Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes in solution and in the solid state

Article abstract of DOI:10.1515/znb-2018-0104

Reaction of Mn(NCS)₂ with pyrazole leads to the formation of three compounds with the compositions Mn(NCS)₂(pyrazole)₄ (1), [Mn(NCS)₂]₂(pyrazole)₆ (2) and Mn(NCS)₂(pyrazole)

Full text of DOI:10.1515/znb-2018-0104

Z. Naturforsch. 2018; aop
AFloekrsemj JoachtiimoanndoChfrisdtiia-n Naänthedr*polynuclear Mn(II) thiocyanate
pyrazole complexes in solution and in the solid
state
https://doi.org/10.1515/znb-2018-0104
1 Introduction
Received May 23, 2018; accepted July 21, 2018
Abstract: Reaction of Mn(NCS)2 with pyrazole leads to Thiocyanate anions are versatile ligands that can coor-
the formation of three compounds with the compositions dinate to metal cations in many different ways. The most
Mn(NCS)2(pyrazole)4 (1), [Mn(NCS)2]2(pyrazole)6 (2) and prominent coordination is the so-called N- or S-terminal
Mn(NCS)2(pyrazole)2 (3). Compound 1, already reported in coordination, in which the anionic ligands are only con-
the literature, consists of discrete complexes, in which the nected via the N or the S atom to the metal centers [1–7].
Mn(II) cations are octahedrally coordinated by four pyra- Compared to the N-coordination the latter mode is rare
zole ligands and two terminally N-bonded thiocyanate and only found with strong chalcophilic cations like,
anions. In compound 2 each of the two Mn(II) cations are e.g. Ag(I), Pd(II) or Pt(II) [8–13]. From a structural point
coordinated octahedrally by three pyrazole ligands and of view the bridging modes are much more interesting,
one terminal as well as two bridging thiocyanate anions, because in this case metal cations can be linked into a
which link the metal cations into dimers. In compound variety of motifs like, e.g. dimers, chains or layers [14–20].
3 also octahedrally coordinated Mn(II) cations are pre- The large number of coordination modes and the struc-
sent but they are linked into chains via centrosymmetric tural diversity of such compounds are expressed by the
pairs of μ-1,3-bridging thiocyanate anions. Upon heating fact, that an increasing number of different polymorphic
compound 1 loses the pyrazole co-ligands stepwise and or isomeric modifications of thiocyanate compounds were
is transformed into the chain compound 3 via the dimer reported recently [21–24]. Moreover, thiocyanate anions
2 that is formed as an intermediate. Magnetic measure- can mediate magnetic exchange and in this context
ments on compounds 2 and 3 reveal dominating anti- many papers reported on new magnetic compounds with
ferromagnetic interactions, as already observed for 1D several of them showing magnetic ordering upon cooling
Mn(NCS)2 coordination compounds with pyridine based [25–41]. Our investigations focus on thio- and selenocy-
co-ligands.
anate compounds with 3D metal cations, like, e.g. Mn(II),
Fe(II), Co(II), and Ni(II) which are additionally coordi-
nated by N-donor co-ligands. In most cases two different
compounds are obtained. Discrete complexes with the
general composition M(NCX)2(L)4 (X=S, Se and Lꢀ=ꢀco-
ligand) with octahedral coordination of the metal cations
and terminally N-bonded anionic ligands as well as com-
pounds with the composition M(NCX)2(L)2, in which the
octahedrally coordinated metal cations are linked by
μ-1,3-bridging anionic ligands into chains or layers
[42–48]. In solution the discrete complexes are usually
more stable, which means that the bridging compounds
are sometimes difficult to prepare. However, if the com-
plexes are heated the co-ligands can be removed in a dis-
crete step, which leads to the formation of the bridging
compounds in quantitative yield. In some cases metastable
compounds like, e.g. polymorphs or isomers are obtained
that are different from those obtained from solution. It is
noted, that the synthesis of coordination compounds by
typical solid state synthesis is not uncommon and several
Keywords: crystal structures; magnetic properties; Mn
coordination compounds; pyrazole; thermal properties;
thiocyanate ligands.
Dedicated to: Professor Bernt Krebs on the occasion of his 80th
birthday.
