Synthesis, Crystal Structures and Properties of Polymorphic and Isomeric Nickel(II)thiocyanate Coordination Compounds with 3-Bromopyridine as Coligand

Article abstract of DOI:10.1002/zaac.202000483

Reaction of different molar ratios of Ni(NCS)₂ and 3-bromopyridine in water, methanol or acetonitrile leads to the formation of two polymorphs of composition Ni(NCS)₂(3-bromopyridine)₄ (1-I and 1-II), as well as Ni(NCS)₂(3-bromopyridine)₂(H₂O)₂ (2), Ni(NCS)₂(3-Bromopyridine)₂(CH₃OH)₂ (3), Ni(NCS)₂(3-bromopyridine)₂ ? CH₃CN (4) and Ni(NCS)₂(3-bromopyridine)₂ (5). Compounds 1-I, 1-II, 2 and 3 consist of discrete octahedral complexes with terminal N-bonded anionic ligands. In compound 4 the Ni cations are cis-cis-trans coordinated and linked into corrugated chains by pairs of μ-1,3-bridging thiocyanate anions. Solvent mediated conversion experiments prove that form 1-I represents the thermodynamically stable polymorph at room temperature. TG-DTA measurements reveal that upon heating compounds 1-I, 1-II, 2 and 3 lose their coligands stepwise and transform into the new crystalline phase 5 that can also be obtained from solution if the reaction is performed in n-butanol. If the acetonitrile solvate molecules are removed from compound 4, it also transforms into 5. DC magnetic measurements for compound 4 show a maximum, which is indicative for antiferromagnetic ordering, whereas for compound 5 no magnetic ordering is observed. For both compounds, the ferromagnetic exchange constants were determined.

Full text of DOI:10.1002/zaac.202000483

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.202000483
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
1
2
Synthesis, Crystal Structures and Properties of Polymorphic
and Isomeric Nickel(II)thiocyanate Coordination
Compounds with 3-Bromopyridine as Coligand
3
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[a]
[b]
[a]
Christoph Krebs, Magdalena Ceglarska, and Christian Näther*
Dedicated to Prof. Dr. Christoph Janiak on the occasion of his 60th birthday.
1
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Reaction of different molar ratios of Ni(NCS) and 3-bromopyr-
idine in water, methanol or acetonitrile leads to the formation
room temperature. TG-DTA measurements reveal that upon
heating compounds 1-I, 1-II, 2 and 3 lose their coligands
stepwise and transform into the new crystalline phase 5 that
can also be obtained from solution if the reaction is performed
in n-butanol. If the acetonitrile solvate molecules are removed
from compound 4, it also transforms into 5. DC magnetic
measurements for compound 4 show a maximum, which is
indicative for antiferromagnetic ordering, whereas for com-
pound 5 no magnetic ordering is observed. For both com-
pounds, the ferromagnetic exchange constants were deter-
mined.
2
of two polymorphs of composition Ni(NCS) (3-bromopyridine)
2
4
(
1-I and 1-II), as well as Ni(NCS) (3-bromopyridine) (H O) (2),
2 2 2 2
Ni(NCS) (3-Bromopyridine) (CH OH)
(3),
Ni(NCS) (3-
2
2
2
3
2
bromopyridine) ·CH CN (4) and Ni(NCS) (3-bromopyridine) (5).
2
3
2
2
Compounds 1-I, 1-II, 2 and 3 consist of discrete octahedral
complexes with terminal N-bonded anionic ligands. In com-
pound 4 the Ni cations are cis-cis-trans coordinated and linked
into corrugated chains by pairs of μ-1,3-bridging thiocyanate
anions. Solvent mediated conversion experiments prove that
form 1-I represents the thermodynamically stable polymorph at
[12–21]
Introduction
magnetic properties.
However, in those cases in which
compounds with bridging thiocyanate anions are not available
from solution, thiocyanate coordination compounds that con-
tain only terminal N-bonded anionic ligands can be heated,
which usually leads to a stepwise removal of the coligands, and
the irreversible formation of compounds with bridging thiocya-
There is a problem in numbering which was solved.Coordina-
tion compounds based on thiocyanate anions have attracted
much interest in recent years, which can partly be traced back
due to their versatile coordination behaviour leading to
[1–13]
[3]
structures of different dimensionality.
In most compounds
nate anions. In most cases, compounds with 1D or 2D
the anionic ligands are only terminal N-bonded to the metal
cations, whereas the synthesis of compounds with bridging
thiocyanate ligands is sometimes more complicated if less
chalcophilic paramagnetic 3d metal cations are used. This is a
pity, because this ligand is able to mediate reasonable magnetic
exchange leading to compounds that can show different
thiocyanate networks are obtained. For the 2D compounds only
very few networks of different topology are reported, in which
e.g. the metal cations are linked into dimers that are further
connected into layers by single thiocyanate anions or in which
[22–23]
the layers consist of only single anionic ligands.
