New isomeric Ni(NCS)2 coordination compounds: Crystal structures, magnetic properties as well as: Ex situ and in situ investigations on their synthesis and transition behaviour

Article abstract of DOI:10.1039/d0ce00181c

The reaction of Ni(NCS)₂ with 3-ethylpyridine in water leads to the formation of two known modifications of Ni(NCS)₂(3-ethylpyridine)₄ (1-I and 1-II) as well as of Ni(NCS)₂(3-ethylpyridine)₂(H₂O)₂ (2) that consist of discrete complexes. If the synthesis is performed in ethyl acetate, the new compound [Ni(NCS)₂(3-ethylpyridine)₂]_n (3-lc) formed that comprises linear and corrugated Ni(NCS)₂ chains in one crystal. By changing the solvent to dichloromethane, a solvate of compound 3 is obtained that consists exclusively of corrugated chains (3c-CH₂Cl₂). 3c-CH₂Cl₂ is unstable and transforms immediately into 3-lc. Upon heating the precursor complexes 1-I, 1-II and 2, the 3-ethylpyridine ligands are removed in two steps leading to a mixture of 3-lc and an additional isomer of 3 (3-l) in the first step that decomposes upon further heating into a compound with the composition [Ni(NCS)₂(3-ethylpyridine)]_n (4). Ex and in situ XRPD measurements reveal that a mixture of two modifications (4-I and 4-II) is always formed, preventing their structure determination by XRPD. Time dependent investigations in solution prove that 3-l is formed under kinetic control and transforms into 3-lc within several hours that is thermodynamically stable at roomerature. Structure analysis of 3-l shows that in contrast to 3-lc and 3c-CH₂Cl₂ this isomer consists exclusively of linear Ni(NCS)₂ chains. Magnetic measurements of the new chain compounds 3-l and 3-lc shows χT values that are typical for Ni(ii) cations with S = 1. For 3-l the exchange constant was determined by fitting of the magnetic data leading to a value that is similar to that of [Ni(NSC)₂(2,2′-bipyridine)₂]_n.

Full text of DOI:10.1039/d0ce00181c

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DOI: 10.1039/D0CE00181C
ARTICLE
New isomeric Ni(NCS) coordination compounds: crystal
2
structures, magnetic properties as well as ex situ and in situ
investigations on their synthesis and transition behaviour
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
c,d
b
Carsten Wellm, Tristan Neumann, Magdalena Ceglarska, Gianpiero Gallo, Michał Rams, Robert
c
a*
DOI: 10.1039/x0xx00000x
E. Dinnebier and Christian Näther
The reaction of Ni(NCS)
ethylpyridine) (1-I and 1-II) as well as of Ni(NCS)
synthesis is performed in ethyl acetate, the new compound Ni(NCS)
and corrugated Ni(NCS) chains in one crystal. By changing the solvent to dichloromethane, a solvate of compound 3 is
obtained that consists exclusively of corrugated chains (3c-CH Cl ). 3c-CH Cl is unstable and transforms immediately into 3-
2
with 3-ethylpyridine in water leads to the formation of two known modifications of Ni(NCS)
(3-ethylpyridine) (H O) (2) that consist of discrete complexes. If the
(3-ethylpyridine) (3-lc) formed that comprises linear
2
(3-
4
2
2
2
2
2
2 n
]
2
2
2
2
2
lc. Upon heating the precursor complexes 1-I ,1-II and 2, the 3-ethylpyridine ligands are removed in two steps leading to a
mixture of 3-lc and an additional isomer of 3 (3-l) in the first step that decomposes upon further heating into a compound
2 n
with the composition [Ni(NCS) (3-ethylpyridine)] (4). Ex and in situ XRPD measurements reveal that a mixture of two
modifications (4-I and 4-II) is always formed, preventing their structure determination by XRPD. Time dependent
investigations in solution prove that 3-l is formed under kinetic control and transforms into 3-lc within several hours that is
thermodynamically stable at room-temperature. Structure analysis of 3-l shows that in contrast to 3-lc and 3c-CH
isomer consists exclusively of linear Ni(NCS) chains. Magnetic measurements of the new chain compounds 3-l and 3-lc
shows χT values that are typical for Ni(II) cations with S = 1. For 3-l the exchange constant was determined by fitting of the
magnetic data leading to a value that is similar to that of [Ni(NSC) (2,2’-bipyridine)
2 2
Cl this
2
2
2 n
] .
by, e.g. mixed crystal formation.31, 35-43 In this context, we have
reported on the crystal structures and magnetic properties of many
Introduction
coordination polymers with the composition [Ni(NCS)
2
(L)
4
] and
The development of strategies for the synthesis of coordination
compounds with predefined structures and desired physical
properties is still an important goal in modern coordination
4
4-47
[
2 2 n
Ni(NCS) (L) ] .
. In the latter, the thiocyanate N and S atoms, as
well as the N atoms of the coligands are mostly each in trans-
position, which leads to the formation of linear chains and this is
usually found for thiocyanate coordination polymers with most 3d
1
-9
chemistry. Even, if several convincing strategies are reported, in
some cases the concept of crystal engineering is stretched to the
4
6
cations (Figure 1). Linear chains are also observed for the
compound with 4-benzoylpyridine but in these cases, a cis-cis-trans
coordination is observed, in which the apical coligands are still trans
9
-19
limit, e.g., when a different polymorph or isomer was discovered.
This is frequently observed for coordination compounds based on
thiocyanate anions that can show a large number of different
coordination modes, which can lead to structures of different
4
7
to each other, whereas the thiocyanate N and S atoms are cis.
There are also many other cis-cis-trans isomers, in which the organic
coligands are in cis-position and the thiocyanate N or S atoms are cis
or trans to each other, which in this case leads to the formation of
2
0-33
dimensionality.
We became interested in this anionic ligand
because it can mediate reasonable magnetic exchange, which allows
studying structure property relationships.
nature of the cation and the connectivity of the ligand, a variety of
magnetic properties can be observed that can further be modified
2
9-31, 34
Depending on the
2
6
corrugated chains. In contrast, Ni(II) thiocyanate compounds with
4
8
layered networks are rare.
