New Cd thio- and selenocyanato coordination compounds and their impact on the structures and reactivity of their paramagnetic counterparts

Article abstract of DOI:10.1002/ejic.201100745

Treatment of cadmium(II) thio- and selenocyanate with pyridazine leads to the formation of new cadmium(II)thiocyanato and selenocyanato coordination compounds [Cd(NCS)₂(pyridazine)₄] (1A), [Cd(NCSe) ₂(pyridazine)₃]_n (2A), [Cd(NCS) ₂(pyridazine)₂]_n (1B), [Cd(NCSe) ₂(pyridazine)₂]_n (2B) and [Cd(NCS) ₂(pyridazine)]_n (1C) which were characterised by single-crystal X-ray diffraction. Investigations of the thermal degradation behaviour of 1A and 2A using simultaneous differential thermoanalysis and thermogravimetry as well as X-ray powder diffraction, IR- and Raman spectroscopy prove that on heating, the pyridazine-rich compounds 1A and 2A decompose in a stepwise manner leading in the first TG step to the formation of the pyridazine-deficient compounds [Cd(NCS)₂(pyridazine) ₂]_n (1B) and [Cd(NCSe)₂(pyridazine) ₂]_n (2B) as intermediates. While the selenocyanato compound decomposes on further heating, for the thiocyanato compound an additional TG step is observed, in which a pyridazine-deficient 1:1 compound of composition [Cd(NCS)₂(pyridazine)]_n (1C) is formed. The structures and thermal reactivity are discussed and compared with that of related transition metal thiocyanato and selenocyanato coordination compounds with pyridine and pyrazine as the coligand. More importantly, on the basis of these investigations, the hitherto unknown structures of the ligand-deficient paramagnetic counterparts were determined. The crystal structures and thermal degradation behaviour of new Cd^II thiocyanato and selenocyanato coordination compounds are reported. The latter act as structural models for their paramagnetic counterparts. Copyright

Full text of DOI:10.1002/ejic.201100745

FULL PAPER
DOI: 10.1002/ejic.201100745
New Cd Thio- and Selenocyanato Coordination Compounds and Their Impact
on the Structures and Reactivity of Their Paramagnetic Counterparts
[a]
[a]
[a]
[a]
Jan Boeckmann, Inke Jeß, Thorben Reinert, and Christian Näther*
Keywords: Cadmium / Selenium / N ligands / Magnetic properties / Thermochemistry
Treatment of cadmium(II) thio- and selenocyanate with
pyridazine leads to the formation of new cadmium(II)
thiocyanato and selenocyanato coordination compounds
deficient compounds [Cd(NCS)
2 2 n
(pyridazine) ] (1B) and
[Cd(NCSe) (pyridazine) (2B) as intermediates. While the
2
2 n
]
selenocyanato compound decomposes on further heating, for
the thiocyanato compound an additional TG step is observed,
in which a pyridazine-deficient 1:1 compound of composition
[
Cd(NCS)
2A), [Cd(NCS)
(2B) and [Cd(NCS)
2
(pyridazine)
(pyridazine)
(pyridazine)]
4
]
(1A), [Cd(NCSe)
(1B), [Cd(NCSe)
(1C) which were
2
(pyridazine)
3 n
]
(
2
2
]
n
2
(pyrid-
azine)
2
]
n
2
n
2 n
[Cd(NCS) (pyridazine)] (1C) is formed. The structures and
characterised by single-crystal X-ray diffraction. Investi-
gations of the thermal degradation behaviour of 1A and 2A
using simultaneous differential thermoanalysis and thermo-
gravimetry as well as X-ray powder diffraction, IR- and Ra-
man spectroscopy prove that on heating, the pyridazine-rich
compounds 1A and 2A decompose in a stepwise manner
leading in the first TG step to the formation of the pyridazine-
thermal reactivity are discussed and compared with that of
related transition metal thiocyanato and selenocyanato coor-
dination compounds with pyridine and pyrazine as the co-
ligand. More importantly, on the basis of these investigations,
the hitherto unknown structures of the ligand-deficient para-
magnetic counterparts were determined.
Introduction
ing neutral coligands) intermediates in which the anions be-
come μ-1,3 bridging and can therefore mediate magnetic
Interest and investigations on coordination compounds
with paramagnetic metal centres which are interlinked by
means of small-sized anions and might therefore enable co-
operative magnetic phenomena have continuously increased
[
5,6,7]
exchange interactions.
