Synthesis, thermal and magnetic properties of new coordination compounds based on Mn(NCS)2 with 2-chloropyrazine and 2-methylpyrazine as neutral co-ligand

Article abstract of DOI:10.1002/zaac.201300361

Reaction of manganese(II) thiocyanate with 2-chloropyrazine leads always to the formation of a compound of composition Mn(NCS)₂(2- chloropyrazine)₄ (1-Mn/Cl) that consists of discrete complexes, in which the manganese cation is coordinated by two terminal thiocyanato anions and four 2-chloropyrazine ligands. In contrast, with 2-methylpyrazine only an aqua complex of composition Mn(NCS)₂(2-methylpyrazine)₂(H ₂O)₂ (1-Mn/CH₃) is obtained that also consists of discrete octahedrally coordinated complexes. Moreover, a few single crystals of Mn(NCS)₂(2-chloropyrazine)₄·Mn(NCS) ₂(2-chloropyrazine)₂(H₂O)₂·2- chloropyrazine trisolvate (2-Mn/Cl) and Mn(NCS)₂(2-methylpyrazine) ₂(H₂O)₂·Mn(NCS)₂(H ₂O)₄ (2-Mn/CH₃) were accidently obtained but no larger amounts are available. On heating, 1-Mn/Cl and 1-Mn/CH₃ transforms into new compounds of composition Mn(NCS)₂(L)₂ (L = 2-chloropyrazine) (4-Mn/Cl) and 2-methylpyrazine (3-Mn/CH₃). Surprisingly on further heating 1-Mn/CH₃ looses additional 2-methylpyrazine ligands and transforms into a new compound of composition Mn(NCS)₂(2-methylpyrazine) (4-Mn/CH₃). Compound 4-Mn/Cl is isotypic to its cobalt(II) analog and 4-Mn/CH₃ is isotypic to Cd(NCS)₂(2-methylpyrazine) reported recently and therefore, both structures were refined by the Rietveld method. The crystal structures of both compounds are strongly related. They consists of dimeric units, in which each two manganese cations are linked by pairs of μ-1, 3-bridging thiocyanato anions, which are further connected into layers by single μ-1, 3-bridging anionic ligands. In contrast to 4-Mn/Cl, in 4-Mn/CH₃ these layers are further linked into a 3D coordination network by the 2-methylpyrazine ligands. Magnetic measurements reveal that 1-Mn/Cl, 1-Mn/CH₃, and 3-Mn/CH ₃ shows only Curie- or Curie-Weiss paramagnetism, whereas 4-Mn/Cl and 4-Mn/CH₃ shows antiferromagnetic ordering at T_N = 22.9 K and at 26.5 K. The results of these investigations are compared with those obtained for related compounds. Copyright

Full text of DOI:10.1002/zaac.201300361

ARTICLE
DOI: 10.1002/zaac.201300361
Synthesis, Thermal and Magnetic Properties of New Coordination
Compounds based on Mn(NCS) with 2-Chloropyrazine and
2
2
-Methylpyrazine as neutral Co-Ligand
Susanne Wöhlert, Tom cˇ e Run cˇ evski, Robert E. Dinnebier,[b] and Christian Näther*[a]
[
a]
[b]
Keywords: Crystal structures; Thiocyanato coordination compounds; Thermal properties; Magnetic properties; Manganese
Abstract. Reaction of manganese(II) thiocyanate with 2-chloropyr-
azine leads always to the formation of a compound of composition
1-Mn/CH
into a new compound of composition Mn(NCS)
). Compound 4-Mn/Cl is isotypic to its cobalt(II) analog
and 4-Mn/CH is isotypic to Cd(NCS) (2-methylpyrazine) reported
recently and therefore, both structures were refined by the Rietveld
method. The crystal structures of both compounds are strongly related.
They consists of dimeric units, in which each two manganese cations
are linked by pairs of μ-1,3-bridging thiocyanato anions, which are
further connected into layers by single μ-1,3-bridging anionic ligands.
3
looses additional 2-methylpyrazine ligands and transforms
2
(2-methylpyrazine)
Mn(NCS)
2
(2-chloropyrazine)
4
(1-Mn/Cl) that consists of discrete (4-Mn/CH
3
complexes, in which the manganese cation is coordinated by two ter-
minal thiocyanato anions and four 2-chloropyrazine ligands. In con-
trast, with 2-methylpyrazine only an aqua complex of composition
3
2
Mn(NCS)
also consists of discrete octahedrally coordinated complexes. More-
over, few single crystals of Mn(NCS) (2-chloropyrazine)
Mn(NCS) (2-chloropyrazine) (H O) ·2-chloropyrazine trisolvate (2-
Mn/Cl) and Mn(NCS) (2-methylpyrazine) (H O) ·Mn(NCS) (H O)
2-Mn/CH ) were accidently obtained but no larger amounts are avail-
able. On heating, 1-Mn/Cl and 1-Mn/CH transforms into new com-
pounds of composition Mn(NCS) (L) (L = 2-chloropyrazine) (4-Mn/
). Surprisingly on further heating obtained for related compounds.