*Corresponding author: Christian Näther, Institut für Anorganische
Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2,
24118 Kiel, Germany, Fax: +49-431-8801520,
E-mail: cnaether@ac.uni-kiel.de
Aleksej Jochim: Institut für Anorganische Chemie, Christian-
Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, 24118 Kiel,
Germany
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2ꢀ ꢀA. Jochim and C. Näther: Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes
approaches have already been reported [49–52]. However, is at the borderline values usually observed for terminal
in most cases 1D compounds are obtained, in which the and bridging thiocyanate anions and in this case no pre-
metal cations are linked by pairs of anionic ligands into dictions can be made. However, for compounds 2 and 3
chains. Dependent on the nature of the metal cation the crystals suitable for single crystal X-ray diffraction analy-
magnetic exchange along the chain is usually different. sis could be prepared and structurally characterized.
For, e.g. Ni(II) and Co(II) it is ferromagnetic, whereas for
compounds based on Mn(NCS)2 it is usually antiferromag-
netic [32–34, 53–55]. For the latter usually simple para- 2.2 Crystal structures
magnetic behavior is observed, but some of them show
antiferromagnetic ordering upon cooling [53–55].
However, what is common to all of the compounds
2.2.1 Crystal structure of [Mn(NCS)2]2(pyrazole)6 (2)
is the fact, that they always contain pyridine derivatives Compound 2 crystallizes in the monoclinic space group
as co-ligands, which are usually substituted in 4-posi- P21/n with the asymmetric unit consisting of one Mn(II)
tion. Most of these ligands are relatively volatile and this cation, two thiocyanate anions and three pyrazole mole-
might be the reason, why they can easily be removed by cules in general positions. Each of the Mn(II) cations is
thermal treatment, leading to the formation of the bridged octahedrally coordinated by three pyrazole molecules as
compounds. Therefore, the question arises if similar com- well as one terminal and two μ-1,3-bridging thiocyanate
pounds can be prepared with other co-ligands and how anions thus producing a dinuclear complex, as already
this will influence the thermal behavior and the magnetic indicated by the IR spectroscopic measurements (Fig. 1).
properties. In the beginning we selected pyrazole as a
The Mn–N distance to the terminal thiocyanate anion
ligand, for which already some discrete complexes with of 2.162(2) Å is slightly shorter than that to the bridg-
the composition M(NCS)2(pyrazole)4 have been reported ing anionic ligand of 2.1854(2) Å, which might be traced
with M=Mn [56], Co [57], and Ni [57, 58]. Compounds with back to steric repulsion (Table 1). The Mn–N distances to
bridging anionic ligands and these cations are unknown the pyrazole ligands between 2.232(2) and 2.257(2) Å are
but there is one 1D Cd compound with the composition significantly longer than that to the thiocyanate anions
[Cd(NCS)2(pyrazole)2]n, which indicates that more of such (Table 2).
coordination polymers might be available [59].
The bond angles, which range from 84.99(5) to
95.11(5)° and from 174.77(5)° to 177.35(8)°, indicate a slight
distortion of the coordination polyhedron. This can be
quantified using the values of the octahedral angle vari-
ance σθ‹oct›2 and the mean octahedral quadratic elongation
λoct introduced by Robinson et al. [60]. Comparing the cor-
responding values for compound 2 (σθ‹oct›2ꢀ=ꢀ7.21, λoctꢀ=ꢀ1.01)
2 Results and discussion
2.1 Synthesis
The reaction of Mn(NCS)2 with pyrazole in different molar
ratios yielded three different crystalline phases, of which
one could be identified by X-ray powder diffraction (XRPD)
as Mn(NCS)2(pyrazole)4 (1) reported recently. For the other
two phases elemental analyses suggested a composition
of [Mn(NCS)2]2(pyrazole)6 (2) and Mn(NCS)2(pyrazole)2
(3). An IR spectroscopic measurement on compound 2
has shown that two bands for the CN stretching vibra-
tion of the thiocyanate anions are observed at 2068 and at
2097 cm−1. The first value is very similar to that observed
in 1 (2064 cm−1), indicating that terminally bound anionic
ligands are present in 2. The second value is strongly
shifted to higher values and in the range for those, typi-
cally observed for bridging anionic ligands. Therefore, it is
highly likely that compound 2 consists of dimers with ter-
minal and bridging thiocyanate anions. For compound 3
Fig. 1:ꢀView of the dinuclear complex 2 with labeling and
displacement ellipsoids drawn at the 50% probability level.
the CN stretch is surprisingly observed at 2072 cm−1 which Symmetry codes: A: –xꢁ+ꢁ1, –yꢁ+ꢁ1, –zꢁ+ꢁ1.