In some cases however, the li-
gand-deficient compounds can also be prepared in solution
and therefore crystallised and structurally characterised by
single crystal X-ray diffraction but they are frequently only
accessible through thermal decomposition reactions. Unfor-
tunately this leads to the formation of microcrystalline pow-
ders with sometimes small particles and broad reflection
profiles and, therefore, indexing of their powder pattern is
difficult to achieve. However, this problem might be suc-
cessfully overcome if compounds were prepared showing
similar structural features and which consist of chalcophilic
metal cations that, in contrast to terminal bonded anions,
prefer a μ-1,3 bridging coordination mode. These condi-
tions are perfectly fulfilled by coordination compounds
over the last years.[ In connection with this, azido (N ),
1]
–
3
–
carboxylato (RCO , R = H, or an organic remainder) and
2
–
cyanido (CN ) coordination compounds which show inter-
esting magnetic behaviour like metamagnetism or slow re-
[
2]
laxation of the magnetisation have already been reported.
In this context we have reported the first thiocyanato
–
–
(
NCS ) and selenocyanato (NCSe ) compounds which
[3,4]
show such behaviour.
However, because the terminal co-
ordination mode of these anions is energetically favoured,
μ-1,3 bridging thio- and selenocyanatos of Mn, Fe, Co and
Ni are sometimes difficult to prepare in solution. In this
context, we have reported an alternative strategy for the ra-
tional synthesis of such compounds in which ligand-rich
II
based on Cd thio- or selenocyanate which exhibit struc-
II
tures that are very often comparable with that of the Mn ,
II
II
II
[6,8]
Fe , Co and Ni analogues.
Due to the higher chalco-
(ligand-rich = rich on neutral coligands) precursor com-
II
philicity of the Cd metal cations, such compounds prefer
a μ-1,3 bridging coordination mode and, therefore, the cor-
responding ligand-deficient intermediates can easily be
crystallised from solution and structurally characterised by
single-crystal X-ray diffraction. If they are isotypic with
their paramagnetic counterparts obtained by thermal de-
composition, the structures of the latter can simply be de-
termined by Rietveld refinement. This is one of the reasons
why we have started systematic investigations of cadmium
pounds based on transition metal thio- or selenocyanates
with only terminal bonded anions and additional neutral
coligands are thermally decomposed leading to the phase-
pure formation of ligand-deficient (ligand-deficient = lack-
[
a] Institut für Anorganische Chemie,
Christian-Albrechts-Universität zu Kiel,
Max-Eyth-Straße 2, 24098 Kiel, Germany
Fax: +49-431-8801520
E-mail: cnaether@ac.uni-kiel.de
Supporting information for this article is available on the thio- and selenocyanato complexes.
WWW under http://dx.doi.org/10.1002/ejic.201100745.
5502
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Eur. J. Inorg. Chem. 2011, 5502–5511

Cd Thio- and Selenocyanato Coordination Compounds
In the course of our project we also investigated corre- crystals of all compounds and this can easily be performed
sponding compounds with pyridazine as coligand which at room-temperature or under solvothermal conditions.
can act as monodentate or a bidentate ligand. In the former
case, only one of the two N atoms is involved in metal coor-
dination, whereas in the latter two different metal cations Structural Investigations
are linked by the pyridazine ligand. There are a very few
[
7,9,10]
Structure of the 1:4 Compound [Cd(NCS) (pyridazine) ]
2 4
examples
where this ligand forms 1:4 complexes and
(1A)
there are also examples in which both coordination modes
are found in the same structure.[11,12] Within this project we
The pyridazine-rich 1:4 compound [Cd(NCS) (pyrid-
2
have synthesised ligand-rich compounds with Mn, Fe, Co azine) ] (1A) crystallises in the centrosymmetric triclinic
4
and Ni but we were not able to obtain ligand-deficient com- space group P 1¯ with one formula unit in the unit cell and
II
[9]
pounds with μ-1,3 bridging anions using conventional solu- is isostructural with the Co compound reported recently.
tion synthesis. With Ni, for example, we obtained a trinu- The cadmium cation is located on a centre of inversion and
clear complex of composition [Ni (NCS) (pyridazine) ] in is coordinated by six nitrogen atoms from two terminal N-
3
6
6
which the pyridazine coligand acts as a monodentate and bonded thiocyanato anions and four terminal bonded
bidentate ligand and, besides terminal N-bonded thiocyan- pyridazine ligands, all of them in general positions, within
ato anions, μ-1,1 N-bridging anions are also found.[ How- a slightly distorted octahedral coordination geometry (Fig-
ever, a large number of ligand-deficient intermediates can ure 1 and Table 1).
12]
easily be prepared by thermal decomposition which is the
case, for example, for [Mn(NCS) (pyridazine) ]. The latter
2
4
transforms into three different intermediates on heating.
Unfortunately we were not able to extract any structural
information and we therefore decided to investigate the cor-
responding compounds with cadmium thio- and seleno-
cyanate. Here we report on our investigations.