Regarding
such 2D networks, compounds based on Co(NCS) and Ni(NCS)2
2
are of special interest, because with both cations the magnetic
exchange is usually ferromagnetic and at low temperatures
ferromagnetic ordering is observed. In this case, the critical
temperatures are always higher for Ni(II) than for Co(II), which
allows the tuning of the critical temperatures by mixed crystal
[
a] C. Krebs, Prof. Dr. C. Näther
Institute of Inorganic Chemistry
Christian-Albrechts-University of Kiel
Max-Eyth-Straße 2
24118 Kiel
Germany
E-mail: cnaether@ac.uni-kiel.de
b] M. Ceglarska
Institute of Physics, Jagiellonian University
Łojasiewicza 11, 30-348 Kraków
Poland
Supporting information for this article is available on the WWW
under https://doi.org/10.1002/zaac.202000483
[24–26]
formation.
In contrast, much more examples for compounds that
consist of chains are reported. In nearly all cases the metal
cations are octahedrally coordinated and linked into chains by
[
[27–38]
pairs of thiocyanate anions.
In such compounds the metal
cations are always linked to three pairs of chemically identical
donor atoms, which corresponds to a MA B C system, for which
2
2 2
five geometrical isomers can exist. This includes the all-trans,
three cis-cis-trans, and the all-cis coordination. The all-cis isomer
would form a pair of stereoisomers, but because of geometrical
reasons, it is unlikely that for this kind of chains this isomer will
exist. For the other isomers, several examples are reported in
the literature. In most cases, compounds with an all-trans
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coordination are reported, which leads to the formation of
pyridine) ) indicating the formation of two polymorphic mod-
ifications, of which one is obtained after a short (1-II) and
4
1
2
3
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[30,38–43]
linear chains.
Linear chains are also obtained if the
thiocyanate S and N atoms are cis, whereas the coligands are
another after a much longer reaction time (1-I). The CN
[
13,44]
À 1
still trans.
For the other cis-cis-trans coordinations corru-
stretching vibration is observed at 2074 cm (1-I) and at
[
31–32,39, 45–46]
À 1
gated chains are formed.
The linear chains with Co
2086 cm (1-II), which points to the presence of N-terminal
and Ni are of special interest, because in both cases
ferromagnetic magnetic exchange interactions along the chains
are observed and the compounds with Co show 1D or 3D
bonded anionic ligands (Figure S2 and S3). Therefore, it can be
assumed that these modifications consist of discrete complexes,
in which the Ni cations are octahedrally coordinated by two N-
bonded thiocyanate anions and four 3-bromopyridine ligands.
[34–38,46]
ferromagnetic ordering.
Concerning the chemical and structural properties of Co-
NCS) and Ni(NCS) coordination compounds, several similar-
If Ni(NCS) and 3-bromopyridine are reacted in ratio 1:2 two
2
1
1
1
1
1
1
1
1
1
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5
(
different crystalline phases are obtained from water and
methanol (Figure S1). For these compounds, preliminary ther-
mogravimetric measurements indicate the presence of water
and methanol, which together with the results from elemental
2
2
ities are observed. If the same coligand is used, in most cases
compounds of the same compositions are obtained that in
several cases are isotypic. So if polymorphic or isomeric
compounds with Co(NCS) are accessible, these compounds can
analysis
bromopyridine)(H O)
leads
to
a
composition
(2) and
of
Ni(NCS) (3-
2
2
often also be prepared with Ni(NCS) . However, we have found
Ni(NCS) (3-
2
2
2
2
examples where a certain compound with Ni(NCS) can easily
bromopyridine)(CH OH) (3). For these compounds, the CN
3 2
2
À 1
be prepared whereas no access to the corresponding Co(NCS)2
compound was found. This is the case for, e.g. the acetonitrile
solvate Ni(NCS) (4-(boc-amino)pyridine) ·CH CN, which shows
stretching vibration is observed at 2127 cm for 2 and at
À 1
2092 cm for 3 (Figure S4 and S5). Especially for 2 this value is
in the range expected for μ-1,3-bridging anionic ligands, but it
is well known that the CN stretching vibration is shifted to
higher values if the metal cations are additionally coordinated
by O-donor coligands. Therefore, these compounds should
consist of discrete octahedral complexes, in which the Ni
cations are coordinated by two terminal N-bonded anionic
ligands as well as two 3-bromopyridine ligands and two water
or methanol molecules.