The reasons why for some compounds linear, for some other
corrugated chains are observed remain unclear as all ligands consist
of pyridine derivatives with small variations of the substituents in the
a. Institute of Inorganic Chemistry, Kiel University, Max-Eyth-Straße 2, 24118 Kiel,
Germany
4
-position. For the compound with 4-chloropyridine as coligand, two
b.
isomers were obtained, with one of them containing linear, the other
Institute of Physics, Jagiellonian University, Łojasiewicza 11, 30348 Kraków,
Poland.
47
corrugated chains. The compound with the linear chains can only
c.
Max-Planck-Institute for Solid State Research, Heisenbergstraße 1, 70569
be prepared by thermal decomposition of a 4-chloropyridine-rich
precursor, whereas the corrugated chains are exclusively obtained
from solution, indicating that the former structure is predefined in
the precursor.
Stuttgart, Germany
Department of Chemistry and Biology “A. Zambelli”, University of Salerno, Via
d.
Giovanni Paolo II, 132, 84084 Fisciano (SA), Italy
†
Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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Concerning the magnetic properties of these compounds, significant compounds 3-l and 3-lc were investigated by magnetViciewanAdrticslepeOcnilifniec
differences are found in the magnetic exchange that depends heat measurements and for 3-l the magneticDeOxIc:h10a.n10g3e9c/oDn0sCtEa0n0t1w81aCs
especially on the chain geometry, but a detailed analysis shows that determined which is not possible for 3-lc.
there is no simple relationship between the exchange constant and
selected structural parameters like, bond lengths and angles or the
interplanar angles between the Ni(NCS) Ni units.
2
4
7
Results
Synthetic investigations. The reaction of Ni(NCS)
2
with 3-
ethylpyridine in water leads to the formation of the literature known
modification of Ni(NCS) (3-ethylpyridine) (1-I) that consists of
2
4
discrete complexes (Figure S1). IR and Raman spectroscopic
investigations and comparison of its X-ray powder diffraction (XRPD)
pattern with that calculated from single crystal data reveal that a
pure phase was obtained (Figure S2 and S3). If this experiment is
repeated and the precipitate that forms is immediately filtered off,
the second known modification 1-II of this compound is obtained
pure, obviously under kinetic control (Figure S4 and S5). To obtain
new 3-ethylpyridine deficient compounds, the amount of coligand
was reduced leading to the formation of a new crystalline phase with
the composition [Ni(NCS)
2 2 2 2
(3-ethylpyridine) (H O) ] (2). Even though
for this compound the CN stretching vibration of the anionic ligand is
-1
-1
observed at 2113 cm in the IR and at 2118 cm in the Raman
spectrum, no definite conclusion on the coordination of the anions
can be made (Figure S6). However, single crystals of this new phase
can easily be obtained and crystal structure analysis shows that a
discrete octahedral aqua complex has formed. It is noted that
coordination of water to such thiocyanate complexes shifts the CN
stretching vibration to higher wavenumbers and in such cases, one
cannot distinguish between terminal and bridging thiocyanate
anions. Comparison of the experimental XRPD pattern with that
calculated prove that a pure phase was obtained (Figure S7)
To avoid the coordination of water, reactions were performed in
different solvents and from ethyl acetate a new crystalline phase was
obtained for which elemental analysis suggested composition of
Figure 1. Ni coordination and chain structures in different 1D Ni(NCS)
polymers retrieved from literature.
2
coordination
[
Ni(NCS)
2
(3-ethylpyridine)
2
] (3-lc). The CN stretching vibration is
-1
-1
observed at 2103 cm and at 2105 cm in the IR and the Raman
spectrum, which because water is absent indicates that in this
crystalline phase the Ni(II) cations are linked by the anionic ligands
(Figure S8). Single crystals for 3-lc were obtained and characterized
by single crystal X-ray diffraction (SC-XRD), which reveals that in this
compound the cations are linked by pairs of anionic ligands into
chains and that both, linear and corrugated chains are present in the
same crystal which was never observed before. A comparison of the
experimental XRPD pattern with that calculated proves that a pure
phase has been obtained (Figure S9). During our attempts to prepare
single crystals of 3-lc, crystals of an additional phase were obtained
However, in the course of our investigations on the influence of the
coligand on the magnetic properties, we became interested in 3-
ethylpyridine as coligand, for which some thiocyanate coordination
4
9, 50
compounds with Zn(II), Cd(II) and Cu(I) are already reported.
With Ni, only two polymorphs of the discrete complex Ni(NCS)
ethylpyridine) are known (1-I and 1-II) in which the Ni(II) cations
are octahedrally coordinated by two terminal N-bonded thiocyanate
2
(3-
4
5
1
anions and four 3-ethylpyridine ligands (Figure S1). Compounds in
which the metal cations are linked into chains by pairs of µ-1,3-
bridiging thiocyanate anions are unknown. During these
investigations, we obtained many new compounds, including one
2 2
from dichloromethane (3c-CH Cl ), which also consists of chains but
2 2
that comprises corrugated chains (3c-CH Cl ) and one that consists
which contains additional dichloromethane solvate molecules. If this
compound is immediately measured it is shown that the CN
stretching vibrations of the anionic ligands is shifted to slightly higher
values compared to that in 3-lc (Figure S10). Single crystal structure
analysis proves that in contrast to 3-lc, this compound contains only
corrugated chains (see below) and a comparison of its experimental
pattern with that calculated proves that a pure phase has been
obtained (Figure S11). However, 3c-CH Cl is unstable at room
2 2
temperature and decomposes rapidly into 3-lc because of the loss of
solvate molecules (Figure S12).
of the common linear chains with an all-trans-coordination (3-l). In
solution 3-l transforms in a new crystalline phase that was shown to
contain both, linear and corrugated chains (3-lc) within one crystal,
which to our knowledge is unprecedented in literature. Furthermore,
it indicates that different species might be present in solution. We
also discovered one new aqua complex (2) that upon heating
transforms into a mixture of two new modifications with the
composition [Ni(NCS)
of 3-l and 3-lc as intermediates like it is the case for the precursor
complexes [Ni(NCS) (3-ethylpyridine) (1). The two chain
2 n
(3-ethylpyridine)] (4-I and 4-II) via a mixture
2
4
]
2
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Thermoanalytical investigations. To check if additional 3- obtained (Figure S18-S21). All these experiments indVicieawteArttichleaOt ntlhinee
ethylpyridine deficient phases are available by thermal ligand formation of these crystalline phases dependDsOoI:n10t.h10e3k9i/nDe0tCicEs0o0f18th1Ce
removal, measurements using thermogravimetry and differential reaction and that 3l might form under kinetic control.