Results and Discussion
Synthetic Aspects
In order to examine the number and nature of the CdII
coordination compounds that can be prepared in solution,
different ratios of the metal salts and the neutral N-donor
coligand pyridazine were combined in acetonitrile, water or
pure coligand and the precipitates formed were filtered off
and investigated by XRPD measurements. These experi-
II
ments showed that with Cd thiocyanate, three different
II
crystalline phases occur whereas with Cd selenocyanate
only two of them can be found. The results of elemental
Figure 1. Molecular structure of compound 1A with labelling and
displacement ellipsoids drawn at the 50% probability level. Sym-
metry transformation used to generate equivalent atoms:
analysis indicate that reaction of Cd(NCS) or Cd(NCSe)2
2
in pure coligand leads to the formation of a pyridazine-rich
A: –x, –y + 1, –z + 1. (a packing diagram is shown in Figure S1
1:4 thiocyanato compound of composition [Cd(NCS)2- of the Supporting Information).
(
pyridazine) ] (1A) and a pyridazine-rich 1:3 selenocyanato
4
compound of composition [Cd(NCSe) (pyridazine) ] (2A).
2
3 n
Table 1. Selected bond lengths [Å] and angles [°] for 1A. Symmetry
code: A: –x, –y + 1, –z + 1.
Reaction of Cd(NCSe) with pyridazine in water and aceto-
2
nitrile with a molar ratio down from 1:10 to 1:1 (ratio metal
salt to coligand) results in only one crystalline phase of a
pyridazine-deficient 1:2 compound of composition
[
Cd(NCS)
2
(pyridazine)
4
] (1A)
2.287(3) N(1)–Cd(1)–N(21)
2.386(2) N(1)–Cd(1)–N(21A) 91.94(9)
2.421(2) N(11)–Cd(1)–N(21) 86.85(8)
180.0 N(11)–Cd(1)–N(21A) 93.15(8)
85.76(10) N(11)–Cd(1)–N(11A) 180.0
azine-deficient 1:2 compound of composition [Cd(NCS)2- N(1)–Cd(1)–N(11A) 94.24(10) N(21)–Cd(1)–N(21A) 180.0
pyridazine) ] (1B), whereas reaction of equivalent molar
Cd(1)–N(1)
Cd(1)–N(11)
Cd(1)–N(21)
N(1)–Cd(1)–N(1A)
88.06(9)
[
Cd(NCSe) (pyridazine) ] (2B). Reaction of Cd(NCS)2
2 2 n
with pyridazine in water and acetonitrile with a molar ratio
down from 1:10 to 1:2 leads to the formation of a pyrid- N(1)–Cd(1)–N(11)
(
2
n
amounts of Cd(NCS) with pyridazine in water and aceto-
The shortest metal to metal separation between the com-
nitrile leads to the formation of an additional phase of com- plexes amounts to 8.0308(8) Å.
position [Cd(NCS) (pyridazine)] (1C). According to the The metal–nitrogen distances range between 2.287(3)
2
2
n
XRPD measurements, compounds 1B and 2B should be and 2.421(2) Å and the angles around the metal cations
isotypic. Based on these results we tried to prepare single range between 85.76(10) and 94.24(10)° (Table 1). In the
Eur. J. Inorg. Chem. 2011, 5502–5511
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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J. Boeckmann, I. Jeß, T. Reinert, C. Näther
FULL PAPER
crystal structure, the discrete complexes are arranged into Table 2. Selected bond lengths [Å] and angles [°] for 2A. Symmetry
codes: A: –x, –y + 1, –z + 1; B: –x + 1, –y, –z.
columns which are elongated in the direction of the crystal-
lographic b axis and these columns are further arranged
into layers in the bc plane (Figure S1).
[
2 3 n
Cd(NCSe) (pyridazine) ] (2A)
Cd(1)–N(1)
Cd(1)–N(2)
Cd(1)–N(11)
Cd(2)–N(21)
Cd(2)–N(31)
Cd(2)–N(41)
Cd(2)–N(51)
Cd(2)–Se(2)
2.300(3)
2.318(3)
2.376(3)
2.388(3)
2.400(3)
2.354(3)
2.368(3)
N(1)–Cd(1)–N(2)
N(1)–Cd(1)–N(11) 93.84(12)
N(2)–Cd(1)–N(11) 86.31(12)
93.09(13)
Structure of the 1:3 Compound [Cd(NCSe) (pyridazine) ]
2
3 n
(2A)
Se(2)–Cd(2)–Se(3)
178.400(16)
N(21)–Cd(2)–Se(2) 89.40(7)
N(21)–Cd(2)–Se(3) 92.20(7)
N(31)–Cd(2)–Se(2) 91.82(7)
The pyridazine-rich 1:3 compound [Cd(NCSe) (pyrid-
2
azine) ] (2A) crystallises in the triclinic centrosymmetric
3
n
¯
space group P1 with four formula units per unit cell. The
2.8003(5) N(31)–Cd(2)–Se(3) 86.58(7)
2.8151(5) N(21)–Cd(2)–N(31) 177.57(11)
2.322(3)
2.294(4)
2.371(3)
asymmetric unit consists of three cadmium cations two of Cd(2)–Se(3)
Cd(3)–N(3)
N(3)–Cd(3)–N(3B) 180.0
N(3)–Cd(3)–N(61) 93.24(13)
N(3)–Cd(3)–N(4)
N(4)–Cd(3)–N(61) 89.64(13)
which are located on a centre of inversion and one in a
Cd(3)–N(4)
general position, four selenocyanato anions and six pyrid-
Cd(3)–N(61)
92.56(14)
azine ligands, all of them located in general positions (Fig-
ure 2).