2 2 2 2 3
(2-methylpyrazine) (H O) (1-Mn/CH ) is obtained that
a
2
4
·
In contrast to 4-Mn/Cl, in 4-Mn/CH
into a 3D coordination network by the 2-methylpyrazine ligands. Mag-
netic measurements reveal that 1-Mn/Cl, 1-Mn/CH , and 3-Mn/CH
shows only Curie- or Curie-Weiss paramagnetism, whereas 4-Mn/Cl
and 4-Mn/CH shows antiferromagnetic ordering at T = 22.9 K and
at 26.5 K. The results of these investigations are compared with those
3
these layers are further linked
2
2
2
2
2
2
2
2
2
2
4
3
3
(
3
3
3
N
2
2
Cl) and 2-methylpyrazine (3-Mn/CH
3
Introduction
ligands, in which the metal cations are linked by bridging an-
ionic ligands.[
26–31]
Some of those compounds can be prepared
Investigations on the synthesis, structures, and magnetic
properties of new coordination compounds make an important
field in coordination chemistry[
in solution, other, however, are accessible only by thermal de-
composition of suitable precursor compounds.[
32,33]
The syn-
1–7]
and studies on the corre-
thesis of coordination compounds by classical solid state meth-
lation between the composition and the structures of such
compounds and their magnetic properties are of special inter-
ods is not unusual and different methods are reported in litera-
ture.[
34–37]
In the course of our investigations, several new
[
8–13]
est.
compounds were prepared, some of them showing a slow re-
In this context, thio- and selenocyanato coordination com-
pounds are of special interest because of the dependency of
the magnetic behavior on the coordination mode and the nature
of the metal cations, e.g. cooperative magnetic phenomena and
spin crossover.[
laxation of the magnetization.[
38–42]
Such compounds are of
special importance because of the potential for future practical
applications.[
43–47]
Following our approach, 1D and 2D com-
14–25]
pounds can be selectively prepared by using mono- or biden-
In the focus of our research are the magnetic properties of tate N-donor co-ligands, which allows to study the influence
transition metal thio- or selenocyanato coordination com- of the structure on the magnetic properties in more detail.
pounds based on Mn, Fe, Co, and Ni and different N-donor
Recently we reported new coordination polymers based on
Mn(NCS)2 and pyridine, 1,2-bis(4-pyridyl)-ethylene (4-bpe)
*
Prof. Dr. C. Näther
[48–50]
and 1,2-bis(4-pyridyl)-ethane (4-bpa).
In these structures
Fax: +49-431-8801520
E-Mail: cnaether@ac.uni-kiel.de
the metal cations are linked by pairs of μ-1,3-bridging thiocy-
anato anions forming chains, which unlike in the case of the
pyridine compound, are connected into layers. Magnetic mea-
surements reveal that for all of the compounds antiferromag-
netic ordering is observed. To study the influence of the top-
ology of the thiocyanato network on the magnetic properties
in more detail, we tried to prepare the corresponding com-
pounds with 2-chloro- and 2-methylpyrazine as neutral co-li-
[
[
a] Institut für Anorganische Chemie
Christian-Albrechts-Universität zu Kiel
Max-Eyth-Straße 2
24118 Kiel, Germany
b] Max-Planck-Institute for Solid State Research
Heisenbergstraße 2
70569 Stuttgart, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300361 or from the au-
thor.
2
648
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 639, (14), 2648–2656

2
Coordination Compounds based on Mn(NCS) with 2-Chloropyrazine and 2-Methylpyrazine
gands. It should be noted that in the structures of similar com- Crystal Structures of 1-Mn/Cl, 1-Mn/CH , 2-Mn/Cl, and
3
II
II
II
pounds based on Fe , Co , and Ni thiocyanates, surprisingly, 2-Mn/CH3
instead of linear chains, a 2D thiocyanato network is formed,
The compound 1-Mn/Cl crystallizes in the monoclinic space
a very rare and unusual observation.[
51–54]
In this context, the
group P2 /n with two formula units in the unit cell. The asym-
1
question arises whether Mn(NCS) will form similar 2D net-
2
metric unit consists of one manganese(II) cation located on a
center of inversion and one thiocyanato anion as well as two
-chloropyrazine ligands in general positions. Each cation is
coordinated by two terminal N-bonded thiocyanato anions and
four N-bonded neutral co-ligands into discrete complexes (Fig-
ure 1 left). It should be noted that only the nitrogen atom of
the co-ligand that is not adjacent to the bulky chlorine substitu-
work with these ligands and how this will influence the mag-
netic properties of these compounds. Herein we report on these
investigations.
2
Results and Discussion
ent is involved in metal coordination. The MnN distances are
Synthesis
6
in the range of 2.144(3) Å to 2.345(3) Å with angles around
the manganese(II) cation of 87.24(9)° to 92.76(9)° and 180°
(see Table S1, Supporting Information).
At the beginning of our investigations, different molar ratios
of Mn(NCS) and 2-chloropyrazine or 2-methylpyrazine (1:4,
2
1
:2, 1:1, 2:1, 4:1) were stirred in water, methanol, ethanol, and
acetonitrile at room-temperature and the products were investi-
gated by X-ray powder diffraction. Independent on the actual
stoichiometry and the solvent used in the synthesis, only one
compound with 2-chloropyrazine (1-Mn/Cl) and one with 2-
methylpyrazine (1-Mn/CH ) were obtained. The structures of
3
these compounds were found not to be isotypic. Elemental
analysis reveal that the composition of 1-Mn/Cl is
Mn(NCS) (2-chloropyrazine) and that the ratio between
2
4
Mn(NCS) and 2-methylpyrazine is 1:2:2 in 1-Mn/CH . The
2
3
asymmetric CN stretching vibration observed in the IR spec-
–
1
–1
trum was found at 2067 cm for 1-Mn/Cl and at 2079 cm
for 1-Mn/CH indicating that only terminal N-bonded thiocy-
3
anato anions are present (see Figures S1 and S2, Supporting
Information). From these investigations there are no hints for Figure 1. View of the coordination spheres in 1-Mn/Cl (left) and 1-
Mn/CH
3
(right; black = manganese, dark-grey = sulfur / chlorine, grey
the occurrence of additional compounds, in which the manga-
nese cations are linked by bridging thiocyanato anions.