2
2
3
[34]
an interesting structural behaviour. In the crystal structure of
this compound a very rare cis-cis-trans coordination is observed
in which the S atom of the thiocyanate anions and the N atoms
of the neutral coligands are in cis-position, whereas the
thiocyanate N atoms are in trans-position. The metal cations are
linked by the anionic ligands into corrugated chains that are
further connected into layers by intermolecular NÀ H···O hydro-
gen bonding. These layers are stacked in a way that channels
are formed, in which the acetonitrile solvate molecules are
located. The solvent can be removed in a topotactic reaction
If the reaction is performed in acetonitrile in a metal to
coligand ratio of 1:4 compound 1-I is obtained but lowering
the ratio to 1:2 leads to the formation of a new crystalline
phase that might contain additional acetonitrile as solvate
molecules. This is confirmed by elemental analysis, from which
a composition of (Ni(NCS) (3-bromopyridine) ·CH CN (4) can be
[45]
leading to a change from space group P2 /c to C2/c.
1
In the course of our systematic investigations on thiocya-
nate coordination compounds we became interested in Ni-
2
2
3
(
NCS) compounds with 3-bromopyridine as coligand, for which
assumed. For this compound the CN stretching vibration of the
2
À 1
only some structures with Cd, Zn and Cu are reported in the
thiocyanate anions is observed at 2113 cm and because in
[47–51]
Cambridge Structural Database.
Despite the formation of
this case only N-donor coligands are present this points to the
presence of μ-1,3-bridging thiocyanate anions (Figure S6). The
presence of acetonitrile as a solvent is indicated by a band at
several discrete complexes, we obtained two different chain
compounds, of which one contains the usual linear chains with
an all-trans coordination, whereas the second compound
consists of corrugated chains and a structure, which is very
similar to that of Ni(NCS) (4-(boc-amino)pyridine) ·CH CN. Here
À 1
2248 cm , which corresponds to the CN stretching vibration of
the acetonitrile molecules.
In further experiments, single crystals were obtained for all
five phases that were characterized by single crystal X-ray
diffraction, which, e.g., proves the formation of two polymor-
phic modifications for compound 1 (Table S1 and S2).
2
2
3
we report on our investigations.
Results and Discussion
Synthesis and Characterization
Crystal structures
Reaction of Ni(NCS) with 3-bromopyridine in different molar
Crystal structures of 1-I and 1-II
2
ratios in water, methanol or acetonitrile leads to the formation
of five different crystalline phases. If Ni(NCS) is reacted with 3-
Form 1-I crystallizes in the triclinic space group P-1 with Z=2
and its crystal structure contains two crystallographically
independent complexes, that are located on centres of
inversion (Figure S7). Form 1-II crystallizes in the tetragonal
2
bromopyridine in ratio 1:4 in water or methanol using very
short reaction times of a few minutes the same crystalline phase
is obtained (Figure S1). If the products are isolated after 2 d, a
further reaction product has formed, which in water and
methanol is identical. Elemental analysis reveals that for all of
space group I4 /acd with Z=8 and contains only one crystallo-
1
graphically independent Ni cation that is located on the 4-fold
screw inversion axis (Figure S7). In both forms, the Ni cations
them the chemical composition is identical (Ni(NCS) (3-bromo-
2
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are octahedrally coordinated by two terminal N-bonded
In the crystal structure of both compounds the discrete
1
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thiocyanate anions and four 3-bromopyridine ligands (Figure 1:
left and Figure S7). Bond lengths are comparable in all
complexes and from the bond lengths and angles it is obvious
that all octahedra are slightly distorted (Table S3 and S4). This is
in agreement with calculations of the octahedral angle variance
which leads to values of 10.3190 (Ni1) respectively 3.5062 (Ni2)
for 1-I and of 2.5842 for 1-II. The value of the mean octahedral
quadratic elongation amounts to 1.0050 (Ni1) respectively
complexes are linked by intermolecular OÀ H···S hydrogen
bonding between the water, respectively methanol OÀ H H
atoms and the thiocyanate S atoms (Table S9 and S10 and
Figure S10 and S11). In compound 3 additional CÀ H···N hydro-
gen bonding is present but from the H···N distances and the
CÀ H···N angles it is obvious that these correspond to a very
weak interaction (Table S10). For compounds 1-I, 1-II, 2 and 3
the calculated X-ray powder patterns were compared with the
experimental patterns, which proves that in all cases pure
samples have been obtained (Figure S12–S15).
[52]
1
.0025 (Ni2) for 1-I and 1.0016 for 1-II.
In the crystal structure of 1-I the discrete complexes are
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
linked by intermolecular CÀ H···S hydrogen bonding into a 3D
network (Table S5 and Figure S8). There are many additional
CÀ H···N hydrogen bonds but from the H···S distances and the
CÀ H···N angles it is obvious that these hydrogen bonds
correspond to only weak interactions (Table S5). In the crystal
structure of 1-II a completely different arrangement of the
discrete complexes is observed (Figure S8). In this form, strong
intermolecular CÀ H···S hydrogen bonding is observed that also
connects the complexes into a 3D network (Table S6 and
Figure S8) but two of such networks interpenetrate to form a
dense structure.
