Investigations on the influence of the metal center coordination on the magnetic properties of Mn thiocyanato coordination polymers

Article abstract of DOI:10.1016/j.ica.2015.03.030

Reaction of manganese(II) thiocyanate with the monodentate ligand 4-benzylpyridine (bp) leads to the formation of two compounds of composition Mn(NCS)₂(4-benzylpyridine)₄ (1-bp) and Mn(NCS)₂(4-benzylpyridine)₂ (2-bp). Compound 1-bp forms discrete complexes in which the Mn cations are coordinated by four 4-benzylpyridine ligands and two terminal N-bonding thiocyanato anions within slightly distorted octahedra. In compound 2-bp the metal cations are surrounded by two cis-coordinating 4-benzylpyridine ligands, two cis-coordinating S-bonded thiocyanato anions and two trans-coordinating N-bonded anionic ligands. The Mn cations are linked into zig-zag-like chains by pairs of μ-1,3-bridging anionic ligands. DTA-TG measurements on 1-bp prove that 2-bp is obtained as intermediate. Magnetic measurements on the chain compound 2-bp show dominating antiferromagnetic interactions between the Mn centers. On cooling a maximum is observed in the susceptibility curve indicative for an antiferromagnetic transition. The results of the magnetic measurements are compared with those obtained for other Mn thiocyanato chain compounds in which the thiocyanato anions are trans-coordinated.

Full text of DOI:10.1016/j.ica.2015.03.030

Inorganica Chimica Acta 432 (2015) 96–102
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Inorganica Chimica Acta
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Investigations on the influence of the metal center coordination on the
magnetic properties of Mn thiocyanato coordination polymers
⇑
Stefan Suckert, Susanne Wöhlert, Christian Näther
Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, 24118 Kiel, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of manganese(II) thiocyanate with the monodentate ligand 4-benzylpyridine (bp) leads to the
formation of two compounds of composition Mn(NCS)2(4-benzylpyridine)4 (1-bp) and Mn(NCS)2(4-ben-
zylpyridine)2 (2-bp). Compound 1-bp forms discrete complexes in which the Mn cations are coordinated
by four 4-benzylpyridine ligands and two terminal N-bonding thiocyanato anions within slightly dis-
torted octahedra. In compound 2-bp the metal cations are surrounded by two cis-coordinating 4-ben-
zylpyridine ligands, two cis-coordinating S-bonded thiocyanato anions and two trans-coordinating N-
Received 29 January 2015
Received in revised form 19 March 2015
Accepted 26 March 2015
Available online 3 April 2015
Keywords:
bonded anionic ligands. The Mn cations are linked into zig–zag-like chains by pairs of
l-1,3-bridging
Coordination polymers
Manganese(II) thiocyanate
Thermal properties
Magnetic properties
anionic ligands. DTA–TG measurements on 1-bp prove that 2-bp is obtained as intermediate. Magnetic
measurements on the chain compound 2-bp show dominating antiferromagnetic interactions between
the Mn centers. On cooling a maximum is observed in the susceptibility curve indicative for an
antiferromagnetic transition. The results of the magnetic measurements are compared with those
obtained for other Mn thiocyanato chain compounds in which the thiocyanato anions are trans-
coordinated.
Ó 2015 Published by Elsevier B.V.
1. Introduction
centers are linked by the anionic ligands into chains [35–37]. In
this context we have reported on a number of one-dimensional
Thiocyanato anions are versatile ligands that offer a broad num-
ber of different bonding modes. The most common motif is the
terminal bonding through the nitrogen atom [1–7] or to a smaller
extend through the sulfur atom [8–10]. Besides this, a large num-
(1D) and two-dimensional (2D) thiocyanato coordination polymers
in which the metal cations are always linked by pairs of thio-
cyanato anions into linear chains, that are either terminated by
monodentate or connected into layers by bridging N-donor co-li-
gands (Fig. 1) [38–49]. However, with some other ligands a few
2D thiocyanato networks are observed, where the metal cations
are bridged by either pairs, or single thiocyanato anions into layers
but even in these structures a trans coordination of the thiocyanato
anions is observed [50,51].