Single crystals of both compounds were prepared and char-
acterized by single-crystal X-ray analysis. The bulk material of
=
nitrogen, light-grey = carbon, white = hydrogen). ORTEP plots of
both compounds can be found in Figures S6 and S7 (Supporting Infor-
mation).
1
-Mn/CH was shown to be phase pure (Figure S3, Supporting
The compound 1-Mn/CH crystallizes in the triclinic space
3
3
¯
Information). However, some of the powder patterns of 1-Mn/ group P1 with one formula in the asymmetric unit. One man-
Cl showed additional reflections, especially if stored at ambi- ganese(II) cation is located on a center of inversion, whether
ent conditions, indicating the presence of an additional crystal- the thiocyanato anions, the 2-methylpyrazine ligand, and the
line phase, which gains in amount when 1-Mn/Cl is exposed water molecule are on a general position. In the crystal struc-
to the atmosphere. By storing the powder for a longer period ture each manganese(II) cation is coordinated by two terminal
of time it transforms completely into a hydrate phase (3-Mn/ N-bonded thiocyanato anions and two 2-methylpyrazine li-
Cl) with an approximate composition of Mn(NCS) (2-chloro- gands as well as two O-bonded water molecules (Figure 1
2
pyrazine) (H O) . The trials for solving the crystal structure, right). The MnN O octahedra are slightly distorted with dis-
2
2
x
4 2
so far, did not resulted in solution, however, the phase was tances in the range of 2.172(2) Å to 2.3131(17) Å and angles
indexed in a monoclinic unit cell (space group P2 /c) and a = around the metal(II) cation ranging from 88.14(9)° to
1
16.879(5) Å, b = 9.854(3) Å, c = 15.039(6) Å, β = 83.53(1)° 91.86(9)° and 180° (see Table S2, Supporting Information).
(
see Figure S4, Supporting Information). IR investigations The discrete complexes are connected through intermolecular
–
1
–1
shows two bands at 2064 cm and 2082 cm indicating that OH···S hydrogen bonding [3.2607(19) Å] into chains, which
only terminal coordinated thiocyanato anions are present (see are elongate in the direction of the crystallographic a axis.
Figure S5, Supporting Information). Moreover, a broad band These chains are further connected into layers through inter-
–
1
is observed in the region between 3000 and 3500 cm indicat- molecular OH···N(2-methylpyrazine) hydrogen bonding
ing that water is present.
[2.8223(2) Å] (see Figure S8, Supporting Information).
Within these investigations, crystals of two further com-
The compound 2-Mn/Cl crystallizes in the triclinic space
¯
pounds of composition Mn(NCS) (2-chloropyrazine) · group P1 with one formula unit in the unit cell. The asymmet-
2
4
Mn(NCS) (2-chloropyrazine) (H O) ·2-chloropyrazine
tri- ric unit consists of two crystallographically independent man-
2
2
2
2
solvate (2-Mn/Cl) and Mn(NCS) (2-methylpyrazine) (H O) · ganese(II) cations located on centers of inversion. One
2
2
2
2
Mn(NCS) (H O) (2-Mn/CH ) were obtained by accident.
metal(II) cation is coordinated by two terminal N-bonded
2
2
4
3
Z. Anorg. Allg. Chem. 2013, 2648–2656
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C. Näther et al.
ARTICLE
thiocyanato anions, and four 2-chloropyrazine ligands and the studied by simultaneous thermogravimetry and differential
second metal(II) cation is coordinated by two terminal N- thermoanalysis. On heating to 300 °C two mass loss steps are
bonded thiocyanato anions, two 2-chloropyrazine ligands, and observed for 1-Mn/Cl and three for 1-Mn/CH , accompanied
3
two water molecules (see Figure S9, Supporting Information). with respective endothermic events in the DTA curve (Fig-
The Mn N O octahedra are slightly distorted with distances ure 3).
2
10 2
ranging from 2.131(2) Å to 2.370(2) Å and angles around the
manganese(II) cations in the range of 87.98(7)° to 92.02(7)°,
and of 180° (see Table S3, Supporting Information). In the
crystal structure cavities are found between the discrete com-
plexes, in which additional non-coordinating 2-chloropyrazine
ligands are present. One of these ligands is on a general posi-
tion, whereas the second is disordered on a center of inversion.
The discrete complexes are connected through intermolecular
O–H···N hydrogen bonding [2.808(3) Å and 2.884(3) Å] into a
3D coordination network.
The compound 2-Mn/CH3 crystallizes in the tetragonal
space group P4 with four formula units in the unit cell. The
3
asymmetric unit consists of two crystallographically indepen-
dent manganese(II) cations, one coordinated by two terminal
N-bonded thiocyanato anions, two 2-methylpyrazine ligands,
and two O-bonded water molecules and the second one coordi-
nated by two terminal N-bonded thiocyanato anions and four
O-bonded water molecules (Figure 2). All atoms are located
on a general position. The Mn N O octahedra are slightly dis-
Figure 3. DTG, TG, and DTA curves for 1-Mn/Cl (left) and 1-Mn/
–
1
CH
3
(right). Heating rate 4 K·min , N
2 2 3
atmosphere, Al O crucible,
2
6 6
Δm = mass loss /%, T
P
= peak temperature /°C.
torted with distances ranging from 2.153(3) Å to 2.296(3) Å
and angles around the manganese(II) cations in the range of
The experimental mass loss of Δmexp = 35.7% in the first
and Δmexp = 36.2% in the second step of 1-Mn/Cl are in
agreement with that calculated for the removal of two 2-chlo-
ropyrazine ligands in each step (Δmcalc = 36.4%). These re-
sults indicate that in the first heating step a compound of com-
position Mn(NCS) (2-chloropyrazine) (4-Mn/Cl) is formed,
85.06(11)° to 94.57(12)° and 177.19(15)° to 178.34(11)° (see
Table S4, Supporting Information). In the crystal structure the
manganese(II) octahedra are connected through intermolecular
hydrogen bonding into a 3D coordination network (see Table
S5, Supporting Information).