Crystal structure of 4
Compound 4 crystallizes in the monoclinic space group C2/c
with 4 formula units in the unit cell. The asymmetric unit
consists of one Ni cation that is located on the 2-fold rotation
axis as well as one thiocyanate anion, one 3-bromopyridine
ligand and one acetonitrile molecule in general positions
(Figure S16). The acetonitrile solvate molecule is disordered
around a centre of inversion and therefore was refined with
only half occupation. If the structure is refined in space groups
of lower symmetry the disorder still remains.
In the crystal structure of 4 the Ni cations are octahedrally
coordinated by two N- and two S-bonding thiocyanate anions
and two 3-bromopyridine ligands, as already indicated from the
IR spectroscopic measurements. The Ni cations show a cis-cis-
trans coordination with the thiocyanate S and the 3-bromopyr-
idine N atoms in cis position, whereas the thiocyanate N atoms
are trans to each other. As mentioned in the introduction, in
most chain compounds an all-trans coordination is observed,
whereas compounds with this kind of cis-cis-trans coordination
Crystal structures of 2and 3
Compounds 2 and 3 crystallize in the monoclinic space groups
P2 /c (2) and C2/c (3) with Z=2 respectively 4. As expected
1
from the TG measurements, elemental analysis and IR spectro-
scopy both compounds consist of discrete solvato complexes,
in which the Ni cations are coordinated by two terminal N-
bonded thiocyanate anions, two 3-bromopyridine ligands and
two water, respectively methanol molecules (Figure 1 and
Figure S9). In both complexes, the bond lengths and angles
correspond to literature values (Table S7 and S8). The Ni
octahedra are slightly distorted which is obvious from the
octahedral angle variance value of 1.4126 for 2 and of 3.9537
for 3 as well as from the mean octahedral quadratic elongation
are rare. This is observed in Ni(NCS) (4-(Boc-amino)
2
[38]
[
45]
pyridine) ·MeCN, Ni(NCS) (4-benzylpyridine) , Ni(NCS) (1-(2-
2
2
2
2
[53]
aminoethyl)pyrrolidine),
and in Ni(NCS) (2-aminopyridine)
2
[
54]
·Et O.
2
2
The NiÀ N and NiÀ S bond lengths are comparable to those
[52]
of 1.0013 for 2 and of 1.0017 for 3.
found in similar compounds and from the distances and angles
it is obvious that the octahedra are slightly distorted
(
Table S11). This is also confirmed by the value for the mean
octahedral quadratic of 1.0166 and the octahedral angle
variance of 9.1914 calculated using the method given by
[52]
Robinson et al. The Ni cations are linked by pairs of anionic
ligands into chains, which are corrugated because of the cis-cis-
trans coordination (Figure 2: top).
These chains proceed along the crystallographic c-axis and
are linked by weak intermolecular CÀ H···S, CÀ H···Br and CÀ H···N
hydrogen bonding (Table S12). The chains are arranged in a
way that channels are formed in which the acetonitrile solvate
molecules are embedded (Figure 2: bottom).
The crystal structure of compound 4 is very similar to that of
Ni(NCS) (4-(Boc-amino)pyridine) ·MeCN reported recently, in
2
2
which the Ni cations also show a cis-cis-trans coordination and are
linked into corrugated chains (Figure S17). Moreover, the arrange-
ment of chains and the opening of the channels is practically
identical to that in compound 4, which is also reflected in very
Figure 1. View of the discrete complexes in the crystal structure of
-II (left), 2 (mid) and 3 (right). Please note that the complexes in 1-
1
I look similar to that in 1-II. ORTEP plots of 1-I, 1-II, 2 and 3 can be
found in Figures S7 and S9.
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Thermoanalytical investigations for 1-I, 1-II, 2and 3
1
2
3
4
5
6
7
8
9
To investigate if 3-bromopyridine deficient compounds with
bridging thiocyanate anions can be prepared by ligand removal,
TG-DTA measurements were performed for compounds 1-I, 1-II, 2
and 3 at different heating rates (Figure S21-S24). Upon heating the
polymorphic modifications 1-I and 1-II two well resolved mass
steps are observed in the TG curves, which are accompanied with
endothermic events in the DTA curve (Figure 3 and Figure S21
and S22).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
For all mass loss steps of compounds 1-I and 1-II similar values
are found which are in well agreement with that calculated for the
removal of half of the 3-bromopyridine ligands (Δmcalc. =39.2%).
For the solvate complexes, similar observations were made
(
Figure 3). For these compounds the mass loss observed in the
first step is in agreement with the loss of two water (Δmcalc.