thermoanalysis (TG-DTA) were performed for 1-I, 1-II and 2. Upon However, to identify the products that have formed after the second
heating 1-I to 500°C with 1°C/min. four mass losses are observed mass loss, additional TG measurements for 1-I, 1-II and 2 were
that are each accompanied with endothermic events in the DTA performed and the respective residues were investigated by IR
curve. From the DTG curve, it is obvious that all events are reasonably spectroscopy and XRPD (Figure S22 and S23). In all cases the powder
resolved (Figure 2: left). The experimental mass loss in the first step patterns of these samples are almost similar, but for 2 a poorly
is in excellent agreement with that calculated for the removal of two crystalline phase is obtained. All attempts to index these patterns
3
-ethylpyridine ligands (mcalc.: -34.4%), whereas the mass losses in failed, indicating that a mixture of compounds has formed. This is
the following steps suggest the removal of one coligand per step, further supported by the varying intensities of the residue reflections
which should lead to the formation of compounds with the that show a dependency on the nature of the precursor and the exact
composition
[Ni(NCS)
2
(3-ethylpyridine)
2
]
(3),
2
[Ni(NCS) (3- temperature where the intermediates were isolated (Figure S22).
ethylpyridine)]
n
(4) and Ni(NCS)
2
in the first, second and third TG The IR spectra of all intermediates are identical and point to bridging
step. Similar measurements for 1-II reveal the same behavior, anionic ligands (Figure S23).
indicating that the same intermediates will form (Figure S13).
For the aqua complex 2 also three mass losses are observed of which In situ X-ray powder diffraction. In the ex situ measurements, the
the first one is in good agreement with that calculated for the intermediates were always isolated at definite temperatures and
removal of the two water ligands (mcalc.: -8.5%). Upon further therefore, it is difficult to prove if one form of compound 3 or 4 is
heating two more steps occur each suggesting the emission of one 3- formed in the beginning and transforms into a different modification
ethylpyridine ligand (mcalc.: -25.2%; Figure 2: right), indicating that upon heating. Therefore, in situ XRPD measurements were
new intermediates will form that might be similar to that observed performed in open capillaries (Figure 3 and Figure S24). Upon heating
in the TG-DTA measurements of 1-I and 1-II.
form 1-I, starting at about 80°C reflections of a new crystalline phase
occurred. The temperature of this event corresponds roughly to that
observed in the TG-DTA measurements. Because at this temperature
the sample mass does not change, it indicates that an unknown
polymorph of compound 1 forms. It is noted that the same crystalline
phase is also observed in the HTK measurement of 1-II (Figure S24).
Unfortunately, the powder pattern cannot be indexed and therefore,
no structural information is available. However, the formation of
compound 3 starts at about 160°C and these powder patterns are
very similar to that obtained in the ex situ measurements, indicating
that a mixture of 3-l and 3-lc has formed (Figure S24). Upon further
heating, the transformation into compound 4 is observed and at
higher temperatures the remaining 3-ethylpyridine ligands are
2
removed completely leading to the formation of Ni(NCS) (Figure 3).
Figure 2. DTG, TG and DTA curve for 1-I (left) and 2 (right) measured with a heating rate
of 1°C/min. The mass losses in % and the peak temperature (T ) in °C are also given.
p
To identify the intermediates that have formed after each mass loss,
the residues formed after each step were investigated by IR and
XRPD. If their powder patterns are compared with that calculated for
3
-lc, it becomes obvious that this compound has formed together
with an additional crystalline phase (3-l) that is unknown (Figure
S14). Surprisingly, despite the fact that always mixtures of two
different crystalline compounds have formed, the value of the CN
stretching vibration of all three residues is always identical to that of
3
-lc, indicating that this value is identical for 3-l and 3-lc (Figure S15).
The amount of this phase depends on the heating rate and it was
found that with increasing heating rate the amount of 3-lc gets larger
Figure 3. HTK measurement of 1-I in an open capillary. The calculated powder pattern
of 1-I, 3-lc and Ni(NCS) are given in red. For a similar measurement of 1-II please see
(Figure S16 and S17). Therefore, we tried to prepare 3-l by thermal
2
annealing of 1-I and 1-II at 70 and 85°C. At 70°C the formation of figure S24.
compound 3 as a mixture starts after 72 h and is faster at 80°C but
even after longer annealing times always a mixture of 3-l and 3-lc is
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Even for compound 4 the powder pattern is very similar to that them being unsuccessful. However, if a saturated solution of
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DOI: 10.1039/D0CE00181C
2
observed in the ex situ measurements and there is no hint that one Ni(NCS) in water was prepared and overlaid with a solution of 3-
modification forms first and then transforms into a different form ethylpyridine in ethyl acetate, suitable crystals were obtained and
upon further heating. For form 1-II similar observations were made characterized by SC-XRD (see below and experimental section). If the
as for form 1-I.
XRPD pattern of 3-l prepared under kinetic control is compared with
that calculated from single crystal data it is proven that a pure phase
Investigations on the stability and formation of the different has been obtained (Figure S27). IR spectroscopy proves that the
forms in solution value of the CN stretching vibration is identical to that of 3-lc (Figure
In the thermoanalytical measurements always mixtures of S28).
different forms of compounds 3 and 4 were obtained. Therefore, the To investigate the stability of the two forms of compound 4 a mixture
thermodynamic stability of 3-l and 3-lc was investigated in solution of both modifications obtained by a TG measurement was stirred in
using a solvent mediated conversion (slurry) experiment. In this ethanol with an excess of solid and the products that formed were
experiment, a mixture of 3-l and 3-lc obtained from the TG identified by XRPD (Figure 5). From this experiment is obvious that
measurements was stirred with excess of solid in ethanol and the compound 4 directly transforms into 3-l and that the 3-ethylpyridine
products that formed after some time were investigated by XRPD richer compounds are more stable. There is no hint that the
measurements. These measurements clearly show that the reflections of one of the two forms of compound 4 disappear, first
reflection of 3-l disappears within 15 min. of stirring and proves that allowing to isolate it and all this might explain why none of the two
3
-lc represents the thermodynamically stable form at room- forms of compound 4 can be obtained from solution. It is also
temperature (Figure S25). In this context it is noted that the density mentioned that during the transformation of 4 into 3, Ni(NCS)2 will
determined by Pawley fits of powder pattern measured at room form, which explains that a small amount of this crystalline phase is
-3
temperature of 3-lc of 1.385 g/cm is significantly lower that of 3-l present in the residue (Figure 5).
