic to the
paramagnetic analogs.[55,56] Therefore, systematic investi-
gations on the synthesis, the crystal structures as well as the
thermal and spectroscopic properties of thio- and selenocya-
nato coordination compounds are of extraordinary importance
for our project.
In the course of our investigations we decided to study the
influence of larger monodentate N-donor co-ligands on the
thermal reactivity in more detail and for the present study Clbp
was selected, for which no coordination compounds are re-
ported in the Cambridge Structural Database.[57] Within these
as function of the metal cations and the neutral N-donor co-
ligand show different magnetic properties.[36–44] Within this
* 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.201400341 or from the au-
thor.
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investigations we prepared several new compounds based on stretching vibration it can be assumed that in compounds M-2
MnII, FeII, NiII, and CdII, in which the central metal atoms are bridging thiocyanato anions are present (see below).
coordinated by terminal N-bonded anions and which might be
useful as precursors for the preparation of the desired com-
pounds with a bridging coordination. Herein we report on our
results.
Results and Discussion
Synthetic Investigations
To investigate, which compounds are available in solution
different ratios of M(NCS)2 (M = Mn, Fe, Ni, Cd) and 4-(4-
chlorobenzyl)pyridine) (Clbp) were reacted in different sol-
vents at room temperature and the residues obtained were fil-
tered of and investigated by elemental analysis and X-ray pow-
der diffraction (XRPD). Elemental analyses showed that com-
pounds of composition M(NCS)2(4-(4-chlorobenzyl)pyridine)4
(Mn-1, Fe-1/I, Ni-1, and Cd-1) and of composition M(NCS)2-
(4-(4-chlorobenzyl)pyridine)2 (Mn-2, Ni-2, and Cd-2) were
Figure 2. Experimental XRPD pattern of Mn-2, Ni-2, and Cd-2.
formed (Table S1, Supporting Information). For Mn-2 some
deviations from the calculated values are found, indicating that
Solvent mediated conversion experiments of a mixture of
this compound contains some contamination.
Fe-1/I and Fe-1/II prove, that in water Fe-1/II transforms into
XRPD investigations indicate that Mn-1, Fe-1/I, and Cd-1
Fe-1/I and therefore, that Fe-1/I represent the thermodynamic
are isotypic and that Ni-1 crystallizes differently (Figure 1).
stable modification at room temperature (Figure S1 in the Sup-
porting Information).
In further work crystallization experiments were performed
at room temperature and under solvothermal conditions, which
lead to the formation of single crystals of Mn-1, Fe-1/I, Ni-1,
Cd-1 as well as of Mn-2, Ni-2 and Cd-2. Comparison of the
experimental powder patterns of compounds M-1 and M-2
with that calculated from single crystal data proves that Mn-
1, Fe-1/I, Ni-1, Cd-1, and Ni-2 are obtained as pure phases,
whereas Mn-2 is contaminated with Mn-1 and Cd-2 with a
small amount of an additional phase, that cannot be identified
(Figures S2–S8, Supporting Information).
Moreover, the residue obtained with iron at ratio 1:4 shows a
different powder pattern, indicating that a second modification
is obtained (Fe-1/II) that might be contaminated with Fe-1/I
(Figure 1). It is noted, that the powder pattern of Fe-1/II is
similar to that of Ni-1 (Figure 1). IR spectroscopic investi-
gations indicate that the C–N stretching vibrations of com-
pounds M-1 are in the range expected for terminally N-bonded
thiocyanato anions (see below).
Crystal Structures
The compounds M(NCS)2(4-(4-chlorobenzyl)pyridine)4 [M
= Mn (Mn-1), Fe (Fe-1/I), and Cd (Cd-1)] are isotypic and
crystallize in the monoclinic centrosymmetric space group
C2/c with four formula units in the unit cell. The asymmetric
unit consists of one crystallographically independent discrete
complex, which is located on a center of inversion, as well as
of one thiocyanato anion and two 4-(4-chlorobenzyl)pyridine
ligands in general position (Figure 3). Ni(NCS)2(4-(4-chlo-
robenzyl)pyridine)4 (Ni-1) crystallizes monoclinic in space
group P21 with two formula units in the unit cell and all atoms
in general positions.