2
2
which decomposes into manganese thiocyanate in the second
step. The experimental mass loss of Δmexp = 9.2% for 1-Mn/
CH is in agreement with that calculated for the removal of
3
two water molecules in the first heating step (Δmcalc = 9.11%).
These results indicate that in the first TG step a new 1:2 com-
pound of composition Mn(NCS) (2-methylpyrazine) (3-Mn/
2
2
CH ) is formed. The experimental mass loss of Δm
=
3
exp
23.5% in the second step is in very good agreement with the
loss of one 2-methylpyrazine (Δmcalc = 23.8%). Therefore it
can be assumed that the intermediate 3-Mn/CH transforms
3
into a new 1:1 compound of composition Mn(NCS) (2-methyl-
2
pyrazine) (4-Mn/CH ) whether on further heating that decom-
3
poses into manganese(II) thiocyanate.
Similar investigations on the hydrate 3-Mn/Cl show that on
heating water is removed leading to the formation of a com-
pound of composition Mn(NCS) (2-chloropyrazine) (4-Mn/
2
2
3
Figure 2. View of the coordination sphere in 2-Mn/CH (black = man-
ganese, dark-grey = sulfur / oxygen, grey = nitrogen, light-grey = car-
bon, white = hydrogen). An ORTEP plot can be found in Figure S10
Cl) (see Figure S11, Supporting Information).
To verify the nature of the intermediate additional TG ex-
periments were performed and stopped after the first and sec-
ond TG step and the obtained residues were investigated by
elemental analysis and IR spectroscopy (see Figures S12–S14,
Supporting Information). For the 2-chloropyrazine compound
(Supporting Information).
Thermoanalytical Investigations
4
-Mn/Cl the asymmetric CN stretching vibration is observed
–1
In order to investigate whether the compounds with μ-1,3- at 2095 cm indicative for μ-1,3-bridging thiocyanato anions.
bridging thiocyanato anions can be obtained by thermal de- Surprisingly for the 2-methylpyrazine-deficient compound 3-
composition of 1-Mn/Cl and 1-Mn/CH both of them were Mn/CH that exhibit the same stoichiometry as 4-Mn/Cl two
3
3
2
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2
Coordination Compounds based on Mn(NCS) with 2-Chloropyrazine and 2-Methylpyrazine
bands at 2049 cm–1 and 2034 cm–1 are observed, which
strongly indicates that only terminal N-bonded thiocyanato
anions are present. Finally, for 4-Mn/CH ν (CN) is observed
3
as
–
1
at 2099 cm , which is characteristic for μ-1,3-bridging thiocy-
anato anions.
Compound 4-Mn/Cl was obtained as microcrystalline pow-
der with good level of crystallinity. Its crystal structure was
found to be isotypic to the recently reported structure of
[52]
Co(NCS) (2-chloropyrazine) .
A Rietveld refinement was
2
2
performed and the final plot is given in Figure 4.
3
Figure 5. Scattered X-ray intensities of 4-Mn/CH as a function of
diffraction angle at ambient conditions. The observed pattern (dia-
monds) measured in Debye-Scherrer geometry, the best Rietveld fit
profile (line) and the difference curve between the observed and the
calculated profiles (below) and the Bragg reflection positions are
shown (wavelength = 1.540596 Å).
Crystal Structures of 4-Mn/Cl and 4-Mn/CH3
As mentioned above, 4-Mn/Cl is isotypic to its iron and
cobalt analogs, whereas 4-Mn/CH is isotypic to the corre-
3
51]
sponding cadmium compound.[
Therefore, their crystal
structures were refined by the Rietveld method (see Experi-
mental Section). Because the structures of these compounds
Figure 4. Scattered X-ray intensities of 4-Mn/Cl as a function of dif-
fraction angle at ambient conditions. The observed pattern (diamonds)
measured in Debye-Scherrer geometry, the best Rietveld fit profile
(
line) and the difference curve between the observed and the calculated are already known only the most important features are sum-
profiles (below) and the Bragg reflection positions are shown (wave- marized below. In both compounds the metal cations are octa-
length = 0.7093 Å).
hedrally coordinated by two sulfur and two nitrogen atoms of
thiocyanato anions, as well as by two nitrogen atoms of the N-
donor ligands (Figure 6 and Figure S16, Supporting Infor-
mation).
The powder pattern of 3-Mn/CH indicates that this com-
pound has very low crystallinity; being characterized by few
broad reflection (see Figure S15, Supporting Information).
3
Interestingly, the powder pattern is very similar to that of
M(NCS) (2-methylpyrazine) (M = Fe, Co), indicating that the
2
2
structures of these compounds are isotypic.[ However, as in
the case of the iron and the cobalt compounds, the powder
pattern cannot be indexed and the structure of this intermediate
remains to be unknown.