-
3
(
1.419 g/cm ), which indicate that 3-l become thermodynamically
5
2
stable at lower temperatures.
However, it is noted that in the synthesis of 3-lc the reaction product
was isolated after three days, which means that it was performed
under thermodynamic control and thus, one cannot exclude that 3-l
can be obtained from solution under kinetic control. Therefore, the
direct synthesis of 3-l from solution was attempted in ethanol and
the products that formed after different reaction times were
investigated by XRPD. These experiments prove that the new phase
3
-l forms in the beginning under kinetic control and starts to
transform into 3-lc within a few hours (Figure 4). Similar results were
observed in ethyl acetate solution but in this case, the
transformation is much slower, which indicates that the synthesis of
the metastable form 3-l in ethyl acetate is of advantage (Figure S26).
Figure 5. XRPD patterns of the mixture of both modifications of 4 (A), that was stirred in
ethanol for 15 h (B), together with the calculated patterns for Ni(NCS) (C) and 3-l (D).
2
Please note that the transformation of 3-l into 3-lc on further stirring is not shown.
However, the XRPD measurements of the residues obtained from the
TG experiment show that always a mixture of both forms of
compound 4 is obtained but it should be kept in mind that in all cases
they were prepared starting from 1-I, 1-II or 2 as precursors, which
automatically leads to the formation of a mixture of both isomers of
3
3
. In this context, the question arose if this is different whether pure
-l or 3-lc are thermally decomposed. This because it is conceivable
that the structure of one of the forms of 3 can lead exclusively to one
definite form of 4. Therefore, additional TG measurements and in
situ temperature dependent XRPD measurements of pure 3-l and 3-
lc prepared from solution were performed (Figure S29-S32). If the
experimental powder patterns are compared with those obtained by
in situ XRPD measurements of 1-I and 1-II or by ex situ XRPD of the
residues obtained by thermogravimetric measurements, it is obvious
that the ratio between the two forms of 4 is very different,
dependent on the fact whether 3-l or 3-lc is investigated (Figure S33).
This indicates some relationship between 3-l and 3-lc and each one
Figure 4. XRPD pattern of samples isolated at different reaction times if Ni(NCS)
reacted with two equivalents of 3-ethylpyridine in ethanol.
2
is
To obtain structural information on the metastable form 3-l a variety
of crystallization experiments were performed with nearly all of
4
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of the modifications of 4. Unfortunately, it is still a mixture of two the octahedral is slightly distorted (Table S2). This isVieawlsAortioclbe vOinoliunes
forms, which might be the reason why indexing of the powder from the value for the quadratic elongation oDfO1I.:01001.100a39n/dDo0cCtEa0h0e1d8r1aCl
patterns was unsuccessful. Therefore, the structures of these angle variance of 2.3556, calculated according to the method
5
4
modifications remain unknown.
suggested by Robinson. In the crystal structure the discrete
Finally, the transformation of 3c-CH
2
Cl
2
and 3-l into 3-lc is complexes are linked by intermolecular O-HS hydrogen bonding
interesting from a structural point of view, because formally half of between each of the O-H H atoms and the thiocyanate sulfur atoms
the corrugated chains observed in 3c-CH Cl must transform into into layers that are located in the b/c-plane (Figure S37).
2
2
linear chains as observed in 3-lc and half of the linear chains in 3-l
have to transform into corrugated chains in 3-lc. For 3-l this process
should proceed via dissolution and nucleation of a new phase and
will end in the formation of the compound that is thermodynamically
stable at room temperature (3-lc).
However, concerning the transformation of 3l into 3-lc it might be
the case that different species are present in solution. Regardless, if
compounds with the composition [Ni(NCS)
solvate complexes with the composition [Ni(NCS)
ethylpyridine) (solvents) ] might be present, the position of the
2
(3-ethylpyridine)
4
] or
2
(3-
2
2
thiocyanate anions should change from cis to trans, because in 3-l,
all Ni centers show a cis-cis trans coordination, whereas in 3-lc, both,
a cis-cis-trans and an all trans coordination is observed. Therefore,
we tried to measure IR and Raman spectra of saturated solutions of
Figure 6. Crystal structure of 2 with a view of the Ni coordination. For an ORTEP plot of
see Figure S37.
2
1
-I, 3-l and 3-lc in ethyl acetate and ethanol to check, if several
signals for the CN stretching vibrations are observed (Figure S34 and
S35). For a trans configuration one signal in the IR and the Raman
spectra are expected, whereas for cis all vibrations might be
observed in the IR and Raman. Unfortunately, the intensities of the
vibrations are too low, obviously because of the low solubility of the
compounds, but in ethanol and ethyl acetate some bands can be
observed, which are at the detection limit of these methods.
However, for each compound only one signal is observed in the IR
and Raman spectra, which indicate that only a species with a trans
configuration is present. This is also supported by the fact that for
compound 1-I the vibrations are observed at different wavenumbers
in the IR and Raman with lower values in the IR (Figure S34 and S35).
This is expected because the asymmetric stretching vibration can
only be observed in the IR, whereas the symmetric CN stretching
vibration is observable in the Raman and should occur at higher
wavenumbers. For the other compounds, the CN stretch in the IR
cannot be detected. It is also noted that in ethanol different values
are observed for 1-I and 3-l, respectively 3-lc and that for the latter
two compounds the same value is observed. This means that in the
solution of the chain compounds the same species is present, which
is different from that in the solution of 1-I. In any case, there is no
hint for a compound with cis thiocyanate anions because every two
vibrations would be expected in the IR and Raman.