Figure 1. Experimental XRPD pattern of Mn-1, Fe-1/I, Fe-1/II, Ni-1,
In the crystal structures of compounds M-1 the metal cations
and Cd-1.
are coordinated by two nitrogen atoms of two terminal thiocy-
For the M-2 compounds XRPD investigations indicate that anato anions and four nitrogen atoms of terminal bonded 4-(4-
Mn-2 and Ni-2 are isotypic, that Cd-2 exhibits a different chlorobenzyl)pyridine ligands within a slightly distorted octa-
structure and that Mn-2 is contaminated with large amounts of hedral coordination arrangement. The angles around the metal
Mn-1 (Figure 2). Based on the value of the asymmetric C–N cations range between 88.33(17) and 91.39(8)° and the metal-
2
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Transition Metal Thiocyanato Coordination Compounds
Figure 3. Crystal structure of Mn-1 as a representative with atom la-
beling (Ortep plots of Mn-1, Fe-1/I, Ni-1 and Cd-1 are shown in
Figures S9–S12 in the Supporting Information).
Figure 4. Crystal structure of compound Mn-2 as a representative with
atom labeling (Ortep plots of Mn-2, Ni-2, and Cd-2 are shown in
Figures S13–S15 in the Supporting Information).
nitrogen distances range between 2.040(3) and 2.381(2) Å.
(Tables S2–S5, Supporting Information).
The compounds [M(NCS)2(4-(4-chlorobenzyl)pyridine)2]n
(M = Mn, Ni) crystallize in the triclinic centrosymmetric space
¯
group P1 with two formula units in the unit cell. The asymmet-
ric unit consists of two metal cations, which are situated on a
center of inversion as well as two 4-(4-chlorobenzyl)pyridine
and two thiocyanato ligands in general positions (Figure 4).
[Cd(NCS)2(4-(4-chlorobenzyl)pyridine)2]n crystallizes mono-
clinic in space group P21/c with two formula unit in the unit
cell. The asymmetric unit consists of two metal cations, three
thiocyanato anions and three 4-(4-chlorobenzyl)pyridine li-
gands. One metal cation is located on center of inversion; all
other atoms are located in general positions.
In their crystal structures the metal cations are coordinated
by two N-bonded Clbp ligands and two N-bonded μ-1,3 bridg-
ing thiocyanato anions as well as two adjacent S-bonded μ-1,3
bridging thiocyanato anions. The cations are linked into chains
by pairs of μ-1,3 bridging thiocyanato anions. The metal–nitro-
gen distances range between 2.027(2) and 2.335(3) Å as well
as the metal–sulfur distances range between 2.5151(6) and
2.7438(10) Å (Tables S6–S8, Supporting Information).
Figure 5. TG curves for the compounds Mn-1, Fe-1/I, Ni-1, and
Cd-1. Heating rate = 1 °C·min–1.
Thermoanalytical Investigations
the residue formed in the first step is investigated by XRPD it
To check if Clpb deficient compounds are accessible, the is obvious that a mixture of Mn-1 and Mn-2 is obtained (Fig-
precursor compounds M(NCS)2(4-(4-chlorobenzyl) pyridine)4 ure S20, Supporting Information). For Fe-1/I and Cd-1 similar
(M = Mn, Fe, Ni, Cd) were investigated by simultaneous observations were made and there are no indications for ad-
differential thermoanalysis and thermogravimetry (DTA-TG). ditional intermediates. This does not change if all compounds
On heating all M-1 compounds show one mass step at about are investigated by heating rate dependent measurements,
200 °C, which, as function of the metal cation is differently which show that the best resolution is obtained with 1 °C·
resolved (Figure 5).