.8%), respectively methanol molecules (Δmcalc. =11.5%), whereas
=
6
in the second step the remaining 3-bromopyridine ligands are
removed (Δmcalc. =60.0% for 2 and 56.9% for 3). Therefore, these
results indicate that after the first TG step compounds with the
composition Ni(NCS) (3-bromopyridine) were obtained.
2
2
In further experiments, the residues obtained after each
mass loss were isolated and investigated by XRPD, which proves
that always the same crystalline phase (5) has formed (Fig-
ure S25).
Figure 2. View of a chain in the crystal structure of 4 (top) and
arrangement of the chains with view along the crystallographic c-
axis (bottom). An ORTEP plot can be found in Figure S14.
Synthesis and crystal structure of 5
In our previous synthetic experiments, no hint for the formation of
compound 5 in solution was found. Therefore, further synthetic
experiments using different solvents were performed and it was
similar values of the crystallographic b and c axes (Table S13). In
contrast to compound 4, Ni(NCS) (4-(Boc-amino)pyridine) ·MeCN
2
2
crystallizes in space group P2 /c with four formula units in the unit
discovered that the reaction of Ni(NCS) with 3-bromopyridine in
1
2
cell and fully ordered acetonitrile solvate molecules. However, the
acetonitrile solvate molecules can be removed in vacuum which
proceeds via a topotactic reaction and is accompanied with a
change of the Bravais type from primitive to C-centered. If about
half of the solvent molecules are removed the space group
changes to C2/c and in this case, the MeCN molecules are
disordered like it is the case in compound 4.
ratio 1:2 leads to a mixture of compound 1-I and 5 in n-butanol
Determination of the thermodynamic stability of 1-I and
1-II
To prove which of the two polymorphic modifications 1-I and
-II represents the thermodynamically stable form at room
1
temperature, solvent mediated conversion experiments were
performed in which a mixture of both forms in ratio 50:50 was
suspended in MeOH and EtOH with excess of solid. The
resulting suspension was stirred at room temperature and the
residue was investigated by XRPD after 1, 5 and 15 min, which
shows that within 5 min form 1-II has transformed into form 1-I,
which therefore is thermodynamically stable at room temper-
ature (Figure S19 and S20).
Figure 3. TG curves for compounds 1-I, 1-II, 2 and 3 measured with
4
°C/min.
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(
Figure S26). To suppress the formation of the discrete complex,
Investigations on the solvent removal of 4
1
2
3
4
5
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2
3
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2
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5
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0
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2
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4
5
6
7
8
9
0
1
2
3
4
5
6
7
the reactants were used in ratio 1:1 but in this case, a mixture of
5
obtained. In the following experiments the ratio between the
metal salt and the coligand was optimized and with a ratio of
1
The CN stretching vibration of the anionic ligands is observed at
2
anions are present.
As a crystalline powder was obtained in this solvent, we
also performed crystallization experiments in n-butanol and
obtained single crystals, which were characterized by single
crystal X-ray diffraction.
as the major phase and Ni(NCS)2 as the minor phase was
As mentioned above, the crystal structure of compound 4 is very
similar to that of Ni(NCS) (4-(Boc-amino)pyridine) ·MeCN. In the
2
2
latter compound, the solvent can be removed at room temper-
ature in vacuum via a topotactic reaction. The solvent removal can
easily be followed by X-ray powder diffraction, in which a
significant change in the intensity of some of the reflections is
observed. Therefore, we also investigated if the acetonitrile solvate
molecules can also be removed from compound 4 at room
temperature. If a sample of this compound that was stored
overnight under vacuum is investigated by XRPD no changes are
observed in the powder pattern, indicating that the solvate
molecules are still present (Figure 5). However, if compound 4 is
investigated by TG-DTA measurements two mass losses are
observed of which the first one of 7.7% and the second one of
59.5% are in perfect agreement with those calculated for the
removal of the acetonitrile solvate molecules (Δmcalc. =7.7%) in the
first and the 3-bromopyridine ligands (Δmcalc. =59.4%) in the
second step (Figure S30). The XRPD pattern of the residue formed
after the first mass loss is in very good agreement with that
calculated for compound 5. It was also checked whether an
anhydrate of 4 can be obtained at elevated temperatures and
therefore, compound 4 was annealed in vacuum much below the
decomposition temperature observed in the TG measurement.
XRPD measurements show that even this sample has been
transformed into the chain compound 5 (Figure 5) which indicates
that the acetonitrile solvate molecules are much stronger bound
in compound 4 than in Ni(NCS) (4-(Boc-amino)pyridine) ·MeCN.
:1.75 compound 5 can be obtained as a pure phase (Figure S26).