N(1)–Cd(1)–N(1A) 180.0
Cd2 is coordinated by four nitrogen atoms from four ter-
minal N-bonded pyridazine ligands and by two selenium
atoms from two μ-1,3 bridging selenocyanato anions in a
slightly distorted octahedral coordination geometry (Fig- bic space group Pnma with four formula units per unit cell.
II
II
ure 2 and Table 2). The remaining Cd cations are each co- The asymmetric unit consists of one Cd ion and two thio-
ordinated by six nitrogen atoms from two terminal N- or selenocyanato anions (1B and 2B, respectively) situated
bonded pyridazine ligands, two terminal N-bonded and two on a mirror plane as well as one pyridazine ligand in a
μ-1,3 bridging selenocyanato anions in a slightly distorted general position (Figure 3).
II
octahedral coordination geometry (Figure 2 and Table 2).
The Cd ion is coordinated by four N atoms from two
The metal centres are bridged into polymeric chains, each pyridazine ligands and two thio- or selenocyanato anions
through a single selenocyanato anion. These chains are (1B and 2B, respectively) each in a mutual cis orientation
elongated perpendicular to the crystallographic a axis. The and by two S or Se atoms from two adjacent thio- or seleno-
metal–nitrogen distances range between 2.294(4) and cyanato anions within a slightly distorted octahedral coor-
II
2
.400(3) Å and the angles around the metal cations range dination environment (Figure 3 and Table 3). The Cd ions
between 86.16 (12) and 93.84 (12)° (Table 2). The shortest are μ-1,3 bridged by means of the anions into polymeric
metal to metal intrachain separation amounts to chains that are elongated in the direction of the crystallo-
II
II
6
.1618(6) Å, whereas the shortest metal to metal interchain graphic a axis. The Cd ···Cd intrachain separation
separation amounts to 9.0836(12) Å.
amounts to 5.8667(7) Å for 1B and 6.0045(6) Å for 2B,
II
II
whereas the shortest Cd ···Cd interchain separation
amounts to 7.9160(8) Å for 1B and 8.1861(7) Å for 2B.
These chains are further connected by weak S···S interac-
Structures of the 1:2 Compounds [Cd(NCS) (pyridazine) ]
2
2 n
(
1B) and [Cd(NCSe) (pyridazine) ] (2B)
2
2 n
The pyridazine-deficient 1:2 compounds [Cd(NCS)2- tions with a separation of 3.6801(21) Å or Se···Se interac-
pyridazine) ] (1B) and [Cd(NCSe) (pyridazine) ] (2B) are tions with a separation of 3.7802(9) Å into layers which are
(
2
n
2
2 n
isotypic and crystallise in the centrosymmetric orthorhom- located in the crystallographic ac plane.
Figure 2. Molecular structure of compound 2A with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry
transformation used to generate equivalent atoms: A: –x, –y + 1, –z + 1; B: –x + 1, –y, –z. (a packing diagram of 2A is shown in Figure
S2 of the Supporting Information).
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Eur. J. Inorg. Chem. 2011, 5502–5511

Cd Thio- and Selenocyanato Coordination Compounds
Figure 3. Molecular structure of compound 1B as a representative example with labelling and displacement ellipsoids drawn at the 30%
3
3
3
probability level. Symmetry transformation used to generate equivalent atoms: A: x Ϫ ½, y, –z + /
2
; B: x + ½, y, –z + /
2
2
; C: x, –y + / ,
z. (a packing diagram of 1B is shown in Figure S3 and an ORTEP plot of 2B is shown in Figure S4 of the Supporting Information).
Table 3. Selected bond lengths [Å] and angles [°] for 1B and 2B. adjacent μ-1,3 bridging thiocyanato anion within a dis-
3
3
Symmetry code: A: x – ½, y, –z + /
2
2
; B: x + ½, y, –z + / ; C: x, –y
torted octahedral coordination geometry (Figure 4 and
Table 4).
3
+
/2
, z.