min–1 (Figures S16–19, Supporting Information). In contrast,
For Mn-1 the mass loss of the first step does not correspond Ni-1 shows two good resolved mass steps and the experimental
to that calculated for the removal of two Clbp ligands and if mass loss of 39.7% in the first and 39.0% in the second TG
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step is in moderate agreement with the calculated mass loss Table 1. Values of the asymmetric C–N stretching vibration for com-
pounds M-1 and M-2 as well as for the corresponding compounds with
for the removal of two 4-(4-chlorobenzyl)pyridine ligands
(Δmcalcd. = –41.2%). If the residue formed after the first mass
pyridine retrieved from literature.[38,40]
step is investigated by XRPD it is proven that Ni-2 has formed Compound
νas(CN) /cm–1 Compound
νas(CN) /cm–
1
as a pure phase (Figure 6).
Cd-1
Mn-1
Fe-1/I
Ni-1
Cd(NCS)2(Pyr)4 2050
Mn(NCS)2(Pyr)4 2060
Fe(NCS)2(Pyr)4 2066
Ni(NCS)2(Pyr)4 2082
2054
2051
2056
2071
Cd-2
Mn-2
Fe-2
Ni-2
Mn(NCS)2(Pyr)2
Mn(NCS)2(Pyr)2
Mn(NCS)2(Pyr)2
Mn(NCS)2(Pyr)2
2107
2094
–
2117
2097
2090
2093
2110
This clearly shows that an assignment of the coordination
mode for different compounds only on the basis of IR spectro-
scopic data might be sometimes difficult to achieve.
Magnetic Investigations
Compound Ni-2, in which the central metal atoms are linked
by pairs of μ-1,3 bridging thiocyanato anions was investigated
for its magnetic properties. It is noted that compounds M-1
consist of discrete complexes and therefore, only Curie or Cu-
rie-Weiss behavior is expected as observed for related com-
pounds reported recently.[38,40] As shown above, compound
Mn-2 is contaminated with Mn-1 and therefore, were not in-
vestigated.
Figure 6. Experimental XRPD pattern of the residue obtained after
the first mass step in thermal decomposition of compound Ni-1 (A),
experimental XRPD pattern for Ni-2 obtained from solution (B) and
calculated XRPD for compound Ni-2 (C).
The temperature dependence of the susceptibility χ was
measured as function of temperature for Ni-2 and only para-
magnetic behavior is observed. The experimental magnetic
moment at room-temperature retrieved from the (8χT)1/2 curve
of about 2.8 μB is in perfect agreement with that calculated
for NiII in high-spin configuration (2.82 μB). Analyzing the
magnetic data using an Curie-Weiss fit, leads to an effective
magnetic moment of 2.89 μB and a positive Weiss constant of
16.5 K On cooling the χT product increases indicating domina-
ting ferromagnetic interactions between the Ni cations and af-
terwards the susceptibility curve passes a maximum (Figure 7).
Further investigations using temperature dependent XRPD
measurements on Mn-1, Fe-1/I, and Cd-1 indicate that even
for these compounds new Clbp deficient intermediates are
formed, which are of low crystallinity (Figures S21–23, Sup-
porting Information). The powder patterns of these samples do
not correspond to that of compounds M-2 or their mixtures
with compounds M-1 but indexing failed because of their poor
quality. Summarizing, we have found no access to pure sam-
ples of Mn-2.
IR Spectroscopy
To investigate how the value of the C–N stretching vibration
depends on the coordination mode of the ligand and the nature
of the metal cation all compounds were measured by IR spec-
troscopy (Figures S24–31, Supporting Information). These in-
vestigations show that for all compounds with terminal N-
bonded anions; νas(CN) is observed between 2051 and
2071 cm–1 and increases from Mn to Ni (Table 1). A similar
trend is observed for the bridging compounds, for which values
between 2094 and 2117 cm–1 are observed (Table 1). There is
a clear gap between the M-1 and M-2 compounds, which in
this case definitely allows differing between a terminal and a
bridging coordination. If these values are compared with those
for the corresponding compounds with pyridine as reference a
small influence of the co-ligand becomes obvious, because
most values are shifted by several wave numbers.[38,40]
Figure 7. χ and (8χT)1/2 as function of temperature for Ni-2 measured
at Hdc = 1 kOe.