52]
The next thermal product, 4-Mn/CH , exhibits excellent
3
crystallinity and its structure is isotypic to the reported struc-
[51]
ture of Cd(NCS) (2-methylpyrazine) (Figure 5). In this con-
2
text, it should be noted, that the formation of this intermediate
with very low content of an N-donor ligand is quite unusual
and was never observed before (mostly because metal cations
like e.g. Mn, Fe, Co, and Ni are less chalcophilic and prefer
only terminal bonding of the anionic ligands). In this case the
formation of this compound is enforced by thermal decomposi-
tion and, as our results indicate, this compound cannot be ob-
tained in solution. This is unlike similar compounds with cad-
mium because this metal cation is much more chalcophilic and
therefore, such compounds are of extremely importance for the
Figure 6. One layer of manganese(II) cations bridged by thiocyanato
ligands in infinite chains in the crystal structures of 4-Mn/Cl and 4-
Mn/CH . Please note that the N-donor co-ligands are omitted for clar-
3
ity (black = manganese, dark-grey = sulfur, grey = nitrogen, light-grey
= carbon).
structure determination of their paramagnetic counterparts as
shown recently.[
55,56]
The crystal structure of 4-Mn/CH was
3
refined using the Rietveld method and the final refinement plot
is presented in Figure 5.
Z. Anorg. Allg. Chem. 2013, 2648–2656
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2651

C. Näther et al.
ARTICLE
Surprisingly, in both of them, an identical topology of the magnetism is found (see Figure S17–S19, Supporting Infor-
thiocyanato coordination network is observed. This topology mation). The fitting of the magnetic curves following the
is rather rare, and normally it is not observed in this type of Curie-Weiss law, gives Weiss constant of θ = –0.80 K for 1-
coordination polymers. In the structures two manganese cat- Mn/Cl, θ = –0.02 K for 1-Mn/CH , and θ = –1.30 K for 3-
3
ions are linked by pairs of μ-1,3-bridging thiocyanato anions Mn/CH , which are very close to zero. The effective magnetic
3
into dimers, which are further linked by four single μ-1,3- moments μeff for 1-Mn/Cl (5.97 μ ), 1-Mn/CH (6.06 μ ),
B
3
B
bridging anionic ligands, forming infinite layers.
and 3-Mn/CH (6.02 μ ) are a bit higher than the spin-only
3 B
In the structure of 4-Mn/Cl the 2-chloropyrazine co-ligand value in the high-spin state of Mn2+ (S = 5/2, g = 2). These
is coordinated only by the nitrogen atom, which is not adjacent values are in agreement with the room-temperature values re-
1/2
to the bulky chlorine atom. Therefore, this compound consists trieved from the (8χ T) vs. temperature curve, which also
M
of a 2D coordination network (Figure 7 top). On the other shows that in all compounds antiferromagnetic interactions are
hand, in the case of 4-Mn/CH the manganese thiocyanato involved. In this context it is noted that the results obtained
3
layers are linked by bridging 2-methylpyrazine ligands into a for 3-Mn/CH strongly support the results of the IR measure-
3
3D coordination network (Figure 7 bottom).
ments and prove that in this compound only terminal N-
bonded anionic ligands are present.
The magnetic measurements on 4-Mn/Cl and 4-Mn/CH3
show maxima in the χM vs. T curve at T = 22.9 K for 4-Mn/
N
Cl and T = 26.5 K for 4-Mn/CH indicative for antiferromag-
N
3
netic ordering (Figure 8).
3
Figure 7. Crystal structure of 4-Mn/Cl (top) and of 4-Mn/CH (bot-
tom) with view along the crystallographic b axis (black = manganese,
dark-grey = sulfur / chlorine, grey = nitrogen, light-grey = carbon).
Magnetic Investigations
Figure 8. χ
Mn/Cl (top) and 4-Mn/CH
M
and (8χ
M
T)1/2 (inset) as function of temperature for 4-
(bottom) at HDC = 1 kOe.
3
In order to investigate the magnetic properties of all com-
pounds the temperature dependence of the susceptibility was
Fitting the magnetic data according to the Curie-Weiss law
studied applying a magnetic field of HDC = 1 kOe in the tem- gives a strong negative Weiss constant of θ = –45.8 K for 4-
perature range from 300 to 2 K. For the compounds 1-Mn/Cl, Mn/Cl and θ = –41.2 K for 4-Mn/CH , which is in agreement
3
1/2
1
-Mn/CH , and 3-Mn/CH only Curie or Curie-Weiss para- with the (8χ T) vs. temperature curve that prove antiferro-
3
3
M
2
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2
Coordination Compounds based on Mn(NCS) with 2-Chloropyrazine and 2-Methylpyrazine
magnetic interactions. To exclude metamagnetic behavior an nate coordination polymers based on 2-chloropyrazine and 2-
initial curve was measured for both compounds at T = 2 K methylpyrazine were reported. Two new compounds with μ-
in the range of 0–9 kOe, which show linear increasing values 1,3-bridging thiocyanato anions, which cannot be synthesized
typically for antiferromagnetic compounds (see Figures S20 in solution, were prepared using the solid state route, showing
and S21, Supporting Information).
the importance of thermal decomposition reactions for the
It should be noted that in 4-Mn/Cl the observed increase of preparation of compounds with more condensed thiocyanato
the susceptibility at low temperatures might be a hint for networks.
canted antiferromagnetism or a paramagnetic impurity, which
Interestingly, the compounds with the bridging anionic li-
were not detected by X-ray powder diffraction. Therefore ad- gands consist of a 2D thiocyanato network, which is not very
ditional AC measurements were performed and no signal in common and which is completely different from that fre-
the imaginary part (χ ЈЈ) is observed, which means that spin- quently found in compounds with similar co-ligands and iden-
M
canting behavior can be excluded (see Figure S22, Supporting tical ratio between Mn(NCS) and the N-donor ligand. Surpris-
2
Information). In this context it is noted that a different batch ingly all of the compounds with μ-1,3-bridging anions shows
that was stored for some time at room-temperature show only antiferromagnetic interactions and antiferromagnetic ordering,
paramagnetic behavior (see Figure S23, Supporting Infor- which proves that magnetic properties does not strongly de-
mation). X-ray powder diffraction of this product proves that pend on the composition of such compounds and of the top-
4-Mn/Cl is unstable at ambient conditions and transforms into ology of the thiocyanato coordination network.
the hydrate 3-Mn/Cl (see Figure S24, Supporting Infor-
mation).