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A. Jochim and C. Näther: Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexesꢀ
ꢀ3
Table 1:ꢀSelected bond lengths and angles (Å, deg) for compound 2.
Mn(1)–N(1)
2.1854(18) Mn(1)–N(21)
2.1621(19) Mn(1)–N(31)
2.2466(19) Mn(1)–S(1A)
177.35(8) N(21)–Mn(1)–N(31)
89.80(7) S(1)–Mn(1A)
90.11(7) N(11)–Mn(1)–N(31)
90.51(8) N(2)–Mn(1)–S(1A)
92.14(7) N(1)–Mn(1)–S(1A)
92.54(7) N(21)–Mn(1)–S(1A)
90.00(7) N(11)–Mn(1)–S(1A)
87.35(7) N(31)–Mn(1)–S(1A)
2.2315(18)
2.2566(19)
2.7514(7)
90.86(7)
Mn(1)–N(2)
Mn(1)–N(11)
N(2)–Mn(1)–N(1)
N(2)–Mn(1)–N(21)
N(1)–Mn(1)–N(21)
N(2)–Mn(1)–N(11)
N(1)–Mn(1)–N(11)
N(21)–Mn(1)–N(11)
N(2)–Mn(1)–N(31)
N(1)–Mn(1)–N(31)
2.7514(6)
176.57(6)
84.99(5)
95.11(5)
174.77(5)
87.03(5)
89.64(5)
Symmetry code for the generation of equivalent atoms: A: –xꢁ+ꢁ1,
–yꢁ+ꢁ1, –zꢁ+ꢁ1.
Table 2:ꢀHydrogen bonding (Å, deg) for compound 2.
Fig. 2:ꢀCrystal structure of 2 with view along the crystallographic a
axis with intermolecular hydrogen bonding shown as dashed lines.
Dꢁ·ꢁ·ꢁ·ꢁA
Hꢁ·ꢁ·ꢁ·ꢁA
ꢁ<(D–Hꢁ·ꢁ·ꢁ·ꢁA)
N(12)–H(12)ꢁ·ꢁ·ꢁ·ꢁS(1A)
N(12)–H(12)ꢁ·ꢁ·ꢁ·ꢁS(2B)
N(22)–H(22A)ꢁ·ꢁ·ꢁ·ꢁS(2D)
N(32)–H(32A)ꢁ·ꢁ·ꢁ·ꢁS(2E)
3.335(2)
3.622(2)
3.320(2)
3.321(2)
2.73
2.87
2.61
2.51
127.5
144.2
138.1
153.4
Symmetry codes: A: –xꢁ+ꢁ1, –yꢁ+ꢁ1, –zꢁ+ꢁ1; B: –xꢁ+ꢁ1/2, yꢁ+ꢁ1/2, –zꢁ+ꢁ3/2;
D: –xꢁ+ꢁ3/2, yꢁ+ꢁ1/2, –zꢁ+ꢁ3/2; E: xꢁ+ꢁ1/2, –yꢁ+ꢁ1/2, z–1/2.
with those for compound 1 (σθ‹oct›2ꢀ=ꢀ3.05, λoctꢀ=ꢀ1.00) shows
that the coordination octahedron of the dimer 2 is more
distorted than that of the discrete octahedral complex 1.
This is expected as the Mn(II) cation of compound 2 is
coordinated by nitrogen as well as sulfur while in com-
pound 1 the metal cation is coordinated solely by nitrogen
atoms.
The dimeric units are interconnected via hydrogen
bonding between the pyrazole N–H groups and the thiocy-
anate sulfur atoms forming a three dimensional network
(Fig. 2, Table 2).
Fig. 3:ꢀView of a part of a chain in crystals of 3 with labeling
and displacement ellipsoids drawn at the 50% probability level.
Symmetry codes: A: –xꢁ+ꢁ1, –yꢁ+ꢁ1, –zꢁ+ꢁ1; B: –x, –yꢁ+ꢁ1, –zꢁ+ꢁ1; C: x–1,
y, z; D: xꢁ+ꢁ1, y, z; E: –x–1, –yꢁ+ꢁ1, –zꢁ+ꢁ1.