It is mentioned that with cations of relatively low chalcophilic-
ity like, e.g., Mn, Fe, Co or Ni, the compounds with a bridging
coordination are more difficult to prepare because the terminal
coordination is energetically favored. In those cases we have devel-
oped a different procedure for the preparation of bridging thio- and
selenocyanates, which is based on thermal decomposition of com-
pounds in which the metal cations are only terminally coordinated
by the anionic ligands [37,52,53]. In the course of our systematic
investigations we have investigated several thiocyanato coordina-
tion polymers based on manganese(II). In all cases, where the Mn
cations are linked by pairs of anionic ligands into chains we
observed dominating antiferromagnetic interactions, which in sev-
eral cases is connected with antiferromagnetic ordering
ber of bridging motifs like, e.g., l-1,1- [11–13], l-1,3- [14–16] or l-
1,1,3-bridging [17–19] through the nitrogen or the sulfur atom are
observed, but compared to the terminal coordination they are
rather uncommon. In this context compounds based on para-
magnetic transition metal cations are of interest, because depen-
dent on the coordination mode of the anionic ligand different
magnetic properties can be observed. Therefore, several of such
compounds were investigated for their structural and magnetic
properties and some selected examples are given in the reference
list [20–27]. It is noted that in most discrete complexes, in which
the anionic ligands are only terminal bonded paramagnetic behav-
ior is observed [4,28–30] but there are also a number of com-
pounds with terminal anionic ligands, in which, e.g., spin-
crossover occurs [31–34]. However, cooperative magnetic proper-
ties are especially found in thiocyanato compounds where the spin
⇑
Corresponding author.
E-mail address: cnaether@ac.uni-kiel.de (C. Näther).
http://dx.doi.org/10.1016/j.ica.2015.03.030
0020-1693/Ó 2015 Published by Elsevier B.V.

S. Suckert et al. / Inorganica Chimica Acta 432 (2015) 96–102
97
thiocyanato anions and four N-bonded 4-benzylpyridine ligands
into discrete complexes, in which the Mn cations shows a slightly
distorted octahedral geometry (Fig. 2). The Mn–N distances ranges
from 2.170(5) to 2.332(5) Å and the angles from 86.56(5)° to
93.63(17)° and from 178.3(2) to 179.8(8) all these values are in
agreement with those in similar compounds (Table S1).
2-bp crystallizes in the monoclinic space group P21/n with four
formula units in the unit cell. The asymmetric unit consists of one
manganese(II) cation, two thiocyanato anion and two 4-ben-
zylpyridine ligands in general positions. The manganese(II) cation
is coordinated by two terminal N-bonded 4-benzylpyridine ligands
and four
l-1,3-bridging thiocyanato anions within a slightly dis-
torted octahedron with Mn–N distances between 2.1416(18) Å
and 2.7352(6) Å and angles ranging from 81.55(5)° to 96.72(5)°
as well as 171.83(5)° to 175.21(7)° (Fig. 3 and Table S2 in the
Supplementary material).
Fig. 1. View of a linear thiocyanato chain with a trans-coordination of the N and S
atom of the anionic ligand frequently observed in bridged thiocyanato coordination
polymers (L = N-donor co-ligand).
In contrast to all comparable Mn coordination polymers inves-
tigated by our group, the N atoms of the anionic ligands and the 4-
benzylpyridine co-ligands show an alternating cis-coordination.
Each manganese(II) center is linked to neighboring metal cations
[37,39,51,54]. What is common to all these compounds is the fact
that the thiocyanato anions are always trans-coordinated to the
metal centers.
by pairs of
l-1,3-bridging thiocyanato anions into zig–zag-like
In present work we prepared a compound based on the mon-
odentate co-ligand 4-benzyplyridine (bp), in which the Mn cations
are also linked by pairs of thiocyanato anions into chains but in
contrast to all of our other compounds, the co-ligands and two of
the thiocyanato anions are cis-coordinated, whereas the other
thiocyanato anions are still trans-coordinated. In this case the
question rises how the magnetic properties will change by this
coordination. It is noted that no structures of thiocyanato com-
pounds with 4-benzylpyridine are reported in the Cambridge
Structure Database [55]. Herein we report on our investigations.
chains which elongate along the crystallographic a-axis (Fig. 3).