À 1
099 and 2127 cm , clearly indicating that bridging thiocyanate
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
Compound 5 crystallizes in the non-centrosymmetric space
group Pna2 with 12 formula units in the unit cell. The asymmetric
1
unit consists of three crystallographically independent Ni cations,
six thiocyanate anions and 12 3-bromopyridine ligands that are
located in general positions (Figure S27). In the crystal structure of
this compound, each of the three distinct Ni cations is coordinated
octahedrally by two N- and two S-bonding thiocyanate anions as
well as two 3-bromopyridine ligands that are located in the apical
position (Figure 4). The NiÀ N and NiÀ S bond lengths are in the
range of literature values and from the bond lengths and angles it
is obvious that the octahedra are slightly distorted. In contrast to
compound 4, the Ni cations show an all-trans coordination, which
corresponds to the usual arrangement in this class of compounds.
The Ni cations are linked by pairs of thiocyanate anions into linear
chains, which is in agreement with the IR spectrum, in which the
thiocyanate CN stretching vibration is observed at 2099 and
2
compared with that calculated from the single crystal data, it is
proven that compound 5 was obtained as a pure phase
2
2
À 1
127 cm (Figure S28). If the experimental XRPD pattern is
Magnetic measurements
(Figure S29).
Finally, it is noted that the structure refinement leads to
The magnetic properties of the chain compounds 4 and 5 were
investigated by DC magnetic measurements at 1 and 10 kOe in
a temperature range between 2.0 and 300 K (Figure 6). For both
compounds, the χT product increases initially with decreasing
relatively high R values and significant electron density peaks in
the difference map especially in the center of the Ni(NCS) Ni
units are observed. Much effort has been made to get a better
model and details can be found in the Experimental Section.
2
Figure 5. Calculated XRPD pattern for compound 4 (A) and 5 (E) as
well as experimental patterns of a sample of 4 (B) that was stored
for 1 d in vacuum at room temperature (C) and at 100°C (D).
Figure 4. View of a chain in the crystal structure of 5. An ORTEP
plot can be found in Figure S26.
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Journal of Inorganic and General Chemistry
ARTICLE
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Conclusions
1
2
3
4
5
6
7
8
9
In this contribution, several new compounds including polymor-
phic modifications based on Ni(NCS) and 3-bromopyridine were
2
reported. In most cases, simple discrete complexes were obtained
but in one compound a relatively rare cis-cis-trans coordination is
observed that leads to the formation of corrugated chains. If the
precursor complexes are heated, the coligands are emitted
stepwise, which in all cases leads to an intermediate compound
with the same ratio between Ni(NCS) and 3-bromopyridine as
2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
that of the corrugated chain compound. However, XRPD inves-
tigations revealed that a different crystalline phase has formed.
Based on these results further synthetic experiments were
performed in which the new crystalline phase was also obtained
from solution. Single crystal X-ray diffraction has proven that a
different isomer with an all-trans coordination has formed that
consists of linear chains. These results demonstrate the potential
of thermally induced ligand removal for the formation of new
crystalline phases that might easily be overlooked if the synthesis
is only performed in the liquid state. Even if in this case always the
same crystalline phase was obtained, there are several examples
reported in literature, where this approach can lead to metastable
phases that cannot be obtained from the liquid phase.
Figure 6. Temperature dependence of the magnetic susceptibility
measured at 10 kOe for 4 (triangles) and 5 (circles). Lines were
fitted (see text). Inset: Low temperature susceptibility measured at
1 kOe.
temperature, which is indicative for dominating ferromagnetic
interactions within the chains, in agreement with observations
[38]
made for similar Ni(NCS) chain compounds (Figure S31). For Experimental Section
2
compound 4 a maximum of χ(T) is observed at T=3.5 K that
points to an antiferromagnetic ordering. In contrast, for
compound 5 no magnetic ordering is observed down to 2 K.
The magnetic data were analyzed in the frame of the
isotropic spin S=1 chain model with Heisenberg exchange
interaction:
General
Ba(SCN) ·3H O was purchased from Alfa Aesar. NiSO ·6H O and 3-
2 2 4 2
bromopyridine were purchased from Merck. Ni(NCS) was synthe-
2
sized by the reaction of equimolar amounts of NiSO ·6H O and
4
2
Ba(NCS) ·3H O in water. The resulting white precipitate of BaSO
2
2
4
was filtered off and the solvent was removed from the filtrate under
reduced pressure. The purity was checked by XRPD and TG-DTA. All
solvents were used without further purification.
X
X
~
~
z
n
H^ ¼ À J
S � S
S
n
nþ1
B
þ gm Hz
n
n
The J and g values were determined by fitting the
experimental data above 10 K for 4 and above 25 K for 5 using
Synthesis of Ni(NCS) (3-bromopyridine) (1-I)
2 4
Ni(NCS)2 (1.0 mmol, 174.9 mg) was dissolved in MeOH and 3-
bromopyridine (4.0 mmol, 390 μL) was added. The mixture was stirred
for five days, the precipitate was filtered off and dried in air.