2.2.2 Crystal structure of Mn(NCS)2(pyrazole)2 (3)
As in compound 2, the Mn–N distances to the anionic
ligands are shorter than those to the pyrazole co-ligands
Compound 3 crystallizes in the monoclinic space group (Table 3). However, the thiocyanate Mn–N distances are
P21/c with the asymmetric unit containing one thiocy- comparable to those in 2, whereas the Mn–S distance is
anate anion and one pyrazole molecule in general posi- significantly shorter than in the dimer 2, which points to
tions as well as one Mn(II) cation that occupies a center a stronger interaction (compare Tables 1 and 3). The Mn–N
of inversion. The Mn(II) cations are connected via cen- distances to the pyrazole ligands are comparable to those
trosymmetric pairs of thiocyanate anions into chains. Two found in compound 2. It is noted that the C–N distance of
pyrazole molecules occupy the axial positions, whereas the thiocyanate anion is as long as that in the terminally
the two S and two thiocyanate N atoms are located in the N-bonded anion in the dimer 2 and significantly shorter
basal plane in trans-position leading to a slightly distorted than that of the bridging anionic ligand. This might be
octahedral coordination environment (Fig. 3).
the reason why the C–N stretch is shifted to much lower
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4ꢀ ꢀA. Jochim and C. Näther: Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes
Table 3:ꢀSelected bond lengths and angles (Å, deg) for compound 3.
compounds with pyridine derivatives only two different
arrangements of the chains are observed. In one group the
N–N vectors of the pyridine N atoms are parallel, whereas
in the second group they are canted. In the crystal struc-
ture of compound 3, the latter motif is observed (Fig. 4:
bottom).
The single crystal data were used to calculate the
corresponding XRPD patterns, and the results were com-
pared with the experimental pattern showing clearly that
compounds 1, 2 and 3 were obtained as pure phases. For
compound 3, small differences in the peak positions were
found, which can be traced back to the fact that the single
crystal data collection was performed at 170 K. Therefore,
the lattice parameters were additionally determined by a
Pawley fit using the XRPD data measured at room-tem-
Mn(1)–N(1)
ꢂ 2.1660(13)ꢂ Mn(1)–N(11A)
ꢂ 2.1660(13)ꢂ Mn(1)–S(1B)
ꢂ 2.2353(13)ꢂ Mn(1)–S(1C)
ꢂ 2.2353(13)
Mn(1)–N(1A)
ꢂ
ꢂ
2.6850(4)
2.6850(4)
87.60(4)
92.40(4)
93.53(4)
86.47(4)
92.40(4)
87.60(4)
180.0
Mn(1)–N(11)
N(1)–Mn(1)–N(1A)
N(1)–Mn(1)–N(11)
N(1A)–Mn(1)–N(11) ꢂ
N(1)–Mn(1)–N(11A) ꢂ
N(1A)–Mn(1)–N(11A)ꢂ
N(11)–Mn(1)–N(11A)ꢂ
N(1)–Mn(1)–S(1B)
N(1A)–Mn(1)–S(1B)
ꢂ
ꢂ
180.00(7)ꢂ N(11)–Mn(1)–S(1B) ꢂ
88.63(5)ꢂ N(11A)–Mn(1)–S(1B)ꢂ
91.37(5)ꢂ N(1)–Mn(1)–S(1C)
ꢂ
91.37(5)ꢂ N(1A)–Mn(1)–S(1C) ꢂ
88.63(5)ꢂ N(11)–Mn(1)–S(1C) ꢂ
180.0ꢂ N(11A)–Mn(1)–S(1C)ꢂ
86.47(4)ꢂ S(1B)–Mn(1)–S(1C) ꢂ
ꢂ
ꢂ
93.53(4)ꢂ
ꢂ
Symmetry codes for the generation of equivalent atoms: A: –xꢁ+ꢁ1,
–yꢁ+ꢁ1, –zꢁ+ꢁ1; B: xꢁ+ꢁ1, y, z; C: –x, –yꢁ+ꢁ1, –zꢁ+ꢁ1.
values than expected. As in compound 2, the octahedra are perature and in this case perfect agreement is observed
slightly distorted and the octahedral angle variance and (Fig. 5).
mean octahedral quadratic elongation values (σθ‹oct›2ꢀ=ꢀ7.30,
λoctꢀ=ꢀ1.02) indicate that the distortion of the coordination
environment is comparable to that in compound 2.