The intrachain Mn–Mn distance amount to 5.64 Å, whereas the
shortest interchain distance measures 10.69 Å.
Interestingly, in compounds 1-bp and 2-bp the arrangement of
the building blocks is very similar (Fig. 4). The discrete complexes
in 1-bp are stacked in the direction of the crystallographic a-axis
with the Mn(NCS)2 units and the 4-benzylpyridine ligands eclipsed
to each other (Fig. 4: top). Within these stacks the 6-membered
rings of the benzyl ligands are parallel to each other indicative
for
p p interactions. The same arrangement is found in 2-bp with
ꢁ ꢁ ꢁ
the difference that the Mn cations are linked into chains that elon-
gate in the same crystallographic direction as the Mn(NCS)2 units
in 1-bp (Fig. 4: top).
2. Results and discussion
The crystallographic relation becomes also obvious by compar-
ing the unit cell parameters of both compounds (Table 2). The
lengths of the a-axis is very similar, which indicates that the dis-
tance along the chains is determined predominantly by the organic
ligands. For the c-axis also very similar values are found, because
the arrangement of the building blocks is identical in this direction.
The value of the crystallographic b-axis is more than doubled in 1-
bp, which originates from the C-centering of the complexes.
However, because of the zig–zag-like arrangement of the thio-
cyanato chains the distance between neighboring chains along
the b-axis is larger in 2-bp compared to 1-bp (see Fig. 4).
Based on the crystallographic data XRPD pattern were calcu-
lated and compared with the experimental pattern, which indi-
cates that both compounds are obtained as pure materials
(Figs. S5 and S6 in the Supplementary material).
2.1. Synthetic investigations
To investigate how many compounds with 4-benzylpyridine are
available, manganese(II) thiocyanate and this ligand were reacted
in various stoichiometric ratios in water, methanol, acetonitrile
or ethanol at room-temperature and the crystalline solids obtained
were investigated by X-ray powder diffraction (XRPD). These
investigations clearly show that only two different crystalline
phases were obtained. If the reactants are mixed in ratio 1:1 or if
an excess of the co-ligand is used a compound is isolated that
according to elemental analysis exhibits the composition
Mn(NCS)2(4-benzylpyridine)4 (1-bp). If less 4-benzylpyridine is
used in the synthesis a crystalline phase of a composition of
Mn(NCS)2(4-benzylpyridine)2 (2-bp) is obtained. IR-spectroscopic
investigations on 1-bp shows that the asymmetric stretching
vibration m
as(CN) is observed at 2050 cmꢀ1 indicative for the pres-
ence of terminal bonded thiocyanato anions (Fig. S1 in the
2.3. Thermoanalytical investigations
Supplementary material) [56]. For 2-bp this vibration is shifted
The strong structural relation between 1-bp and 2-bp suggests
that a smooth reaction pathway exists between the former and the
latter compounds. Therefore, we tried to prepare 2-bp by thermal
decomposition of 1-bp as already shown for related thiocyanato
coordination polymers. In this context it is mentioned that also
other modifications can sometimes be obtained by this route
[57]. To investigate the thermal behavior compound 1-bp was
investigated by simultaneous differential thermoanalysis and
thermogravimetry (DTA–TG). When heated in a thermobalance to
500 °C, 1-bp exhibits three mass steps in the TG curve, which are
accompanied with endothermic events in the DTA curve (see
Fig. 5). From the DTG curve it is obvious that the first event is rea-
sonably separated which is not the case for the second and third
event. The experimental mass loss of the first TG step
to 2085 cm, which is indicative for a
l-1,3 bridging coordination
of the anionic ligands (Fig. S2 in the Supplementary material)
[56]. In order to structurally characterize the two compounds sin-
gle crystals were prepared and investigated by X-ray structure
analysis.
2.2. Crystal structures
Compound 1-bp crystallizes in the monoclinic space group Cc
with four formula units in the unit cell. The asymmetric unit con-
sists of one manganese(II) cation, two thiocyanato anions and four
4-benzylpyridine ligands which occupy general positions. The
manganese(II) cation is coordinated by two terminal N-bonded

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S. Suckert et al. / Inorganica Chimica Acta 432 (2015) 96–102
Fig. 2. Crystal structure of 1-bp showing the coordination sphere of the Mn cations.