2 2 n
[Cd(NCS) (pyridazine) ] (1B)
Cd(1)–S(1)
Cd(1)–S(2)
2.7931(16) N(1A)–Cd(1)–S(1)
2.6572(16) N(1A)–Cd(1)–S(2)
176.94(13)
97.81(13)
Cd(1)–N(1A)
Cd(1)–N(2B)
Cd(1)–N(11)
S(1)–Cd(1)–S(2)
N(1A)–Cd(1)–N(2B)
N(1A)–Cd(1)–N(11)
2.272(5)
2.306(5)
2.378(3)
79.13(4)
92.02(17)
93.46(8)
N(2B)–Cd(1)–N(11) 88.05(8)
N(2B)–Cd(1)–S(1)
N(2B)–Cd(1)–S(2)
N(11)–Cd(1)–S(1)
N(11)–Cd(1)–S(2)
91.04(13)
170.17(12)
86.64(8)
91.35(8)
[
Cd(NCSe)
2 2
(pyridazine) ]n (2B)
Cd(1)–Se(1)
Cd(1)–Se(2)
Cd(1)–N(1A)
Cd(1)–N(2B)
Cd(1)–N(11)
2.8588(7)
2.7320(7)
2.281(5)
2.332(5)
2.386(4)
78.46(2)
90.71(18)
N(1A)–Cd(1)–Se(1) 177.17(13)
N(1A)–Cd(1)–Se(2) 98.71(13)
N(2B)–Cd(1)–N(11) 86.73(9)
N(2B)–Cd(1)–Se(1) 92.12(12)
N(2B)–Cd(1)–Se(2) 170.58(12)
N(11)–Cd(1)–Se(1) 88.23(9)
N(11)–Cd(1)–Se(2) 92.92(9)
Se(1)–Cd(1)–Se(2)
N(1A)–Cd(1)–N(2B)
N(1A)–Cd(1)–N(11) 91.94(9)
Structure of the 1:1 Compound [Cd(NCS) (pyridazine)]n
2
(
1C)
Figure 4. Packing diagram of compound 1C viewed along the b
The pyridazine-deficient 1:1 compound [Cd(NCS)2- axis (black = metal, dark-grey = nitrogen, light-grey = carbon, grey
=
sulfur, white = hydrogen) (an ORTEP plot of 1C is shown in
(pyridazine)] (1C) crystallises in the centrosymmetric mo-
n
Figure S5 of the Supporting Information).
noclinic space group P2 /n with eight formula units per unit
cell. The asymmetric unit consists of two Cd ions, four
1
II
thiocyanato anions and two pyridazine ligands, all in gene-
ral positions. One of the Cd ions is coordinated by four N μ-1,3 bridging thiocyanato anions into double and single
These dinuclear entities are further linked by means of
II
atoms from two μ -bridging pyridazine ligands, one μ-1,1 chains forming a 2D layer network which is parallel to the
2
II
II
bridging and one μ-1,3 bridging thiocyanato anion, each in crystallographic ac plane (Figure 4). The Cd ···Cd separa-
a mutual cis orientation, and by two S atoms from two ad- tion within the dinuclear entity through the μ-1,1 bridging
jacent μ-1,3 bridging thiocyanato anions within a distorted N-bonded thiocyanato anions amounts to 3.7598(8) Å,
octahedral coordination environment (Figure 4 and whereas the Cd ···Cd intrachain separation through the
Table 4). The remaining Cd ion is coordinated by five N single chain of the μ-1,3 bridging thiocyanato anions
II
II
II
atoms from two μ -bridging pyridazine ligands, one μ-1,1 amounts to 6.5202(8) Å, and that for the double chain of
2
bridging and two μ-1,3 bridging thiocyanato anions, each the μ-1,3 bridging thiocyanato anions amounts to
in a mutual cis orientation, and by one S atom from an 5.6124(9) Å.
Eur. J. Inorg. Chem. 2011, 5502–5511
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J. Boeckmann, I. Jeß, T. Reinert, C. Näther
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Table 4. Selected bond lengths [Å] and angles [°] for 1C. Symmetry step Δm , the formation of a pyridazine-deficient 1:2 inter-
1
code: A: x – ½, –y + ½, z + ½; B: x + ½, –y + ½, z – ½; C: x +
mediate of composition [Cd(NCS) (pyridazine) ] (1B) oc-
2
2 n
1, y, z; D: x – 1, y, z.
curs. The second mass step Δm gives further hints of the
2
[
Cd(NCS) (pyridazine)]
2
n
(1C)
formation of a pyridazine-deficient intermediate of compo-
sition [Cd(NCS) (pyridazine)]n (1C) which itself decom-
Cd(1)–S(1)
Cd(1)–S(2)
2.646(2)
2.674(2)
2.342(6)
2.291(7)
2.415(7)
2.427(6)
2.733(2)
2.281(8)
2.281(6)
2.333(6)
2.430(6)
2.369(6)
S(1)–Cd(1)–S(2)
97.57(7)
92.7(2)
91.4(2)
2
N(1B)–Cd(2)–N(2C)
N(1B)–Cd(2)–N(3)
N(1B)–Cd(2)–S(4)
N(2C)–Cd(2)–N(3)
N(2C)–Cd(2)–S(4)
N(3)–Cd(1)–S(1)
N(3)–Cd(1)–S(2)
N(3)–Cd(2)–S(4)
N(4A)–Cd(1)–S(1)
N(4A)–Cd(1)–S(2)
N(4A)–Cd(1)–N(3)
poses on further heating (For DTG, TG and DTA curves
for compounds 1B and 1C see Figures S6–S7 in the Sup-
porting Information).