2.3 Thermoanalytical investigations
As mentioned above, the Mn(II) cations are linked
into chains by pairs of anionic ligands but the topology To check if compound 1 can be transformed into the chain
of the chains is significantly different from that of the cor- compound 3 as usually observed in such compounds,
responding 1D compounds with pyridine derivatives as measurements using simultaneous differential thermoa-
co-ligands. In these compounds the metal cations and nalysis and thermogravimetry (DTA-TG) were performed
the thiocyanate anions are always co-planar, but in com- (Fig. 6). Upon heating three poorly resolved mass steps are
pound 3, the MnN2S2 planes of neighboring cations are observed, already indicated by the DTG curve, which are
shifted relative to each other, leading to the formation accompanied with endothermic events in the DTA curve
of corrugated chains (Fig. 4: top). However, for the chain (Fig. 6). The experimental mass loss in the first and second
step of 15.3 and 15.4%, respectively, is in good agreement
with that calculated for the loss of one pyrazole molecule
in each step (Δmcalcd – 1 pyrazoleꢀ=ꢀ15.4%). In the third TG
step, the remaining two pyrazole ligands are lost leading
to the formation of Mn(NCS)2 which decomposes upon
further heating. The DTG curve shows that the third step
consists of two different processes that cannot be fully
resolved. However, the fact that only one co-ligand is
removed in the first step indicates that a compound with
the composition Mn(NCS)2(pyrazole)3 is formed, that
might correspond to the dimer 2.
To identify the intermediates of the thermal degra-
dation of compound 1 the residues formed after the first
and second TG step were isolated and analyzed by XRPD
(Fig. 7). The powder diffraction pattern after the first step
is identical with that calculated for compound 2 and that
after the second step corresponds to the chain compound
3. This is surprising, because usually such discrete com-
plexes loose two co-ligands simultaneously and are trans-
formed directly into chain or layer compounds, without
the formation of dinuclear complexes, even if the latter
are available from solution.
Fig. 4:ꢀCrystal structure of 3 with view of a single chain (top) and
along the crystallographic b axis (bottom).
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A. Jochim and C. Näther: Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexesꢀ
ꢀ5
Fig. 6:ꢀDTA, TG and DTG curves for 1 at a heating rate of 1°C min−1.
Fig. 7:ꢀExperimental XRPD patterns of the residues obtained
after the first (A) and second (C) step in the TG measurement of
compound 1, together with the pattern calculated for compounds 2
(B) and 3 (D). For compound 3 the pattern calculated from the lattice
parameters determined by a Pawley fit is shown.
Fig. 5:ꢀExperimental and calculated XRPD patterns for compounds
1, 2 and 3, the calculations being based on the single crystal data.
For compound 3, the lattice parameters obtained from a Pawley fit
of the powder pattern measured at room temperature were also
employed.
of HDCꢀ=ꢀ0.1 T. Upon cooling the product χT first does not
change significantly, but below 100 K it starts do decrease
rapidly (Fig. 8). This behavior indicates dominating anti-
ferromagnetic interactions between the Mn(II) cations
that are connected by the thiocyanate anions. This is also
shown by the values of the Weiss constant derived from
a Curie-Weiss fit leading to values of θꢀ=ꢀ–11.8 K for com-
2.4 Magnetic measurements
The magnetic properties of compounds 2 and 3 were pound 2 and θꢀ=ꢀ–27.1 K for compound 3.
investigated by susceptibility measurements in the tem-
The effective magnetic moment μeff of compound 2
perature range from 300 to 2 K applying a magnetic field at room temperature amounts to μeffꢀ=ꢀ5.92 μB, which is
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ꢀA. Jochim and C. Näther: Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes
3 Conclusions
In the present contribution, new compounds with
the compositions [Mn(NCS)2]2(pyrazole)6 (2) and
Mn(NCS)2(pyrazole)2 (3) have been prepared from reac-
tions carried out in isolution. Both compounds can also
be obtained by thermal decomposition of the known com-
pound Mn(NCS)2(pyrazole)4 (1) which upon heating is
transformed into 3 via 2 as an intermediate. The crystal
structure of [Mn(NCS)2]2(pyrazole)6 consists of dinuclear
compounds in which the two Mn(II) cations are connected
by a pair of thiocyanate anions, while compound 3 forms
chains in which the metal cations are also connected by
pairs of anionic ligands. Therefore, the structure of 1 is
strongly correlated to that of 2 and 3 and can formally be
transformed into these degradation products by stepwise
replacement of the N atoms of the co-ligand in 1 by the
thiocyanate S atoms that had not been involved in metal
coordination. It is noted that a few of such dinuclear com-
plexes have already been described in the literature, but
usually they do not occur as intermediates upon heating
of the corresponding mononuclear complexes, which
might be traced back to the influence of the kinetics of
such solid state reactions. Magnetic investigations on
compounds 2 and 3 have revealed dominating antiferro-
magnetic exchange interactions, which are also observed
in similar compounds containing pyridine derivatives and
other co-ligands. Thus the nature of the co-ligand do not
have a strong influence on the magnetic behavior of such
Mn(NCS)2 coordination compounds.