An ORTEP plot can be found in Fig. S3 in the Supplementary material.
D
m(exp) = 34.1% is much lower than that calculated for the removal
of half of the 4-benzylpyridine ligands ( m(calc) = 39.8%), but the
D
overall mass loss of 78.6% is close to that expected for the removal
of all of the bp ligands. These results indicate that the trans-
formation of 2-bp into 1-bp is incomplete at the end of the first
TG step or that a compound of different stoichiometry has formed.
To identify the intermediate an additional TG measurement was
performed, stopped after the first TG step and the residue obtained
was investigated by XRPD and IR-spectroscopy. A comparison of
the experimental pattern of this residue with that calculated from
single crystal data for 1-bp and 2-bp clearly shows that 2-bp is
obtained but contaminated with significant amounts of the pris-
tine compound 1-bp (Fig. S7 in the Supplementary material ).
This is in agreement with an IR-spectrum of this residue, which
Fig. 3. Crystal structure of 2-bp showing the coordination sphere of the Mn cations.
An ORTEP plot can be found in Fig. S4 in the Supplementary material.
shows two values for the CN-stretching vibrations at 2052 cmꢀ1
and 2085 cmꢀ1
,
which are in perfect agreement with those
observed for 1-bp and 2-bp (Fig. S8).
Fig. 4. Crystal structure of 1-bp (top) and 2-bp (bottom) with view along the crystallographic a-axis.

S. Suckert et al. / Inorganica Chimica Acta 432 (2015) 96–102
99
Fig. 5. DTG, TG and DTA curves of 1-bp at 4 °C/min. Given are the peak
temperatures TP in °C and the mass loss in %.
Fig. 6. TG measurements for 1-bp at different heating rates. Given is the mass loss
in %.
In the following TG measurements at different heating rates
were performed in order to check the influence of the kinetics on
product formation.[58] From these measurements it is obvious
that with decreasing heating rate the resolution becomes better
and that the value for the first mass loss increases to a value, which
is calculated exactly for the removal of two bp ligands
(Dm(calc) = 39.8%; see Fig. 6). If the residue obtained after the first
step is investigated by XRPD, it is proven that the same crystalline
phase is obtained, that was already prepared from solution and
that in both cases pure samples are obtained (Fig. 7).
2.4. Magnetic investigations
In order to characterize compound 1-bp and 2-bp for their mag-
netic properties, the temperature dependence of the susceptibility
was investigated by applying a magnetic field of HDC = 1 kOe in the
temperature range of 300–2 K. Based on the terminal coordination
of the thiocyanato anions only Curie- or Curie–Weiss para-
magnetism is expected for the discrete complex 1-bp.
Consequently, fitting of its magnetic data according to the Curie–
Weiss law gives a value for the Weiss constant which is practically
Fig. 7. XPRD pattern of 2-bp (A), the residue obtained from TG measurements of
compound 1-bp at a heating rate of 1 K/min (B) and the calculated pattern of 2-bp
(C).
zero (Fig. S9 in the Supplementary material). From the
curve it is obvious, that on cooling dominating antiferromagnetic
interactions are observed.
v
ꢁT versus T
expected at low temperatures. Moreover, a field dependent mag-
netization experiment at T = 2 K shows a linear increase of the
magnetization with increasing field, which is in accordance with
antiferromagnetism (Fig. S10 in the Supplementary material).
Finally, the temperature dependence of the AC susceptibility was
measured at different frequencies (Fig. S11 in the Supplementary
material). In this case a frequency independent maximum is
observed in the real part and no signal is observed in the imaginary
part, which clearly shows that only antiferromagnetism is
observed.