As mentioned above, these investigations were performed in
Experimental Section
the scope of investigation of the magnetic properties of com- Materials: MnSO
azine, and Ba(NCS)
used without further purification. Mn(NCS)
action of equimolar amounts of MnSO ·2H
water. The resulting precipitate of BaSO was filtered off and the fil-
trate was concentrated to complete dryness resulting in a white residue
of Mn(NCS) . The purity was checked by XRPD and elemental analy-
4
·2H
2
O, KNCS, 2-chloropyrazine, 2-methylpyr-
O were obtained from Alfa Aesar and were
were prepared by the re-
O and Ba(NCS) ·3H O in
·3H
2
pounds of composition Mn(NCS) (L) with L being different
2
2
2
2
co-ligands. The compounds with pyridine, 4-bpe, and 4-bpa
consist of linear manganese thiocyanato chains and all of them
4
2
2
2
4
show strong antiferromagnetic interactions and antiferromag-
netic ordering on cooling.[
data is given in Table 1.
48–50]
Comparison of the magnetic
2
sis. All crystalline powders were prepared by similar reaction condi-
tions and stirring for 3 d. The obtained residues were filtered off and
Table 1. Comparison of selected magnetic data (at HDC = 1 kOe) for
-Mn/Cl, 4-Mn/CH , Mn(NCS) (pyridine) , Mn(NCS)
(4-bpe) [4-bpe 1,2-bis(4-pyridyl)-ethylene] and was checked by XRPD and elemental analysis.
4(84–-5b0]pa) [4-bpa = 1,2-bis(4-pyridyl)-ethane] retrieved from
4
3
2
2
(pyridazine), washed with water and diethyl ether and dried in vacuo. The purity
2
Mn(NCS)
Mn(NCS)
2
=
2
literature.[
Synthesis of 1-Mn/Cl: Single crystals suitable for X-ray structure de-
termination were obtained by the reaction of Mn(NCS) (25.6 mg,
.15 mmol) and 2-chloropyrazine (52.8 μL, 0.6 mmol) in water (1 mL)
2
T
N
/K
θ /K
0
Mn(NCS)
Mn(NCS)
Mn(NCS)
Mn(NCS)
2
(pyridine)
(4-bpe)
(4-bpa)
2
23.5
26
24
14
22.9
26.5
–37.3
–34.7
–39.3
–25.4
–45.8
–41.2
in a closed snap cap vial. Yellow block-shaped single crystals were
obtained after one week at room-temperature. Yield based on
2
2
2
Mn(NCS)
4.36, H 1.92, N 22.26, S 10.19%; found C 34.31, H 1.90, N 22.22,
S 10.21%. IR (ATR): ν˜ max = 3091 (w), 2099 (w), 2068 (w), 2067 (s),
577 (w), 1516 (m), 1460 (m), 1380 (m), 1288 (m), 1206 (w), 1137
m), 1135 (s), 1058 (s), 1016 (s), 917 (m), 844 (s), 812 (s), 766 (m),
2 2
: 163 mg (86.3%). C18H12MnN10S (629.24): calcd. C
(pyridazine)
3
4
-Mn/Cl
4-Mn/CH
3
1
(
7
Although the compounds with 2-methyl- and 2-chloropyr-
azine show a completely different topology of the thiocyanato
coordination network, strong antiferromagnetic interactions
–
1
34 (m), 635 (m), 489 (s), 435 (m), 409 (s) cm (see Figure S1,
Supporting Information).
and antiferromagnetic ordering is observed, which clearly Synthesis of 1-Mn/CH : Single crystals suitable for X-ray structure
3
proves that the magnetic properties of such compounds does determination were obtained by the reaction of Mn(NCS)
2
(25.6 mg,
.15 mmol) and 2-methylpyrazine (27.4 μL, 0.3 mmol) in water
1 mL) in a closed snap cap vial. Yellow block-shaped single crystals
were obtained after 3 d at room-temperature. Yield based on
Mn(NCS) : 887 mg (74.8%). C12 16MnN (395.36): calcd. C
6.46, H 4.08, N 21.26, S 16.22%; found C 36.51, H 3.98, N 21.47,
S 16.18%. IR (ATR): ν˜ max = 3330 (br), 3167 (br), 2079 (s), 1645 (m),
519 (m), 1477 (m), 1436 (m), 1406 (m), 1386 (m), 1297 (m), 1161
w), 1070 (m), 1027 (m), 978 (m), 941 (m), 844 (s), 788 (m), 745 (m),
0
not dependent on the structure of the thiocyanato network, and
it can be speculated that because of that antiferromagnetism is
always observed for similar compounds. This is also indicated
by the recently reported magnetic investigations on
(
2
H
6 2 2
O S
3
[57]
Mn(NCS) (pyridazine).
Even though the structure of this
2
compound is still unknown, the IR spectroscopic investigations
clearly prove that the metal cations are linked by the thiocyan-
ato ligands and magnetic measurements shows that this com- 663 (m), 603 (br), 477 (m), 413 (s) cm–1 (see Figure S2, Supporting
1
(
pound is an antiferromagnet.