The isomeric chain compounds 3-l and 3-lc crystallize triclinic in
space group P-1 with Z = 2, respectively 4, whereas the solvate 3c-
CH
Table S1). In all of these compounds, the Ni cations are six-fold
coordinated by two N and two S-bonding thiocyanate anions and two
-ethylpyridine coligands and are linked into chains by pairs of µ-1,3-
2 2
Cl crystallizes in the monoclinic space group C2/c with Z = 2
(
3
bridging thiocyanate anions (Figure 1 and Figure S38-S40). Bond
lengths and angles are comparable in all three compounds but show
that the octahedra are slightly distorted (Table S4-S6). This is also
obvious from the mean quadratic elongation and the octahedral
angle variance for 3-I (1.0208 and 7.0526), 3-lc Ni1: 1.0195 and
1
3.9291; Ni2: 1.0191 and 3.3557; Ni3: 1.02 and 3.7623) and 3-CH
2 2
Cl
(1.02 and 14.2716 and 2.3556). However, differences are found in
the actual Ni coordination. In compound 3-l, the thiocyanate N and S
atoms, as well as the pyridine N atom, are always in trans-position,
which leads to the formation of linear chains with only one
crystallographically independent Ni cation in a general position
5
3
(Figure 7: A).
In compound 3-lc both, linear and corrugated chains are present,
which was never observed before in this class of compounds. The
asymmetric unit consists of three crystallographically independent Ni
cations. Ni2 and Ni3 are located on centers of inversion and show an
all-trans coordination, leading to the formation of linear chains as
already observed in compound 3-l (Figure 7: B and C). Differences are
found in the orientation of the apical pyridine coligands, which are
staggered in 3-l (Figure 8: top). In compound 3-lc these ligands are
eclipsed with the pyridine ring planes parallel (Ni2) or perpendicular
Crystal structures. For compounds 2, 3-lc, 3-l and 3c-CH
crystals were obtained and characterized by X-ray diffraction.
Compound 2 crystallizes in the monoclinic space group P2 /c with
2 2
Cl single
1
Z = 2 formula units in the unit cell (Table S1). The asymmetric unit
consists of one 3-ethylpyridine ligand, one thiocyanate anion and
one coordinated water molecule in general positions and one Ni
cation that is located on a center of inversion (Figure S36). The Ni
cations are octahedrally coordinated by two terminal N-bonding
anionic ligands, two 3-ethylpyridine ligands and two water
molecules, each of them in trans-position (Figure 6). Bond lengths
and angles correspond to values given in the literature and show that
(Ni3) to the chain direction (Figure 8: bottom).
In contrast to Ni2 and Ni3, Ni1 is located in a general position and
shows a cis-cis-trans-coordination, in which the thiocyanate N atoms
are still trans to each other, whereas the thiocyanate S and the
pyridine N atoms are each in cis-position, which leads to the
formation of corrugated chains (Figure 7: C).
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It is noted that compared to the all-trans coordination, the cis-cis- (Figure S41 and S42). In 3c-CH
trans-coordination is very rare but was recently observed in, e.g., along the crystallographic c-axis (Figure S43). Finally, it is noted that
2
Cl
2
all chains are parallel and proceed
View Article Online
DOI: 10.1039/D0CE00181C
4
4
[
Ni(NCS)
CH Cl shows the same coordination and geometry of the chains but the angles are between 110 and 120°, indicating only very weak
Figure 7: D).
2
[4-(Boc-amino)-pyridine)
2
]
n
.
However, the solvate 3- in 3-l and 3-lc weak intermolecular C-HN interactions are present,
2
2
(
interactions (Table S7).
Figure 8. View of the linear chains in the crystal structure of 3-l (top) 3-lc (bottom).
Magnetic investigations
The susceptibility of 3-l and 3-lc was measured at 100 and 1000 Oe
between 1.8 and 300 K (Figure 9). The product of magnetic
3
susceptibility and temperature, χT, is equal to 1.19 cm K/mol at 300K
for both compounds. This value corresponds to S = 1 spins with a g
factor of 2.18, which is typical for Ni(II) ions. With decreasing
temperature, χT increases in both cases, but significantly faster for 3-
l. The susceptibility of 3-I can be reproduced in the range from 10 to
3
00 K using the model of S = 1 spin chain, with Heisenberg interaction
with the Hamiltonian: −JΣ HΣ . The approximation
n
S
n
S
n+1+gµ
B
n n
S
4
6
formula proposed in was used and the obtained parameters are:
the exchange constant J = 12.5(1) K and the factor g = 2.15(1). The
fitted curve extrapolated below 10 K deviates from the experimental
data due to the neglected single ion anisotropy of Ni(II) and
interchain interactions. The obtained exchange in 3-l is
4
7
ferromagnetic, similar as for previously reported compounds.
Linear and zigzag chains present in 3-lc may exhibit two very different
exchange interaction and susceptibilities, but only their sum is
measured. Therefore it is not possible to draw a conclusion about the
exchange interaction in each of the chains.
Figure 7. View of the chains in the crystal structure of 3-l (A) 3-lc (B and C) and 3c-CH
2 2
Cl
(D).
Concerning the orientation of the chains in the crystal, in
compound 3-l all chains proceed in the same direction with all
pyridine-Npyridine vectors parallel to each other, which corresponds to
one of the common arrangements in such linear chain compounds
Figure S41). In 3-lc the linear chains proceed in the direction of the
N
(
crystallographic b-axis and are exactly perpendicular to the
corrugated chains that elongate along the a-axis (Figure S42). In this
case, the 3-ethylpyridine ligands are arranged in layers and the steric
repulsion between the pyridine rings of the linear and the corrugated
chain might be responsible that the orientation of the pyridine rings
Figure. 9. Temperature dependence of magnetic susceptibility, χ, of 3-lc (circles) and 3-l
(triangles), measured at 100 and 1000 Oe, shown as the χT product. Solid line is a fit
relative to the chain direction is different in 3-lc compared to 3-l (see text) Inset: zero-field cooled (points) and field cooled (lines) susceptibility.