In contrast, for compound 2-bp a maximum in the
curve at TN = 27.4 K is observed, indicative for antiferromagnetic
ordering (Fig. 8). A fitting of the magnetic data according to the
v versus T
Curie–Weiss law yields
(h = ꢀ44.81 K), indicative for dominating antiferromagnetic inter-
actions, which is also obvious from the progression of the T pro-
a strongly negative Weiss constant
v
duct (Fig. 8). However, a small increase of the susceptibility after
the antiferromagnetic maximum is observed, that might be a hint
for canted antiferromagnetism, which would be possible because
the Mn–N or Mn–S bonds of neighboring cations are canted.
Anyhow, in this case saturation of the susceptibility would be
Therefore, it can be concluded that the small increase in sus-
ceptibility can be traced back to a paramagnetic impurity, which

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S. Suckert et al. / Inorganica Chimica Acta 432 (2015) 96–102
because no other compound is available in this system. From the
susceptibility values one can estimate that less than 2% of this con-
tamination will be enough to explain the experimental susceptibil-
ity curve of 2-bp. This amount is difficult to detect by XRPD.
Unfortunately, we never found access to completely pure samples
for 2-bp, but there is no doubt that this compound shows an
antiferromagnetic transition.
As pointed out in the introduction these results can be compared
with those of related compounds, in which Mn(II) cations are linked
into chains by pairs of thiocyanato anions but in which a different
configuration is found at the metal center. In most cases the co-li-
gands as well as the N and S atoms of the thiocyanato anion are
trans to each other as it is the case in, e.g., [Mn(NCS)2(4-
ethylpyrídine)2]n [44] and [Mn(NCS)2(pyridine)2]n [39] reported
recently (Table 1). Despite their different configuration of the anio-
nic ligands at the metal center both compounds show
antiferromagnetic interactions and an antiferromagnetic transition
as it is the case for compound 2-bp. Even if the intrachain and inter-
chain distances are shorter for these two compounds the Néel tem-
perature as well as the Weiss constant are significantly lower
indicating weaker interactions. There is a further compound
reported in literature that shows a different configuration at the
metal center. In [Mn(NCS)2(2,20-bipyridine)]n the Mn cations are
coordinated by two trans-oriented thiocyanato anions into corru-
gated chains but in contrast to compound 1-bp the bidentate ligand
enforces also a cis-configuration of the two N atoms of the co-li-
gand. However, even for this compound antiferromagnetic interac-
tions are observed, which are stronger than those in the pyridine
and the 4-ethylpyridine compound (Table 1).
Fig. 8.
at HDC = 1 kOe.
v
M and (8
v
M(T ꢀ h))0.5 (inset) as function of temperature for 2-bp measured
Table 1
Comparison of shortest intra- and interchain Mn–Mn distances and selected magnetic
parameters for compounds 2-bp, [Mn(NCS)2(2,20-bipyridine)]n (A), [Mn(NCS)2(4-
ethylpyrídine)2]n (B) and [Mn(NCS)2(pyridine)2]n (C) [39,44].
Compound
2-bp
27.4
A
B
C
TN (K)
h (K)
Intrachain (Å)
Interchain (Å)
23.0
21.5
23.5
ꢀ44.81
ꢀ45.65
ꢀ36.10
5.534
8.886
ꢀ37.34
5.748
8.885
5.641
6.071
10.698
8.371
2.5. Conclusions
was not detected by X-ray powder diffraction as recently observed
in magnetic investigations of similar compounds [51]. To support
this assumptions several batches prepared by synthesis from solu-
tion or by thermal decomposition were investigated, because in
this case it can be assumed that always a different amount of a
contamination is present (Fig. S12 in the Supplementary material).
In all these measurements the antiferromagnetic maximum and a
further increase of the susceptibility at low temperatures is
observed. However, the increase of the susceptibility after the
maximum is always different, which strongly indicates that an
impurity is present, which might correspond to compound 1-bp,
In the present contribution a new Mn thiocyanato coordination
polymer was reported, in which the metal centers are linked into
chains by the anionic ligands. These investigations follow up on
previous investigations on similar compounds that show a trans-
configuration of the anionic and the neutral co-ligands and for
which
dominating
antiferromagnetic
interactions
and
antiferromagnetic ordering are observed. In contrast, in the title
compound the two N-bonded thiocyanato anions are still trans to
the metal centers, but the two S-bonded thiocyanato anions and
the two 4-benzylpyridine co-ligands are each cis-coordinated,
which leads to the formation of corrugated instead of linear chains.