Fig. 8:ꢀTemperature dependence of the χT product for 2 (top) and 3
(bottom) at HDCꢁ=ꢁ0.1 T.
in perfect agreement with the spin only value for a high- 4 Experimental section
spin Mn(II) cation in an octahedral coordination (Sꢀ=ꢀ5/2,
gꢀ=ꢀ2.00). For compound 3 (μeffꢀ=ꢀ6.03 μB) the experimental
4.1 Synthesis
value deviates slightly, which might indicate the presence
of a minor impurity that cannot be detected by XRPD. This
4.1.1 General
is in agreement with the χ vs. T curve for 3, that shows a
maximum which is indicative of antiferromagnetic order-
Ba(NCS)2ꢀ·ꢀ3H2O and pyrazole were obtained from Alfa
ing, but on further cooling the susceptibility increases
again, pointing to a paramagnetic impurity. This has also
been observed for other Mn(NCS)2 compounds with pyri-
dine derivatives as co-ligands [55]. As mentioned above,
the majority of the 1D Mn(NCS)2 compounds reported
in the literature show dominating antiferromagnetic
exchange interactions, which indicates that the co-ligand
has only a minor influence on the overall magnetic behav-
Aesar and used without further purification. Mn(NCS)2
was prepared by the reaction of equimolar amounts of
MnSO4ꢀ·ꢀH2O and Ba(NCS)2ꢀ·ꢀ3H2O in water. The resulting
white precipitate of BaSO4 was filtered off and the fil-
trate was concentrated to complete dryness resulting in a
yellow residue of Mn(NCS)2.
ior. This is in agreement with investigations on com- 4.1.2 Syntheses of Mn(NCS)2(pyrazole)4 (1)
pounds not containing pyridine derivatives, which also
show predominately antiferromagnetic exchange interac- Mn(NCS)2 (171.2 mg, 1.00 mmol) and pyrazole (409.2 mg,
tions [30, 61, 62].
6.0 mmol) were stirred in 0.5 mL ethanol for 1 day. The
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A. Jochim and C. Näther: Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexesꢀ
ꢀ7
colorless residue was filtered off and dried in air. – Ele-
mental analysis for C14H16MnN10S2 (443.4180 g mol−1): C
4.3 X-ray powder diffraction (XRPD)
37.92, H 3.64, N 31.59, S 14.46; found C 37.72, H 3.61, N 31.67, The measurements were performed using a Stoe Trans-
S 14.24.
mission Powder Diffraction System (STADI P) with CuKα1
radiation (λꢀ=ꢀ1.540598 Å) equipped with a MYTHEN 1 K
detector from Dectris and a Ge(111) monochromator from
STOE & Cie.
4.1.3 Syntheses of [Mn(NCS)2]2(pyrazole)6 (2)
The reaction of Mn(NCS)2 (171.2 mg, 1.00 mmol) and
pyrazole (153.5 mg, 2.25 mmol) in 0.6 mL H2O yielded a 4.4 Single-crystal structure analyses
colorless powder after 1 day of stirring. It was filtered off
and dried in air. Single crystals of the compound were Data collections were performed with an imaging plate
obtained by dissolution of Mn(NCS)2 (85.6 mg, 0.50 mmol) diffraction system IPDS-2 from STOE & Cie using MoKα
and pyrazole (68.2 mg, 1.00 mmol) in 0.5 mL ethanol and radiation. Structure solution was performed with Shelxs-
slow evaporation of the solvent. – Elemental analysis for 97 [63] and structure refinement was performed against F2
C22H24MnN16S4 (750.6798 g mol−1): C 35.20, H 3.22, N 29.85, S using Shelxl-2014 [64]. A numerical absorption correc-
17.09; found C 35.35, H 3.26, N 29.94, S 17.27.