Compound 1-I consists of a blue crystalline powder. Elemental analysis
for C H Br N NiS (806.8472 g/mol): C 32.75, H 2.00, N 10.42, S 7.95.
[55]
the approximation formula proposed in. The obtained values
are J=4.35(3) K, g=2.24(1) for 4, and J=2.3(1) K, g=2.28(1) for
5
. The J value for 5 is the smallest in comparison with twelve
[38]
Ni(NCS) L compounds with chain structures reported in ref..
22 16
4
6
2
2
2
Found: C 32.39, H 2.05, N 10.37, S 7.98. For the preparation of single
crystals Ni(NCS) (2.0 mmol, 349.7 mg) and 3-bromopyridine
8.0 mmol, 780.2 μl) were stirred in 2.0 mL methanol for two days. The
The small value of J is one of reasons why the fitted curve starts
to deviate from the experimental points below 25 K, where the
experimental χT has a smooth maximum around 18 K, and
further decreases at lower T. This behavior is an effect of zero-
field splitting of the Ni(II) cations, which cannot be easily
incorporated in the solution of the Hamiltonian given above. A
similar smooth χT(T) maximum was observed for other linear
Ni(NCS) chains with an all-trans N S coordination of the Ni(II)
2
(
precipitate was filtered off and the filtrate was stored at room
temperature leading to suitable crystals within 3 d.
Synthesis of Ni(NCS) (3-bromopyridine) (1-II)
2 4
For the synthesis of compound 1-II the same amounts of reactants
were used as for 1-I, but the precipitate was stirred for only ten
minutes, filtered off and dried in air. A purple crystalline powder was
2
4 2
cation, particularly for compounds with 4-dimethyaminopyri-
[38]
dine and 4-ethylpyridine as ligand. Therefore, this maximum
seems to be due to the nonmagnetic ground state of Ni(II) in
zfs, rather than an effect of antiferromagnetic interactions.
obtained. Elemental analysis for C22
H16Br N NiS (806.8472 g/mol): C
4 6 2
3
2.75, H 2.00, N 10.42, S 7.95. Found: C 32.65, H 2.14, N 10.32, S 7.52.
Single crystals of this compound were obtained after a mixture of
Ni(NCS)2 (0.25 mmol, 43.7 mg) and 3-Bromopyridine (2.5 mmol,
2
43.8 μl) was stored in a closed culture tube in 1.5 mL demin. water at
°
120 C for 3 d.
Z. Anorg. Allg. Chem. 2021, 552–559
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Journal of Inorganic and General Chemistry
ARTICLE
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Synthesis of Ni(NCS) (3-bromopyridine) (H O) (2)
merohedral twin but no improvement was obtained. We also assumed
2
2
2
2
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
monoclinic symmetry and performed twin refinement in all three
possible settings but no changes were detected. In this case, the BASF
parameter refined to 0.5, which clearly indicates that orthorhombic
symmetry is present. Therefore, this structure was refined in the
Compound 2 was obtained by the reaction of Ni(NCS)
74.9 mg) which was dissolved in 1.5 mL demin. water and 3-
(1.0 mmol,
2
1
bromopyridine (1.0 mmol, 98 μl). After three days the residue was
filtered off and dried in air. A lightblue crystalline powder was
obtained. Elemental analysis for C H Br N NiO S (526.8829 g/mol):
orthorhombic space group Pna2 as a racemic twin. It is noted that
1
12
12
2
4
2 2
much of intensity was observed between the reflections along the
crystallographic b-axis, which corresponds to the direction of the
chains (Figure S32). We also measured a second crystal at 100 K using
a Rigaku Synergy diffractometer but no improvement was obtained.
From the experimental data, the reciprocal space was reconstructed,
which clearly shows that much of diffuse scattering is observed along
the b-axis (Figure S33). It is noted that there are no hints for the
formation of an incommensurate structure. However, we are
absolutely sure that our structure model is correct.
C 27.36, H 2.30, N 10.63, S 12.17. Found: C 27.14, H 2.27, N 10.54, S
12.16. Single crystals were obtained by storing a mixture of Ni(NCS)2
(
1.0 mmol, 174.9 mg) and 3-bromopyridine (0.25 mmol, 24.4 μl) in a
closed culture tube in 1.5 mL demin. water at 120°C for 3 d.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
Synthesis of Ni(NCS) (3-bromopyridine) (CH OH) (3)
2
2
3
2
After stirring a mixture of Ni(NCS)2 (2.0 mmol, 349.7 mg) and 3-
bromopyridine (2.0 mmol, 195 μl) in 4.0 mL methanol for four days
the residue was filtered off and a lightblue crystalline powder was
obtained. Elemental analysis for C H Br N NiO S (554.9366 g/mol): C
Selected crystal data and details of the structure refinements are given
in Table S1 and S2.