However, the magnetic exchange is not strongly affected because
the title compound also show stronger antiferromagnetic interac-
tions and an antiferromagnetic transition. This is in agreement
with the results observed for [Mn(NCS)2(2,20-bipyridine)]n
reported recently, that show a cis-arrangement of the anionic
ligands and a similar magnetic behavior. Therefore, our results
strongly indicates that the overall magnetic properties of such
Mn thiocyanato compounds are only minor influenced by the con-
figuration at the metal centers. Unfortunately, independent of the
nature of the metal in most of such compounds linear chains with
a trans-configuration are found and thus, the title compound was
accidently obtained, which means that there is no rational access
to such compounds. Finally, the fact that the bp-rich compound
1-bp transforms into 2-bp on heating might also be correlated with
the observation that both structures are strongly related.
Table 2
Selected crystal data and details on the structure refinements for 1-bp and 2-bp.
1-bp
2-bp
Formula
C
50H44MnN6S2
C26H22MnN4S2
509.54
monoclinic
P21/n
10.1951(4)
14.4957(4)
16.4604(5)
90.854(3)
2432.33(14)
200
MW (g molꢀ1
)
847.97
monoclinic
Cc
9.7926(5)
25.2968(13)
17.7406(10)
90.066(4)
4394.7(4)
293
Crystal system
Space group
a (Å)
b (Å)
c (Å)
b (°)
V (Å3)
T (K)
Z
4
4
Dcalc. (mg m3)
1.282
0.437
1.391
0.736
l
(mmꢀ1
)
hmax (°)
27.00
28.50
Reflections collected
Unique reflections
Rint
16158
8383
0.0553
5931
26454
6149
0.0349
5025
3. Experimental section
Reflections [F0 > 4
r(F0)]
Parameters
533
298
0.0469
0.1060
1.070
3.1. Syntheses
R1 [F0 > 4
r
(F0)]
0.0607
0.1276
1.103
0.398/ꢀ0.231
wR2
GOF
MnSO4ꢁH2O, Ba(NCS)2ꢁ3H2O, KNCS and 4-benzylpyridine were
D
qmax/min (e Åꢀ3
)
0.265/ꢀ0.264
obtained from Alfa Aesar. Mn(SCN) was prepared by the reaction

S. Suckert et al. / Inorganica Chimica Acta 432 (2015) 96–102
101
of equimolar amounts of MnSO4ꢁH2O and Ba(NCS)2ꢁ3H2O in water.
The resulting white precipitate of BaSO4 was filtered of and the fil-
trate was concentrated to complete dryness resulting in a white
residue of Mn(SCN)2. The purity was checked by XRPD and elemen-
tal analysis. All crystalline powders were prepared by stirring of
the reactants in solution for 3 d at room temperature. The residues
were filtered off and washed with water and air-dried.
system is correct. It is noted that for 1-bp ADDSYMM in Platon
detects a pseudo center of inversion, which is valid for 81% of the
complex. The structure can also be refined in space group C2/c
but in this case strong disorder is found for both crystallographi-
cally independent 4-benzylpyridine ligands and very poor reliabil-
ity factors are observed. In contrast, in space group Cc a well
ordered structure is observed and therefore, this space group was
selected. Moreover, the absolute structure can easily be deter-
mined, which would not be possible in the case of higher symme-
try (Flack x-parameter = 0.04(3)). Details of the structure
determination are given in Table 2.
3.2. Preparation of Mn(NCS)2(4-benzylpyridine)4 (1-bp)
Single crystal suitable for X-ray structure determination were
obtained by the reaction of Mn(NCS)2 (25.7 mg, 0.15 mmol) with
3.7. X-ray powder diffraction (XRPD)
4-benzylpyridine (47.8 lL, 0.3 mmol) in 1 mL Methanol a closed
snap cap vial. White block-shaped single-crystals were obtained
after two weeks. A microcrystalline powder was prepared by the
reaction of Mn(NCS)2 (256.7 mg, 1.5 mmol) with 4-benzylpyridine
(956.9 lL, 6.0 mmol). Yield based on Mn(NCS)2: 1136.3 mg (89.3%).