6
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There is no difference between zero-field cooled and field-cooled
curves, and χ(T) increases down to 1.8 K, i.e. samples remain
paramagnetic above this temperature. The deviation between
susceptibilities measured at 100 and 1000 Oe below 3 K for 3-l is due
to the onset of saturation of magnetisation by field. The
magnetisation curve M(H) for 3-l increases steeply with field, as
compared with noninteracting S = 1 spins (see Figure 10), which
confirms the ferromagnetic interactions, and high χT values at low T.
On the other hand, M is still not saturated at 50 kOe, where it reaches
Conclusion
View Article Online
DOI: 10.1039/D0CE00181C
In the present contribution, several new coordination compounds
based on Ni(NCS) and 3-ethylpyridine are reported. For the chain
compounds with a ratio of 1:2 between Ni(NCS) and 3-ethylpyridine
2
2
three forms were discovered. The two metastable forms that either
consist of linear or corrugated chains whereas the third and
thermodynamic stable form contains linear and corrugated chains
within one crystal, which was never observed before in this class of
compounds. To transform these compounds into each other the
metal coordination must change from cis to trans or vice versa, which
indicates that different kinds of species might be present in solution
and that finally, the packing energy determines what kind of isomer
is obtained as solid. However, such species can be in fast equilibria in
solution which might explain that no experimental evidence was
found for this assumption. We also have demonstrated that upon
heating one of the precursor complexes, the new ligand deficient
compounds 4 are obtained via the chain compounds 3 as
intermediate. In this case, always mixtures of the two isomers of 3
are obtained that also transforms into mixtures of the two forms of
2
.0 for 3-lc and 1.85 for 3-l. This is most probably due to anisotropy
of Ni(II) related to zero-field splitting.
4
. If the chain compounds 3-l and 3-lc are investigated separately,
the ratio between the two forms of 4 changes, indicating some
structural relation between the forms of 3 and 4. All this shows that
many new modifications are available if a system is thoroughly
investigated, even if in such cases structure predictions are much
more difficult. Finally, magnetic investigations reveal a magnetic
Figure 10. Magnetisation of 3-l and 3-lc measured at 2 K compared with calculated
dependence for noninteracting, isotropic S = 1 spins with g = 2.18.
exchange constant for 3-l, that is similar to that of [Ni(NSC)
2
(2,2’-
bipyridine) that consist of corrugated chains, which means that
2 n
]
there is no simple correlation between the nature of the co-ligand,
the metal coordination or the geometry of such chains and their
magnetic properties.
The specific heat of 3-lc shows a pronounced peak around 1.3 K
(Figure 11), which clearly marks a magnetic ordering below this
temperature. However, the specific heat of 3-l is inconclusive,
because there is a much smaller peak at the same temperature as for
3
-lc. This could suggest that there was an admixture of 3-lc phase in
Experimental
the 3-l sample, but very similar data were obtained for another batch
of 3-l. Simultaneously, there is no other peak that could be
associated with a magnetic ordering of 3-l, in spite of effectively
stronger ferromagnetic interactions suggested by magnetic
measurements. Qualitatively, the properties of 3-l are similar to the
corrugated chain of [Ni(NSC)
chain of [Ni(NCS) (pyridine)
behaviour is not at hand.
Materials and Methods
Ba(NCS)
Aesar, NiSO
and solvents were used without further purification. Ni(NCS)
was prepared by a reaction of equimolar amounts of
NiSO ·6H O and Ba(NCS) ·3H O in water. The resulting
precipitate of BaSO was filtered off, and the solvent was
removed completely using a rotary evaporator leading to a
2
·3H
2
O and 3-ethylpyridine were obtained from Alfa
4
·6H O was purchased from Merck. All chemicals
2
2
2 2 n
(2,2’-bipyridine) ] and to the linear
2
2 n
] , but the exact modeling of such a
4
2
2
2
4
7
4
2
green residue of Ni(NCS) . The purity was checked by XRPD.
Synthesis of 1-I.
Crystalline powders were obtained by stirring Ni(NCS)
87.4 mg, 0.5 mmol) and 3-ethylpyridine (228 µL, 2 mmol) in
mL H O for 14 d. The purity was checked by XRPD and by IR
and Raman spectroscopy (Figure S2 and S3).
Elemental analysis: calcd (%) C30 NiS
9.71, H 6.01, N 13.93 and S 10.63; found: C 60.02, H 5.65, N
3.74 and S 10.55.
2
(
3
2
H N
36 6
2
(603.48 g/mol): C
5
1
Synthesis of 1-II.
Crystalline powders were obtained by stirring Ni(NCS)
2
Figure 11. Temperature dependence of specific heat, C, measured for 3-l and 3-lc and
shown as C/T.
(87.4 mg, 0.5 mmol) and 3-ethylpyridine (228 µL, 2 mmol) in
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2 4 2
H20Cl N NiS (474.10 g/mol): C
3
mL H
Raman spectroscopy (Figure S4 and S5).
Elemental analysis: calcd (%) C30 NiS
9.71, H 6.01, N 13.93 and S 10.63; found: C 59.67, H 5.89, N Single crystals suitable for x-ray diffraction were obtained by
2
O for 1 d. The purity was checked by XRPD and by IR and Elemental analysis: calcd (%) C17
43.07, H 4.25, N 11.82 and S 13.53; found: C 42.70, H 4.16, N
(603.48 g/mol): C 11.66 and S 12.29.
View Article Online
DOI: 10.1039/D0CE00181C
H N
36 6
2
5
1
3.80 and S 10.24.
solving 3-ethylpyridine (57 µL, 0.5 mmol) in 0.5 mL
dichloromethane and carefully overlaying it with a solution of
Ni(NCS) (174.8 mg, 1 mmol) in 0.5 mL H O. After five days at
2 2
Synthesis of 2.
Crystalline powders were obtained by stirring, Ni(NCS)
2
room temperature single crystals were obtained.