Cd(1)–N(3)
Cd(1)–N(4A)
Cd(1)–N(11)
Cd(1)–N(21)
Cd(2)–S(4)
Cd(2)–N(1B)
Cd(2)–N(2C)
Cd(2)–N(3)
Cd(2)–N(12)
Cd(2)–N(22)
96.75(19)
103.6(2)
87.87(18)
169.62(17)
88.23(17)
165.64(16)
97.09(18)
88.6(2)
To verify the nature of the intermediates formed, ad-
ditional TG measurements were performed and stopped af-
ter the first and second TG step. Elemental analysis of the
residues obtained support the assumption of the formation
of pyridazine-deficient 1:2 and 1:1 intermediates. Final
XRPD investigations of the residues clearly showed that the
pyridazine-deficient compounds 1B and 1C were formed as
pure phases in the first and second TG steps (Figure 6).
91.6(2)
Cd(1)–N(3)–Cd(2) 107.1(3)
Thermoanalytical Investigations
In order to investigate the thermal properties of the li-
gand-rich compounds, simultaneous DTA-TG (differential
thermoanalysis and thermogravimetry) measurements were
performed. On heating the pyridazine-rich compound 1A
in a thermobalance, a stepwise decomposition was ob-
served. In the TG curve three mass steps accompanied with
endothermic events in the DTA curve can be observed (Fig-
ure 5). The mass loss in the first step Δm = 30.6% is in
1
good agreement with that calculated for the removal of two
molecules pyridazine (Δmcalcd. = 29.2%) (Figure 5). The
mass losses of both of the following steps of Δm = 15.3%
2
and Δm = 15.0% are each in reasonable agreement with
3
the calculated mass loss for one molecule pyridazine
(Δmcalcd. = 14.6%) (Figure 5). On the basis of the experi-
mental mass losses, it can be assumed that in the first mass
Figure 6. Experimental XRPD patterns of the intermediates ob-
tained after the first (A) and second (C) heating step of compound
1
A together with calculated XRPD patterns for the 1:2 compound
1
B (B) and the 1:1 compound 1C (D).
If compound 2A is heated in a thermobalance two mass
steps are observed which are not well resolved. Even heat-
ing rate dependent measurements did not improve the reso-
lution of the thermal events (Figure S8 of the Supporting
Information). The experimental mass loss in the first step
of Δm = 14.1% is in good agreement with that calculated
1
for the removal of one molecule pyridazine (Δmcalcd.
4.2%) (Figure 7) and accompanied with an endothermic
event in the DTA curve.
=
1
The experimental mass loss of the following step Δm =
2
28.3% is in agreement with that calculated for the removal
of two molecules pyridazine (Δmcalcd. = 28.5%). Therefore,
based on the experimental mass losses, it can be assumed
that in the first mass step Δm a pyridazine-deficient 1:2
1
intermediate of composition [Cd(NCSe) (pyridazine) ]
2
2 n
(
(
2B) has formed which loses all coligands on further heating
For DTG, TG and DTA curves for compound 2B see Fig-
ure S9 of the Supporting Information). To verify the nature
of the intermediate formed, additional TG measurements
were performed and stopped after the first TG step. XRPD
Figure 5. DTG, TG and DTA curves for compound 1A. Heating
–1
rate: 4 °Cmin ; given are the mass changes in % and the peak
P
temperatures T in °C.
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Eur. J. Inorg. Chem. 2011, 5502–5511

Cd Thio- and Selenocyanato Coordination Compounds
pound 1A, only one band may be observed in the IR spec-
trum with a value which is characteristic for terminal N-
bonded thiocyanato anions (Table 5). For the pyridazine-
rich 1:3 compound 2A, two bands may be observed in the
IR and Raman spectra which support the occurrence of
both terminal N-bonded and μ-1,3 bridging selenocyanato
anions (Table 5).
Table 5. Stretching vibration ν(CN) in the IR and Raman spectra
for the thio- and selenocyanato anions in compounds 1A–1C and
2A–2B.