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Transition Metal Thiocyanato Coordination Compounds
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 Xray
powder diffraction and elemental analysis
This is in agreement with results for compounds with similar
Ni(NCS)2 chains like, e.g. in the two modifications of
Ni(NCS)2(4-ethylpyridine)2, for which paramagnetic behavior
dominating ferromagnetic interactions are observed and for
which the χT vs. T curves looks similar.[52] It is noted, that the
corresponding compound with pyridine is a metamagnet with
an antiferromagnetic ground state.[40] Therefore, it cannot be
excluded that antiferromagnetic ordering will occur at lower
temperatures for Ni-2.
Synthesis of Cd-1: Single crystals suitable for single-crystal X-ray
diffraction were prepared by the reaction of Cd(NCS)2 (0.15 mmol,
34.3 mg) and 4-(4-chlorobenzyl)pyridine (0.15 mmol, 26.4 μL) in eth-
anol (1.5 mL). Colorless crystals were obtained after several days. A
colorless crystalline powder on a larger scale was prepared by stirring
Cd(NCS)2 (114.3 mg, 0.50 mmol), and 4-(4-chlorobenzyl)pyridine
(877.9 μL, 5.00 mmol) in ethanol (5 mL) for 3 d. Yield: 90.7%.
C50H40N6Cl4S2Cd (1043.25 g·mol–1): calcd. C 57.57, H 3.86, N 8.06,
Conclusions
In the presented contribution new thiocyanato coordination
compounds with 4ö-(4-chlorobenzyl)pyridine as co-ligand
were prepared and investigated for their properties. For the
paramagnetic compounds it was found that the compounds
with terminal bonded thiocyanato anions can easily be pre-
pared in solution, whereas not all of the corresponding com-
pounds with bridging anionic ligands are accessible from solu-
tion. The bridging compounds with Mn and Fe can also not be
prepared by thermal decomposition and this might be traced
back to the relatively large co-ligand because similar com-
pounds with smaller co-ligands are easily accessible by this
route. IR spectroscopic investigations reveal that one can eas-
ily differ between the different coordination modes and that
only a small shift is observed for the different cations. Mag-
netic measurements on Ni-2 reveal that only paramagnetic be-
havior without any magnetic anomaly is observed and this is
in agreement with our findings for compounds of same compo-
sition but with slightly different co-ligands. If there is any cor-
relation between the size of the co-ligand and the thermal reac-
tivity of the corresponding coordination compounds will be the
subject of further investigations.
S 6.15%; found C 57.22, H 3.81, N 8.10, S 6.06%. IR (ATR): ν˜max
=
3063 (w), 3038 (w), 2054 (s), 1614 (m), 1558 (w), 1490 (m), 1423
(m), 1222 (m), 1091 (m), 1069 (m), 1015 (s), 856 (m), 804 (s), 788
(s), 592 (s), 487 (s) cm–1.
Synthesis of Mn-1: Single crystals suitable for single-crystal X-ray
diffraction were obtained by a reaction of Mn(NCS)2 (0.3 mmol,
51.3 mg) and 4-(4-chlorobenzyl)pyridine (0.15 mmol, 26.4 μL) in
methanol (1.5 mL). Yellow colored block-shaped crystals were ob-
tained after several days. A white crystalline powder on a larger scale
was obtained by stirring Mn(NCS)2 (171.1 mg, 1.00 mmol), and 4-(4-
chlorobenzyl)pyridine (702.3 μL, 4.00 mmol) in ethanol (5 mL) for 3
d. Yield: 95.2%. C50H40N6Cl4S2Mn (985.79): calcd. C 60.92, H 4.09,
N 8.51; S 6.51%; found C60.82, H 3.97, N 8.55, S 6.39%. IR (ATR):
ν˜max = 3066 (w), 3036 (w), 2051 (s), 1615 (m), 1557 (w), 1488 (m),
1422 (m), 1348 (w), 1223 (m), 1014 (s), 855 (m), 804 (s), 788 (s), 591
(s), 488 (s) cm–1.