(
2
174.8 mg, 1 mmol) and 3-ethylpyridine (114 µL, 1 mmol) in
Single crystal structure analysis
mL H O for 1 d. The purity was checked by XRPD and by IR and
2
Raman spectroscopy (Figure S6 and S7). Elemental analysis: Data collections were performed with an imaging plate
calcd (%)C16 NiO (425.20 g/mol): C 45.20, H 5.22, N diffraction system IPDS-2 from STOE & CIE using Mo-K
3.18 and S 15.08; found: C 45.06, H 4.94, N 11.91 and S 14.75. radiation. Structure solution was performed with SHELXS or
H N
22 4
S
2 2
α
-
1
5
5
2
Single crystals suitable for x-ray diffraction were obtained by SHELXT and structure refinement was performed against F
stirring Ni(NCS)
5
6
2
(174.8 mg, 1 mmol) and 3-ethylpyridine using SHELXL-2018. A numerical absorption correction was
O and 4mL acetone applied using the programs X-RED and X-SHAPE of the program
(228 µL, 2 mmol) in a mixture of 0.5 mL H
2
5
7
for 4 d. The precipitate was filtered off and the filtrate was kept package X-Area. All non-hydrogen atoms were refined with
at room temperature. Single crystals were obtained after anisotropic displacement parameters. The hydrogen atoms
several weeks.
were positioned with idealized geometry (methyl H atoms were
allowed to rotate but not to tip) and were refined isotropically
with Uiso(H) = -1.2 Ueq(C) (-1.5 for methyl H atoms) using a riding
model. For compound 2 the O-H H atoms were located in
Synthesis of 3-I.
Crystalline powders were obtained by stirring Ni(NCS)
2
(174.8 mg, 1 mmol) and 3-ethylpyridine (228 µL, 2 mmol) in a difference map, their bond lengths were set to ideal values and
mixture of 0.5 mL H
2
O and 1.5 mL ethyl acetate for 16 h. The finally they were refined isotropically with Uiso(H) = -1.5 Ueq(O)
Cl the terminal C atom of
the methyl group are disordered and was refined using a split
(389.17 g/mol): C model with sof of 55:45 in 3-l and 80:20 in 3-CH Cl . In this
9.38, H 4.66, N 14.40 and S 16.48; found: C 49.22, H 4.48, N compound the dichloromethane molecule is strongly
4.27 and S 14.18. disordered and because no reasonable split model was found
purity was checked by XRPD and by IR and Raman spectroscopy using a riding model. In 3-l and 3c-CH
Figure S27 and S28).
Elemental analysis: calcd (%)C16
4
1
2
2
(
H N NiO S
18 4 2 2
2
2
Single crystals suitable for x-ray diffraction were obtained by the data were corrected for disordered solvents using the
5
8
solving Ni(NCS)
with ethyl acetate (0.5 mL) and carefully adding 3-ethylpyridine CCDC-1980434 (2), CCDC-1980436 (3-l), CCDC-1980437 (3-lc)
57 µL, 0.5 mmol) to the organic phase. After several weeks at and CCDC-1980435 (3c-CH Cl ) contain the supplementary
2 2
(174.8 mg, 1 mmol) in 0.5 mL H O, overlaying it Squeeze option in Platon.
(
2
2
room temperature single crystals were obtained.
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.
Synthesis of 3-Ic.
Crystalline powders were obtained by stirring Ni(NCS)
2
IR spectroscopy
(174.8 mg, 1 mmol) and 3-ethylpyridine (228 µL, 2 mmol) in
2
mL ethyl acetate for 3 d. The purity was checked by XRPD and IR spectra were recorded at room temperature on a Bruker
Vertex70 FT-IR spectrometer using a broadband spectral range
(389.17 g/mol): C extension VERTEX FM for mid and far IR.
9.38, H 4.66, N 14.40 and S 16.48; found: C 49.30, H 4.35, N
4.11 and S 16.28.
by IR spectroscopy (Figure S8 and S9).
18 4 2 2
Elemental analysis: calcd (%) C16H N NiO S
4
1
Raman spectroscopy
Single crystals suitable for x-ray diffraction were obtained by Raman spectra were recorded at room temperature on a Bruker
stirring Ni(NCS) (174.8 mg, 1 mmol) and 3-ethylpyridine RAM II FT-Raman spectrometer using liquid nitrogen cooled,
228 µL, 2 mmol) in a mixture of 0.5 mL H
2
-1
(
2
O and 4mL acetone highly sensitive Ge detector, 1064 nm radiation and 3 cm
for 4 d. The precipitate was filtered off and the filtrate was kept resolution.
at room temperature. Single crystals were obtained after
Thermoanalytical Measurements
several weeks.
Differential thermal analysis and thermogravimetric (DTA-TG)
measurements were performed in a dynamic nitrogen
2 2
Synthesis of 3c-CH Cl .
Crystalline powders were obtained by stirring Ni(NCS)
2
atmosphere in Al
O
2 3
crucibles using an STA PT1600
(174.8 mg, 1 mmol) and 3-ethylpyridine (228 µL, 2 mmol) in thermobalance from Linseis. The DSC experiments were
2
mL dichloromethane for 5 d. The purity was checked by XRPD performed using a DSC 1 star system with STARe Excellence
and by IR and Raman spectroscopy (Figure S10 and S11).
software from Mettler-Toledo AG under a dynamic nitrogen
atmosphere. All instruments were calibrated using standard
reference materials.
8
| J. Name., 2012, 00, 1-3
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Elemental analysis
5. C. B. Aakeroy, N. R. Champness and C. Janiak, CrVyieswtEAnrtgicCleoOmnlmine,
010, 12, 22-43.
2
DOI: 10.1039/D0CE00181C
For the elemental analysis a vario MICRO cube from Elementar
Analysensysteme GmbH was used.
6
. Z. Arcis-Castíllo, S. Zheng, M. A. Siegler, O. Roubeau, S. Bedoui
and S. Bonnet, Chem. – Eur. J., 2011, 17, 14826-14836.
7
. A. Schoedel, L. Wojtas, S. P. Kelley, R. D. Rogers, M. Eddaoudi and
M. J. Zaworotko, Angew. Chem., 2011, 123, 11623-11626.
X-ray powder diffraction (XRPD)
The XRPD measurements were performed by using a Stoe 8. S. R. Batten, S. M. Neville and D. R. Turner, Coordination
Transmission Powder Diffraction System (STADI P) with CuK
radiation that was equipped with a linear position-sensitive MYTHEN
detector from STOE & CIE.
Polymers: Design, Analysis and Application, The Royal Society of
Chemistry, 2009.
. B. Moulton and M. J. Zaworotko, Chem. Rev., 2001, 101, 1629-
9
1
658.