–
1
Raman bands [cm–1]
Compound
IR bands [cm ]
1A
1B
1C
2A
2B
2061
–
2099 and 2105
1985, 2094 and 2105
2062 and 2113
2097 and 2107
2097 and 2105
1985, 2093 and 2105
2067 and 2117
2105 and 2111
The values found in the IR and Raman spectra for the
pyridazine-deficient compounds 1B and 2B are consistent
with that expected for μ-1,3 bridging anions (Table 5). For
the most pyridazine-deficient compound 1C, values for
Figure 7. DTG, TG and DTA curves for compound 2A. Heating
–1
rate: 1 °Cmin ; given are the mass changes in % and the peak ν(CN) are observed in the IR and Raman spectra which are
P
temperatures T in °C.
characteristic and consistent with μ-1,3 bridging and μ-1,1
bridging thiocyanato anions (Table 5).
measurements showed that compound 2B has formed but
always in a mixture with the precursor 2A and an additional
unknown phase which could not be identified. It might be
that a second ligand-deficient phase or a polymorphic
modification forms on heating but because of the low-reso-
lution it cannot be isolated (Figure S10 in the Supporting
Information).
General Discussion of the Structures and Reactivity
II
In this contribution, Cd thiocyanato and selenocyanato
coordination compounds based on pyridazine as a coligand
were investigated in order to compare their structural and
chemical properties with those found for the corresponding
coordination polymers with pyridine and pyrazine as co-
ligands as well as Cd, Mn, Fe, Co and Ni as counter cat-
ions.
Spectroscopic Measurements
The coordination modes of the thiocyanato and seleno-
With CdII thiocyanate, a pyridazine-rich 1:4 compound
cyanato anions in compounds 1A–1C and 2A–2B (Figure of composition [Cd(NCS) (pyridazine) ] (1A) was observed
2
4
S10-S14 of the Supporting Information) can be additionally consisting of discrete complexes that are identical to those
verified from their vibrational spectra and, therefore, IR in [M(NCS) (pyridine) ] (M = Mn, Fe Co, Ni and Cd) re-
2
4
[
14]
and Raman spectroscopic investigations were performed. In ported recently.
Consequently, similar reactivity is ob-
compounds with terminal N-bonded thio- or selenocyanato served such that on heating a transformation into a ligand-
anions, the asymmetric ν (CN) is expected to be at about deficient intermediate of composition [Cd(NCS) (pyrid-
as
2
–
1 [13]
2
050 cm .
For μ-1,3 bridging thio- or selenocyanato azine) ] (1B) is observed and this intermediate can also be
2 n
anions the asymmetric ν (CN) is shifted to higher wave- isolated for the compounds with pyridine. In contrast to
as
–
1
numbers and can be found Ն 2100 cm whereas for a μ- the pyridine compounds, an additional pyridazine-deficient
,1 bridging anions the asymmetric ν (CN) is shifted to compound of composition [Cd(NCS) (pyridazine)]n (1C)
1
as
2
–
1
lower wavenumbers an can be found Յ 2000 cm . How- can be observed in which the metal cations are additionally
ever, even if the coordination mode is clear from our struc- bridged by the coligand.
II
tural investigations, such measurements can be especially
In contrast, with Cd selenocyanate, no ligand-rich 1:4
helpful in the cases in which no structural information can compound with sixfold N coordination could be prepared
be retrieved from diffraction experiments. In this context it and the most pyridazine-rich compound is represented by
must be kept in mind that the spectroscopic values men- a 1:3 compound (2A) which shows alternating sixfold and
tioned above are based in part on old results and we have fourfold N coordination. The reason for this behaviour can
found that exceptions from these exact numbers are very be traced back to the fact that Se is much softer than S
often discovered. Therefore, such investigations are of gene- and, therefore, with the chalcophilic and soft Cd cations Se
ral interest.
coordination is preferred. In this context it must be men-
These results are in full agreement with our spectroscopic tioned that the structure of 2A in which the metal cations
investigations in which, for the pyridazine-rich 1:4 com- are linked by only one anion is quite unusual and without
Eur. J. Inorg. Chem. 2011, 5502–5511
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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5507

J. Boeckmann, I. Jeß, T. Reinert, C. Näther
FULL PAPER
any precedence in the literature. In most cases the metal(II) compound into a 1:1 compound through additional inter-
cations are linked by two thio- or selenocyanato anions into mediates can be observed. Unfortunately the powder pat-
chains which is also observed, for example, with azido terns of these intermediates are of low quality and, as a
anions. As expected, on heating the 1:3 compound 2A, a result, no structural information can be extracted. However,
transformation into the 1:2 compound 2B can be observed based on the results of this work we have found that the
which is isotypic with 1B and which consists of a 1D coor- powder pattern of the 1:1 Mn compound is very similar to
dination polymer in which the metal cations are each linked that of the Cd compound 1C. To substantiate this compari-
by two μ-1,3 bridging anions. Therefore, the structure of son we determined the structure of the 1:1 intermediate ob-
the 1:3 compound 2A represents a structural intermediate tained from thermal decomposition by Rietveld refinement
between the discrete 1:4 compound and the 1D 1:2 com- based on the structural data of compound 1C (Figure S21
pounds which are frequently observed with all monodentate and Table S1 of the Supporting Information). If the calcu-
ligands. Interestingly, if the crystal structures of all com- lated pattern for the Mn compound is compared with that
pounds are compared, a smooth reaction pathway can be of the intermediate and that of compound 1C it is obvious
found from the ligand-rich structure transformation into that [Mn(NCS) (pyridazine)] has formed in the thermal
2
n
the ligand-deficient intermediates. However, the reason why decomposition reaction and that this compound is isotypic
a 1:3 compound is not observed in the thermal decomposi- with 1C (Figure 8).