14
16
2
4
2 2
30.30, H 2.91, N 10.10, S 11.56. Found: C 29.91, H 2.82, N 9.93, S 11.80.
For the preparation of single crystals Ni(NCS) (0.5 mmol, 87.4 mg) and
CCDC 2052580 (1-I), CCDC 2052581 (1-I), CCDC 2052582 (2), CCDC
2052584 (3) CCDC 2052583 (4) and CCDC 2052585 (5) contain the
supplementary crystallographic data for this paper. These data can
be obtained free charge from the Cambridge Crystallographic Data
Centre via http://www.ccdc.cam.ac.uk/data_request/cif.
2
3
-bromopyridine (0.5 mmol, 48.8 μl) were stirred in 1.0 mL methanol
for two days. The filtrate was stored at room temperature and single
crystals were obtained within 4 d.
Synthesis of [Ni(NCS) (3-bromopyridine) ] ·CH CN (4)
Other physical measurements
2
2 n
3
A greenblue crystalline powder was obtained after stirring Ni(NCS)2
(1.0 mmol, 174.9 mg) and 3-bromopyridine (2.0 mmol, 195 μl) in
2.0 mL acetonitrile for four days. The residue was filtered off and
dried in air. The filtrate was stored at room temperature and single
crystals were obtained after several weeks. Elemental analysis for
C H Br N NiS (531.9048 g/mol): C 31.61, H 2.08, N 13.17, S 12.06.
IR spectra were recorded at RT on a Bruker Vertex70 FT-IR
spectrometer using a broadband spectral range extension VERTEX FM
for full mid and far IR.
For TG-DTA measurements either a STA-PT1000 or a STA-PT1600
thermobalance from Linseis were used. Measurements were per-
1
4
11
2
5
2
formed in Al O crucibles and under a dynamic nitrogen atmosphere.
2 3
Found: C 31.47, H 2.20, N 13.06, S 13.29.
The instruments were calibrated using standard referencing materials
and corrected for buoyancy.
Synthesis of [Ni(NCS) (3-bromopyridine) ] (5)
2
2 n
The XRPD measurements for the characterization of all samples were
performed with a Stoe Transmission Powder Diffraction System (STADI
P) with Cu-Kα1 radiation and a Dectris Mythen 1 K detector with a
Johann-type-Ge(111) monochromator from STOE & CIE.
A green crystalline powder was obtained by stirring Ni(NCS)2
(0.5 mmol, 87.4 mg) and 3-bromopyridine (0.875 mmol, 86 μl) in
1
3
.0 mL n-butanol for 7 d. The filtered off residue was washed with
.0 mL n-heptane and dried in air. Elemental analysis for
The magnetic measurements were performed with a PPMS from
Quantum Design that is equipped with a 9 T magnet. The data
were corrected for the diamagnetic contributions.
C H Br N NiS (490.8523 g/mol): C 29.36, H 1.64, N 11.41, S 13.07.
12
8
2
4
2
Found: C 29.44, H 1.82, N 11.44, S 12.39. Single crystals were prepared
by heating Ni(NCS)2 (0.2 mmol, 34.9 mg) and 3-bromopyridine
(0.2 mmol, 19.5 μl) in 0.3 mL n-butanol up to 90°C. The solution was
cooled to 60°C and annealed at this temperature for two days.
Acknowledgements
Single crystal structure analysis
This project was supported by the Deutsche Forschungsge-
meinschaft (Project No. NA 720/5-2) and the State of Schleswig-
Holstein. We thank Prof. Dr. Wolfgang Bensch for access to his
experimental facilities. Open access funding enabled and
organized by Projekt DEAL.
Data collection was performed using an Imaging Plate Diffraction
System (IPDS-2) from Stoe&Cie with MoÀ Kα radiation. A numerical
absorption correction was performed using X-Red and X-Shape of
[56]
the software package X-Area. The structures were solved with
[57]
2
SHELXT and structure refinement was performed against F using
[58]
SHELXL-2018. The CÀ H hydrogen atoms were positioned with
idealized geometry (methyl H atoms allowed to rotate but not to
tip) and were refined isotropic with Uiso (H)=1.2 Ueq (C) (1.5 for
methyl H atoms) using a riding model. The OÀ H hydrogen atoms
were located in difference map, their bond lengths were set to
ideal values and finally, they were refined isotropically with Uiso
Keywords: coordination polymer · nickel thiocyanate · crystal
structure · isomerism · polymorphism · solid state synthesis
(H)=1.5 Ueq (O) using a riding model.
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Z. Anorg. Allg. Chem. 2021, 552–559
www.zaac.wiley-vch.de
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published by Wiley-VCH GmbH.

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
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