Elemental Anal. Calc. for C50H44N6MnS2 (848.01): C, 70.82; H, 5.23;
The measurements were performed using (1) a PANalytical
X’Pert Pro MPD Reflection Powder Diffraction System with Cu K
a
radiation (k = 154.0598 pm) equipped with a PIXcel semiconductor
detector from PANanlytical and (2) a Stoe Transmission Powder
Diffraction System (STADI P) with Cu
K
a
radiation
N, 9.91; S, 7.56. Found: C, 71.57; H, 5.28; N, 10.06; S, 6.87%. IR
(k = 154.0598 pm) that was equipped with a MYTHEN K1000
detector from STOE & CIE.
(ATR): mmax = 3027 (w), 2909 (w), 2050 (s), 1610 (m), 1558 (m),
1494 (m), 1450 (m), 1419 (m), 1223 (m), 1065 (m), 1012 (s), 859
(m), 837 (m), 797 (s), 733 (s), 703 (s), 617 (s), 559 (s), 483 (s),
459(s).
3.8. Differential thermal analysis and thermogravimetry (DTA–TG-MS)
The heating-rate dependent DTA–TG measurements were per-
formed in a nitrogen atmosphere (purity: 5.0) in Al2O3 crucibles
using a STA-409CD instrument from Netzsch. All measurements
were performed with a flow rate of 75 mL minꢀ1 and were cor-
rected for buoyancy and current effects. The instrument was cali-
brated using standard reference materials.
3.3. Preparation of [Mn(NCS)2(4-benzylpyridine)2]n (2-bp)
Single crystals suitable for X-ray structure determination were
obtained from the filtrate of the reaction above in a closed snap
cap vial. Block-shaped single-crystals were obtained after one
week.
Microcrystalline powders were prepared by the reaction of
3.9. Magnetic measurements
Mn(SCN)2 (153.9 mg, 0,9 mmol) with 4-benzylpyridine (35.1
0.22 mmol) in 1.5 mL Ethanol. Yield based on 4-benzylpyridine:
108.5 mg (96.8%). Elemental Anal. Calc. for 26H22N4MnS2
(509.5575): C, 61.29; H, 4.35; N, 11.00; S, 12.59. Found: C, 60.60;
H, 4.09; N, 11.02; S, 13.20%. IR (ATR): max = 3028 (w), 2906 (w),
2085 (s), 1610 (m), 1556 (m), 1494 (m), 1450 (m), 1421 (m),
1223 (m), 1070 (m), 1015 (s), 937 (m), 857 (m), 833 (m), 792 (s),
730 (s), 701 (s), 616 (s), 560 (s), 484 (s), 471 (s).
lL,
All magnetic measurements were performed using a PPMS
(Physical Property Measurement System) from Quantum Design,
which was equipped with a 9 T magnet. The data were corrected
for core diamagnetism.
C
m
Acknowledgements
This
project
was
supported
by
the
Deutsche
3.4. Elemental analysis
Forschungsgemeinschaft (Project No. Na 720/3-1) and the State
of Schleswig-Holstein. We thank Prof. Dr. Wolfgang Bensch for
access to his experimental facilities. Special thanks to Inke Jess
for the single crystal measurements.
CHNS analysis was performed using an EURO EA elemental ana-
lyzer, fabricated by EURO VECTOR Instruments and Software.
3.5. Spectroscopy
Appendix A. Supplementary material
All IR data were obtained using an ATI Mattson Genesis Series
FTIR Spectrometer, control software: WINFIRST, from ATI Mattson.
CCDC 1054774 and 1054775 contains the supplementary crys-
tallographic data for 1-bp and 2-bp, respectively. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary
data associated with this article can be found, in the online version,
at http://dx.doi.org/10.1016/j.ica.2015.03.030.
3.6. Single-crystal structure analyses
Single-crystal data collections were carried out on an imaging
plate diffraction system: Stoe IPDS-2 with Mo K
a radiation. The
structures were solved with Direct Methods using SHELXS-97 and
structure refinements were performed against F2 using SHELXL-97
[59]. Numerical absorption correction was applied using programs
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