Synthesis of Fe-1: Single crystals suitable for single-crystal X-ray dif-
fraction were obtained by a reaction of FeCl2·4H2O (0.15 mmol,
29.8 mg), KNCS (0.3 mmol, 29.2 mg) and 4-(4-chlorobenzyl)pyridine
(0.6 mmol, 105.4 μL) in acetonitrile (1.5 mL). Red colored block-
shaped crystals were obtained after several days. A red-brown crystal-
line powder on a larger scale was obtained by stirring FeCl2·4H2O
(198.8 mg, 1.00 mmol), KNCS (194.4 mg, 2.00 mmol) and 4-(4-chlo-
robenzyl)pyridine (1629.3 μL, 4.00 mmol) in H2O (5 mL) and EtOH
(3 mL) for 4 d. Yield: 92.7%. C50H40Cl4FeN6S2 (986.70): calcd. C
60.86, H 4.09, N 8.52; S 6.50%, found C 60.84, H 4.04, N 8.36, S
5.68%. IR (ATR): ν˜max = 3070 (w), 3039 (w), 2915 (w), 2056 (s),
2015 (m), 1613 (s), 1557 (m), 1488 (s), 1422 (s), 1406 (m), 1222 (m),
1091 (m), 1013 (s), 855 (m), 804 (s), 788 (s), 591 (s), 489 (s) cm–1.
Experimental Section
Synthesis: MnSO4·H2O, NiSO4·6H2O, CdSO4·8/3H2O, KNCS, and
FeCl2·4H2O were obtained from Merck, Ba(NCS)2·3H2O and 4-(4-
chlorobenzyl)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 open vessels in the
respective solvents at room temperature. The residues were filtered off
and washed with appropriate solvents and dried in air. The purity of
all compounds was checked by X-ray powder diffraction and elemental
analysis
Synthesis of Ni-1: Single crystals suitable for single-crystal X-ray dif-
fraction were prepared by Ni(NCS)2 (0.15 mmol, 26.3 mg) and 4-(4-
chlorobenzyl)pyridine (0.6 mmol, 105.4 μL). After few days, light-
blue well-shaped single crystals were obtained. A light-green crystal-
line powder on a larger scale was obtained by stirring Ni(NCS)2
(174.9 mg, 0.50 mmol), and 4-(4-chlorobenzyl)pyridine (1222 μL,
6.00 mmol) in ethanol (5 mL) for 3 d. Yield: 97.6%. C50H40N6Cl4S2Ni
(989.54): calcd. C 60.69, H 4.07, N 8.49, S 6.48%; found C 60.35, H
4.06, N 8.64, S 6.24%. IR (ATR): ν˜max = 3074 (w), 3031 (w), 2086
(m), 2069 (s), 1610 (m), 1558 (m), 1489 (s), 1423 (s), 1222 (m), 1090
(m), 1016, 917 (w), 788 (s), 650 (w), 592 (s), 485 (s) cm–1.
Cd(NCS)2: Ba(NCS)2·3H2O (3.076 g, 10 mmol) and CdSO4·8/3H2O
(2.566 g, 10 mmol) were stirred in water (100 mL). The white precipi-
tate of BaSO4 was filtered off and the water was removed from the
filtrate by heating. The final product was dried by 80 °C. The homo-
geneity of the product was investigated by Xray powder diffraction
and elemental analysis.
Mn(NCS)2: Ba(NCS)2·3H2O (17.9 g, 58.44 mmol) and MnSO4·6H2O
(9.9 g, 58.44 mmol) were stirred in water (400 mL). The white precipi-
Synthesis of Mn-2: Single crystals suitable for single-crystal X-ray
tate of BaSO4 was filtered off and the water evaporated using a rotary diffraction were prepared by slow evaporation of the filtrate of the
evaporator. The homogeneity of the product was investigated by Xray
powder diffraction and elemental analysis.
reaction of Mn(NCS)2 (3.0 mmol, 511.0 mg), and 4-(4-chlorobenzyl)
pyridine (0.75 mmol, 131.8 μL) in 4 mL acetonitrile.