Information).
Synthesis of 2-Mn/Cl: Single crystals suitable for X-ray structure de-
termination were obtained by the reaction of Mn(NCS) (25.6 mg,
2
Conclusions
In the presented contribution, investigations on the synthe- 0.15 mmol) and 2-chloropyrazine (137.0 μL, 1.5 mmol) without sol-
sis, thermal and magnetic properties of manganese(II) thiocya- vent. Yellow block-shaped single crystals were obtained after 2 d.
Z. Anorg. Allg. Chem. 2013, 2648–2656
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2653

C. Näther et al.
ARTICLE
Synthesis of 2-Mn/CH
3
: Single crystals suitable for X-ray structure (m), 659 (m), 476 (m), 435 (s) cm–1 (see Figure S14, Supporting Infor-
determination were obtained by the reaction of Mn(NCS)
.15 mmol) and 2-methylpyrazine (13.7 μL, 0.15 mmol) in ethanol
1 mL) in a closed test-tube at 120 °C. Yellow block-shaped single Single Crystal Structure Analysis: Single crystal data collections
crystals were obtained on cooling after two weeks.
were carried out with an imaging plate diffraction system (Stoe IPDS-
) with Mo-K radiation. The structures were solved with direct meth-
Elemental Analysis and IR Data of the Residue obtained in the ods using SHELXS-97 and structure refinements were performed
2
(25.6 mg,
mation).
0
(
1
α
2
[58]
First TG Step by Thermal Decomposition of 1-Mn/Cl:
MnN (400.17): calcd. C 30.01, H 1.51, N 21.00, S 16.03%;
found C 30.05, H 1.50, N 20.98, S 16.05% IR (ATR): ν˜ max = 3076
against F using SHELXL-97. Numerical absorption correction was
C
10
H
6
6
S
2
applied using programs X-RED and X-SHAPE of the program package
[
59–61]
X-Area.
displacement parameters. All hydrogen atoms were positioned with
w), 1173 (w), 1136 (s), 1056 (s), 1015 (s), 949 (w), 918 (w), 840 (s), idealized geometry and were refined isotropic with Uiso(H) =
All non hydrogen atoms were refined with anisotropic
(w), 2095 (s), 1575 (w), 1516 (m), 1448 (m), 1389 (s), 1284 (w), 1207
(
7
–
1
69 (m), 735 (m), 639 (m), 439 (m), 474 (m), 438 (m), 415 (s) cm
–1.2 Ueq(C) (1.5 for methyl hydrogen atoms) using a riding model.
The O–H hydrogen atoms were located in a difference map, their bond
lengths were set to ideal values and finally they were refined using a
(see Figure S12, Supporting Information).
Elemental Analysis and IR Data of the Residue obtained in the riding model with Uiso(H) = –1.5 U (O). The crystal of compound
eq
First TG Step by Thermal Decomposition of 1-Mn/CH
12MnN (359.33): calcd. C 40.11, H 3.37, N 23.39, S 17.85%;
found C 39.63, H 3.34, N 23.25, S 17.93%. IR (ATR): ν˜ max = 2049
3
:
1-Mn/Cl is non-merohedrally twinned. Both individuals were indexes
separately and from the orientation matrices the twin matrix was calcu-
lated (0 0 –1 0 –1 0 –1 0 0). Afterwards symmetry related reflections
were merged and a data file in HKLF-5 format was calculated and
used in the refinement (BASF: 0.26253). The crystal of 2-Mn/CH3
was racemically twinned and therefore, a twin refinement was per-
formed (BASF parameter: 0.2392). Details of the structure determi-
nation are given in Table 2.
C
12
H
6 2
S
(
(
(
s), 2034 (s), 1603 (w), 1516 (m), 1482 (m), 1440 (m), 1389 (m), 1304
m), 1258 (m), 1182 (m), 1152 (m), 1077 (m), 1033 (m), 985 (w), 964
w), 829 (m), 742 (m), 660 (m), 483 (m), 421 (s) cm (see Figure
–1
S13, Supporting Information).
Elemental Analysis and IR Data of the Residue obtained in the
Second TG Step by Thermal Decomposition of 1-Mn/CH
MnN (265.22): calcd. C 31.70, H 2.28, N 21.12, S 24.18%;
found C 31.81, H 2.23, N 21.20, S 24.34%. IR (ATR): ν˜ max = 2099
3
:
X-ray Powder Diffraction (XRPD): The data collection of 1-Mn/Cl,
C
7
H
6
4
S
2
1-Mn/CH
with a PANalytical X’Pert Pro MPD reflection powder diffraction sys-
tem with Cu-K radiation (λ = 0.15406 Å) equipped with a PIXcel
m), 1189 (w), 1159 (m), 1083 (m), 1029 (m), 985 (w), 830 (m), 786 semiconductor detector from PANanlytical. The data collection of
3 3 3
, 3-Mn/CH , 4-Mn/Cl, and 4-Mn/CH were performed
(
(
s), 2091 (s), 1518 (w), 1485 (m), 1438 (m), 1390 (m), 1302 (m), 1257
α
Table 2. Selected crystal data and details on the structure refinements. Please note that the structure of 4-Mn/Cl and 4-Mn/CH
3
were determined
by Rietveld refinements and the values of the figures of merit are as defined in TOPAS 4.2.