tion was applied using the programs X-Red and X-Shape
of the program package X-Area [65–67]. All non-hydro-
gen atoms were refined with anisotropic displacement
parameters. The hydrogen atoms were positioned in
idealized geometry and were refined isotropically with
4.1.4 Synthesis of Mn(NCS)2(pyrazole)2 (3)
Suitable single crystals for X-ray structure determina- Uiso(H)ꢀ=ꢀ–1.2 Ueq(C) using a riding model. Selected crystal
tion were obtained by the reaction of Mn(NCS)2 (68.2 mg, data and details of the structure refinements can be found
0.50 mmol) with pyrazole (34.1 mg, 0.50 mmol) in 0.5 mL in Table 4.
ethanol. Slow evaporation of the solvent yielded light
yellow crystals. A powder was obtained through stirring
of Mn(NCS)2 (171.2 mg, 1.00 mmol) and pyrazole (45.5 mg,
0.67 mmol) in 0.3 mL n-butanol for 3 days. – Elemental
analysis for C8H8MnN6S2 (307.2617 g mol−1): C 31.27, H 2.62,
N 27.36, S 20.87; found C 31.29, H 2.65, N 27.11, S 21.03.
Table 4:ꢀSelected crystal data and details of the structure
determinations for 2 and 3.
2
3
Formula
MW, g mol−1
Crystal system
Space group
a, Å
C22H24N16S4Mn2
750.68
Monoclinic
P21/n
C8H8N6S2Mn
307.26
Monoclinic
P21/c
4.2 Methods
9.9294(4)
11.5780(6)
14.2236(6)
92.048(3)
1634.14(13)
170(2)
5.5528(3)
6.9757(3)
15.7409(9)
95.364(4)
607.05(5)
170(2)
CHNS analysis was performed using an EURO EA elemen-
tal analyzer, fabricated by EURO VECTOR Instruments.
b, Å
c, Å
DTA-TG measurements were performed in a dynamic β, deg
V, Å3
T, K
nitrogen atmosphere in Al2O3 crucibles using a STA-
PT1600 thermobalance from Linseis. The instrument was
Z
2
2
calibrated using standard references materials. All meas-
urements were performed with a flow rate of 75 mL min−1
and were corrected for buoyancy.
D
calcd, g cm−3
1.53
1.68
μ, mm−1
θmax, deg
1.1
1.4
27.004
23075
25.991
8386
Refl. collected
Refl. unique
Rint
Min./max. transm.
Refl. [F0ꢁ>ꢁ4 σ(F0)]
Parameters
IR spectra were recorded at room temperature on a
Bruker Vertex70 FT-IR spectrometer using a broadband
spectral range extension VERTEX FM for full mid and
far IR.
3569
1190
0.1035
0.702/0.937
3147
0.0257
0.587/0.716
1113
Magnetic measurements: All magnetic measure-
200
79
ments were performed using a PPMS (Physical Property R1 [F0ꢁ>ꢁ4 σ(F0)]
0.0392
0.1079
1.074
0.0233
0.0629
1.106
wR2
Measurement System) from Quantum Design, which was
GOF
equipped with a 9 Tesla magnet. The data were corrected
Δρmax/min, e Å−3
0.36/–0.41
0.28/–0.26
for core diamagnetism.
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ꢀꢀꢀꢁ
8ꢀ ꢀA. Jochim and C. Näther: Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes
[24] T. Neumann, M. Ceglarska, M. Rams, L. S. Germann,
CCDC 1844920 (2) and 1844921 (3) contain the sup-
R. E. Dinnebier, S. Suckert, I. Jess, C. Näther, Inorg. Chem.
2018, 57, 3305.
plementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
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Z. Naturforsch.ꢃ
ꢃ2018 | Volume x | Issue x(b)
Graphical synopsis
Aleksej Jochim and Christian Näther
Formation of di- and polynuclear Mn(II)
thiocyanate pyrazole complexes in solu-
tion and in the solid state
https://doi.org/10.1515/znb-2018-0104
Z. Naturforsch. 2018; x(x)b: xxx–xxx
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