10. J.-P. Brog, C.-L. Chanez, A. Crochet and K. M. Fromm, RSC Adv.,
013, 3, 16905.
1. S. A. Bourne, Supramolecular Isomerism, John Wiley & Sons, Ltd,
012.
2. J.-P. Zhang, X.-C. Huang and X.-M. Chen, Chem. Soc. Rev., 2009,
8, 2385-2396.
In situ X-ray powder diffraction
2
Temperature dependent in situ XRPD measurements were carried
out on a Bruker D8-Advance powder diffractometer in Debye-
Scherrer geometry with Cu-Kα1 radiation from primary Ge(111)-
Johannson-type monochromator and Våntec detector. The samples
were loaded into 0.5 mm diameter quartz capillaries, which were
spun during the measurements. The patterns were measured in a 2θ
range from 2.0° to 40.0°. Total scan time of 3 hours was applied per
each measurement. The temperature was adjusted using a TC-
transmission furnace from mri. The samples were heated from 30°C
to 250°C in 20 °C steps with a heating rate of 1°C/min. During each
step, a diffraction pattern was collected, after a delay time of 5
minutes to ensure thermal equilibration of the sample.
1
1
2
3
1
1
3. C. Janiak, Dalton Trans., 2003, 2781-2804.
4. A. J. Blake, N. R. Brooks, N. R. Champness, M. Crew, D. H. Gregory,
P. Hubberstey, M. Schröder, A. Deveson, D. Fenske and L. R.
Hanton, Chem. Commun., 2001, 1432-1433.
5. H. Ohtsu and M. Kawano, Chem. Commun. , 2017, 53, 8818-8829.
6. I. J. Vitorica-Yrezabal, S. Libri, J. R. Loader, G. Minguez
Espallargas, M. Hippler, A. J. Fletcher, S. P. Thompson, J. E.
Warren, D. Musumeci, M. D. Ward and L. Brammer, Chem. Eur.
J., 2015, 21, 8799-8811.
1
1
Magnetic measurements
Magnetic measurements were performed using a Quantum Design 17. J. Tao, R.-J. Wei, R.-B. Huang and L.-S. Zheng, Chem. Soc. Rev.,
Magnetic Properties Measurement System 5 XL. Powders were
2012, 41, 703-737.
packed into gelatin capsules and a few drops of nujol were added. 18. F. A. Mautner, M. Scherzer, C. Berger, R. C. Fischer, R. Vicente
The diamagnetic contributions of the gelatin capsule and the core
and S. S. Massoud, Polyhedron, 2015, 85, 20-26.
diamagnetism were subtracted, using measured and calculated 19. T. Neumann, G. Gallo, I. Jess, R. E. Dinnebier and C. Näther,
values, respectively.
CrystEngComm 2020, 22, 184-194.
2
2
0. D. A. Buckingham, Coord. Chem. Rev., 1994, 135, 587-621.
1. C. Näther, S. Wöhlert, J. Boeckmann, M. Wriedt and I. Jess, Z.
Anorg. Allg. Chem., 2013, 639, 2696-2714.
Specific heat measurements
Specific heat was measured by the relaxation technique using a
Quantum Design PPMS. Powders were pressed into pellets with no 22. F. A. Mautner, C. Berger, R. C. Fischer and S. S. Massoud,
binder. ApiezonN grease was used to ensure thermal contact of the
samples with the microcalorimeter. The heat capacity of the grease 23. E. Shurdha, S. H. Lapidus, P. W. Stephens, C. E. Moore, A. L.
Polyhedron, 2016, 111, 86-93.
was measured before each run and subtracted from the measured
data.
Rheingold and J. S. Miller, Inorg. Chem., 2012, 51, 9655-9665.
24. F. A. Mautner, R. C. Fischer, L. G. Rashmawi, F. R. Louka and S. S.
Massoud, Polyhedron, 2017, 124, 237-242.
2
2
2
2
2
3
3
5. J. Palion-Gazda, I. Gryca, A. Maroń, B. Machura and R. Kruszynski,
Polyhedron, 2017, 135, 109-120.
6. S. Wöhlert, T. Runčevski, R. E. Dinnebier, S. G. Ebbinghaus and C.
Näther, Cryst. Growth Des., 2014, 14, 1902-1913.
7. J. Werner, T. Runčevski, R. Dinnebier, S. G. Ebbinghaus, S. Suckert
and C. Näther, Eur. J. Inorg. Chem., 2015, 2015, 3236-3245.
8. B. Machura, A. Świtlicka, J. Mroziński, B. Kalińska and R.
Kruszynski, Polyhedron, 2013, 52, 1276-1286.
9. C. D. Mekuimemba, F. Conan, A. J. Mota, M. A. Palacios, E.
Colacio and S. Triki, Inorg. Chem., 2018, 57, 2184-2192.
0. J. Palion-Gazda, B. Machura, F. Lloret and M. Julve, Cryst. Growth
Des., 2015, 15, 2380-2388.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This
project
was
supported
by
the
Deutsche
Forschungsgemeinschaft (Project No. Na 720/5-2) and the State
of Schleswig-Holstein and by National Science Centre, Poland
(Project no. 2017/25/B/ST3/00856). We thank Prof. Dr. W.
Bensch for access to his experimental facilities.
1. E. Shurdha, C. E. Moore, A. L. Rheingold, S. H. Lapidus, P. W.
Stephens, A. M. Arif and J. S. Miller, Inorg. Chem., 2013, 52,
10583-10594.
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DOI: 10.1039/D0CE00181C
ARTICLE
Entry for the Table of Contents
New isomeric Ni(NCS) coordination compounds: crystal structures, magnetic
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properties as well as ex situ and in situ investigations on their synthesis and
transition behaviour
Carsten Wellm, Tristan Neumann, Magdalena Ceglarska, Gianpiero Gallo, Michał Rams, Robert E. Dinnebier and Christian
Näther
Some stable and metastable isomeric Ni(NCS) chain compounds were synthesized and investigated for their
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stability, their thermal and their transformation behavior in solution and the solid state. Their structures were
determined single crystal X-ray diffraction and their magnetic were properties investigated by susceptibility and
specific heat measurements.
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