1
-Mn/Cl
1-Mn/CH
3
2-Mn/Cl
2-Mn/CH
3
4-Mn/Cl
Cl
400.17
monoclinic
P2 /c
4-Mn/CH
MnN
265.22
monoclinic
P2 /n
3
Formula
MW /g·mol–1
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
C
18
H12Cl
4
MnN10
S
2
C
12
H16MnN
6
O
2
S
2
C
40
H31Cl
9
Mn
2
N
22
O
2
S
4
C
14
H24Mn
2
N
8
O
6
S
4
C
10
H
6
2
MnN
6
S
2
C
7
H
6
4 2
S
629.24
monoclinic
P2 /n
395.37
638.53
tetragonal
triclinic
triclinic
¯
¯
1
P1
P1
P4
3
1
1
12.1305(9)
7.1695(3)
14.639(1)
90
90.942(9)
90
1273.0(1)
200
2
1.642
0.71073
1.132
27.07
2729
2729
0.0381
–
7.004(1)
8.255(1)
9.317(1)
109.13(2)
111.33(22)
99.32(2)
449.2(1)
293
10.5531(9)
11.2649(11)
12.6071(11)
85.047(11)
84.632(10)
87.936(11)
1486.0(2)
200
13.545(1)
13.545(1)
15.005(2)
90
90
90
2753.2(3)
200
4
1.540
0.71073
1.263
25.97
26326
5390
0.0662
–
10.761(25)
9.570(21)
15.854(33)
90
96.92(12)
90
1620.82(1)
293
4
1.615
0.7093
–
38
1365
–
8.469(19)
9.433(24)
12.867(27)
90
94.90(12)
90
1024.15(2)
293
γ /°
V /Å3
T /K
Z
D
1
1
4
calc /mg·m3
1.461
0.71073
0.983d
27.00
3881
1900
0.0317
–
1.575
0.71073
1.026
26.00
15111
5709
0.0313
–
–
–
1.612
1.540596
–
60
303
–
–
1.488
2.317
1.787
–
λ /Å
μ /mm–1
θmax /°
Measured refl.
Unique refl.
R
int
–
R
exp
3.689
5.908
4.594
–
R
wp
–
–
2216
–
–
1526
–
–
4723
R
p
Refl. with
Ͼ 4σ(F
Parameters
[F Ͼ 4σ(F
(all refl.)
GOF
4793
F
o
o
)
162
)] 0.0420
108
365
310
70
–
–
1.601
–
62
–
–
1.558
–
R
1
o
o
0.0332
0.0935
1.025
0.0392
0.1055
1.050
0.0370
0.0925
0.997
wR
2
0.1413
1.115
1.033/–0.450
Δρmax/min /e·Å–3
0.290 / –0.464
1.594 / –1.063
0.313 / –0.391
2
654
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2648–2656

2
Coordination Compounds based on Mn(NCS) with 2-Chloropyrazine and 2-Methylpyrazine
1
-Mn/Cl, 1-Mn/CH
formed by Stoe transmission powder diffraction system (STADI-P)
with Cu-K radiation (λ = 154.0598 pm) that was equipped with a
3
, 3-Mn/CH
3
, 4-Mn/Cl, and 4-Mn/CH
3
were per-
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Rietveld Refinements: Rietveld refinement
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background coefficients (Chebyshev polynomials), unit cell param-
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[
61]
Selected crystallographic data are listed
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this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
[
[
[
[
[
[
[
[
[
[
[
numbers CCDC-957591 (1-Mn/CH
3
), -957592 (1-Mn/Cl), -957593
), -957594 (2-Mn/Cl), -957595 (4-Mn/CH ) and -957596
4-Mn/Cl) (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk,
(2-Mn/CH
3
3
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(
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2 3
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Netzsch. The instrument was calibrated using standard references ma-
terials. All measurements were performed with a heating rate of
–1
4
K·min–1 and a low rate of 75 mL·min .
Magnetic Measurements: All magnetic measurements were per-
formed with a PPMS (Physical Property Measurement System) from
Quantum Design, which was equipped with a 9 Tesla magnet. The data
were corrected for core diamagnetism.
2
006, 2006, 1381.
Supporting Information (see footnote on the first page of this article):
[
[
[
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IR spectra for compounds 1-Mn/Cl, 1-Mn/CH
3
, 3-Mn/Cl, 4-Mn/Cl,
. ORTEP plots of 1-Mn/Cl, 1-Mn/CH
, 2-Mn/Cl, experimental XRPD pattern of the residue in
. Crystal structures of 4-Mn/Cl,
magnetic measurements of 1-Mn/Cl, 1-Mn/CH
, 4-Mn/Cl, 4-Mn/CH
3
2
-Mn/CH
-Mn/CH
3
, 4-Mn/CH
3
3
,
3
the first heating step of 1-Mn/CH
3
4
3
-Mn/CH
-Mn/CH
3
,
3
,
3
3
.
[
[
Acknowledgements
[34] S. L. James, C. J. Adams, C. Bolm, D. Braga, P. Collier, T.
Friscic, F. Grepioni, K. D. M. Harris, G. Hyett, W. Jones, A.
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This project was supported by the Deutsche Forschungsgemeinschaft
Project No. Na 720/3–1) and the State of Schleswig-Holstein. We
(
[
35] C. J. Adams, M. A. Kurawa, M. Lusi, A. G. Orpen, Crys-
thank Prof. Dr. Wolfgang Bensch for access to his experimental facili-
ties. Special thanks to Inke Jess for the single crystal measurements
and Maren Rasmussen as well as Henning Lühmann for the magnetic
measurements.
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Z. Anorg. Allg. Chem. 2013, 2648–2656
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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2655

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Received: July 22, 2013
Published Online: September 20, 2013
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© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2648–2656