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Synthesis of Ni-2: Single crystals suitable for single-crystal X-ray dif-
Elemental Analysis of the Residue Obtained in the Thermal De-
fraction were obtained by a reaction of Ni(NCS)2 (0.15 mmol, composition: Isolated in the first heating step (see thermoanalytical
investigations) of compound Ni-1. Calculated for the ligand-deficient
compound Ni-2: C26H20N4Cl2S2Ni (582.20): calcd. C 53.64, H 3.46,
N 9.62; S 11.02%; found C 53.53, H 3.39, N 9.50, S 11.03%.
26.3 mg) and 4-(4-chlorobenzyl)pyridine (0.3 mmol, 52.7 μL) in water
(1.5 mL) at 105 °C in a closed 10 mL glass culture tube. Light-blue
colored crystals were obtained after several days. A light-blue crystal-
line powder on a larger scale was obtained by stirring Ni(NCS)2
(349.7 mg, 4.00 mmol), and 4-(4-chlorobenzyl)pyridine (176 μL,
1.00 mmol) in ethanol (5 mL) for 10 d. Yield: 93.7%.
C26H20N4Cl2S2Ni (582.20): calcd. C 53.64, H 3.46, N 9.62, S 11.02%;
found C 53.45, H 3.42, N 9.88, S 11.03%. IR (ATR): ν˜max = 2910
(w), 2118 (s), 1613 (m), 1559 (w), 1489 (m), 1423 (m), 1223 (w),
1094 (m), 1067 (m), 1014 (m), 919 (w), 852 (m), 807 (m), 787 (s),
656 (w), 597 (s), 492 (s) cm–1.
Differential Thermal Analysis and Thermogravimetry: The DTA-
TG measurements were performed in a dynamic nitrogen atmosphere
(purity: 5.0) in Al2O3 crucibles with a STA-409CD thermobalance
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.
Single-Crystal Structure Analysis: The investigations were per-
formed with the imaging plate diffraction system (IPDS-1 for Cd-1;
IPDS-2 for Mn-1, Fe-1, Ni-1, Mn-2, Ni-2) with Mo-Kα-radiation from
Synthesis of Cd-2: Single crystals suitable for single-crystal X-ray
diffraction were obtained by a reaction of Cd(NCS)2 (0.30 mmol, STOE & CIE. The structure solution was performed with direct meth-
ods using SHELXS-97 and structure refinements were performed
against F2 using SHELXL-97. All non-hydrogen atoms were refined
with anisotropic displacement parameters. The hydrogen atoms were
positioned with idealized geometry and were refined with fixed iso-
tropic displacement parameters [Uiso(H) = 1.2·Ueq(Caromatic) using a
riding model. For compounds Mn-1, Fe-1, and Cd-1 the Cl atom is
disordered over two sites and was refined using a split model. The
crystal of compound Ni-1 is racemically twinned and therefore, a twin
refinement was performed (BASF parameter: 0.28401).
68.6 mg) and 4-(4-chlorobenzyl)pyridine (0.15 mmol, 26.3 μL) in
acetonitrile (1.5 mL) at room temperature. Colorless crystals were ob-
tained after several days. A colorless crystalline powder on a larger
scale was obtained by stirring Cd(NCS)2 (114.3 mg, 0.50 mmol), and
4-(4-chlorobenzyl)pyridine (93.8 μL, 0.50 mmol) in ethanol (2 mL)
and H2O (1 mL) for 3 d. Yield: 75.2%. C26H20CdCl2N4S2 (635.91):
calcd. C 49.11, H 3.17, N 8.81, S 10.09%; found C 49.12, H 3.09, N
8.93, S 10.22%. IR (ATR): ν˜max = 2108 (s), 1665 (m), 1609 (m), 1558
(w), 1491 (m), 1425 (m), 1286 (w), 1225 (m), 1092 (m), 1070 (m),
1017 (s), 918 (w), 855 (m), 786 (s), 669 (w), 594 (s), 482 (s) cm–1.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-1021251 (Mn-1), CCDC-1021533 (Fe-1), CCDC-
Elemental Analysis: CHNS analysis was performed with an EURO
EA elemental analyzer, fabricated by EURO VECTOR Instruments
and Software.
Table 2. Selected crystal data and details on the structure determinations for compounds M-1 (M = Cd, Mn, Fe, Ni) and M-2 (M = Cd, Mn,
Ni).
Cd-1
Mn-1
Fe-1
Ni-1
Cd-2
Mn-2
Ni-2
Formula
MW /g·mol–1
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
C50H40CdN6Cl4S2 C50H40Cl4MnN6S2
C50H40Cl4FeN6S2 C50H40Cl4N6NiS2 C78H60Cd3Cl6N12S6 C26H20Cl2MnN4S2 C26H20Cl2N4NiS2
1043.20
monoclinic
C2/c
985.74
monoclinic
C2/c
986.65
monoclinic
C2/c
989.51
monoclinic
P21
1907.64
monoclinic
P21/c
578.42
582.19
triclinic
triclinic
¯
¯
P1
P1
18.9719(13)
9.7143(5)
27.6679(19)
90.000
106.855(8)
90.000
4880.1(5)
293
19.0051(8)
9.6769(4)
27.8212(9)
90.00
106.656(3)
90.000
4901.9(3)
293
18.8321(6)
9.5826(2)
27.6478(10)
90.00
106.794(3)
90.00
13.199(3)
13.613(3)
13.454(3)
90.000
95.54(3)
90.000
2406.1(8)
293
17.4730(6)
8.2738(4)
29.5128(13)
90.000
107.970(3)°
90.000
4058.5(3)
200
9.0790(10)
11.0140(15)
14.898(3)
73.854(13)
82.870(13)
68.830(9)
1333.9(3)
200
9.0222(4)
10.7966(5)
14.9511(7)
73.166(4)
83.501(4)
67.963(4)
1292.11(10)
200
γ /°
V /Å3
4776.5(3)
293
T /K
Z
4
4
4
2
2
2
2
Dcalc /g·cm–3
μ /mm–1
θmax /°
1.420
0.793
28.06
1.336
0.613
26.00
1.372
0.669
27.53
1.366
0.753
26.00
1.561
1.181
25.45
1.440
0.874
26.99
1.496
1.142
27.00
Measured refl.
Rint
Unique reflns.
20586
0.0768
5805
19496
0.0251
4793
29617
0.0338
5454
17043
0.0380
9281
36322
0.0460
7435
15000
0.0471
5789
18683
0.0413
5641
Refl. [Fo
4σ(Fo)]
Parameters
Ͼ
4223
296
3844
4575
6826
6148
4497
4398
295
296
569
541
319
320
R1 [Fo Ͼ 4σ(Fo)] 0.0438
0.0489
0.1232
1.058
0.0491
0.1074
1.075
0.0575
0.1140
1.108
0.0417
0.0793
1.092
0.0333
0.0870
1.026
0.0421
0.0939
1.047
wR2 [all data]
GOF
0.1035
1.026
Δρmax/min /e·Å–3
0.500/ –0.526
0.418/ –0.366
0.417/ –0.337
0.270/ –0.177
0.706/ –0.654
0.310/ –0.375
0.349/ –0.427
6
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Transition Metal Thiocyanato Coordination Compounds
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J. Werner, T. Neumann, C. Näther
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Received: July 25, 2014
Published Online: ᭿
8
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Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z14341
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Date: 06-10-14 17:16:29
Pages: 9
z201400341e.xml
Transition Metal Thiocyanato Coordination Compounds
J. Werner, T. Neumann, C. Näther* ................................. 1–9
Synthesis, Structures, and Properties of Transition Metal Thi-
ocyanato Coordination Compounds with 4-(4-Chlorobenzyl)
pyridine as Ligand
Z. Anorg. Allg. Chem. 0000, 0–0
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9