tion reaction of the 1:4 pyridazine compound is unclear.
From previous investigations we know that the kinetics of
the different reactions might play a role and that different
products can be observed on heating rate dependent mea-
surements, for example.[ Therefore, it might be that such
15]
1:3 compounds were overlooked. In any case, the results
clearly show that even such simple reactions are much more
complicated to understand and might proceed by means of
additional metastable intermediates that are sometimes dif-
ficult to identify.
Moreover, differences between sulfur and selenium were
also obvious because only with thiocyanate can a 1:1 com-
pound (1C) be observed. In this structure, the pyridazine
coligand becomes μ-1,2 bridging and one of the thiocyan- Figure 8. Experimental XRPD pattern of the intermediate ob-
2
ato anions becomes μ-1,1 bridging and, therefore, the tained after the second heating step of compound [Mn(NCS) -
(
1
[
pyridazine)
:1 compound [Mn(NCS)
Cd(NCS) (pyridazine)] (1C) (C).
4
] (A) together with calculated XRPD patterns for the
number of Cd–N bonds increases. Consequently, in the case
of thiocyanate it can be assumed that the difference between
N- and S-bonding is not as pronounced as it is the case for
Se-bonding and therefore the formation of a ligand-de-
ficient 1:1 selenocyanato compound is suppressed.
2
(pyridazine)] (B) and the 1:1 compound
n
2
n
Conclusion
Our approach to use the diamagnetic cadmium thio- and
selenocyanates as structural models for their paramagnetic
Impact on the Structures of the Paramagnetic Counterparts
Based on our results, it is indicated that the cadmium counterparts seems to be very fruitful. It could be shown
thio- and selenocyanato coordination polymers show sim- that changing the metal source from the harder metals such
ilar structural and thermal behaviour to that of the para- as Mn, Fe, Co and Ni to Cd results in the formation of
magnetic cations but, in contrast, the latter prefer a bridg- ligand-deficient compounds with higher condensed net-
ing instead of a terminal coordination. Consequently, li- works, one of which is isotypic with its paramagnetic coun-
gand-deficient compounds with Cd might be easily crystal- terpart. This seems to be one of the most important results
lised and these compounds can act as structural models for of our investigations which is of extraordinary importance
the corresponding paramagnetic ligand-deficient intermedi- for future work in which we will systematically investigate
ates in those cases where they are isotypic. In this context the magnetic properties of such materials. In this context
we wish to mention that coordination compounds with we would like to mention that we have prepared several
pyridazine and the paramagnetic metals Mn, Fe, Co and Ni ligand-deficient intermediates of different stoichiometry
are currently being investigated in our group. With these with different monodentate ligands by thermal decomposi-
metal cations, only the ligand-rich 1:4 compounds can be tion but most of their structures are still unknown. It is
prepared in solution whereas ligand-deficient intermediates highly likely that several of them are isotypic either with
are not accessible. This is disappointing because, especially their Cd-based thio- or selenocyanato analogues. Therefore,
in these compounds, cooperative magnetic phenomena the preparation and characterisation of the corresponding
might be observed. However, first results for the Mn com- Cd compounds will be the subject of our future investi-
pound show that on heating, a transformation of the 1:4 gations.
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Eur. J. Inorg. Chem. 2011, 5502–5511

Cd Thio- and Selenocyanato Coordination Compounds
room temp. for 3 d. Single crystals suitable for single-crystal X-ray
diffraction were prepared by the same method but without stirring.
Experimental Section
Syntheses: Cd(NO
3
)
2
·4H
2
O and CdSO
4 2
·8H O were obtained from
C
10
H
8
CdN
H 1.5, N 17.2. IR (KBr): ν˜ = 2121 (s), 2108 (s), 1624 (wb), 1573
m), 1569 (m), 1454 (w), 1449 (w), 1414 (m), 1394 (w), 1287 (w),
068 (m), 989 (w), (m), 969 (m), 762 (m), 745 (w), 674 (w), 667
6 2
Se (482.5): calcd. C 24.8, H 1.6, N 17.4; found C 24.6,
Merck. KNCSe, Ba(NCS)
2
·3H O and pyridazine were obtained
2
from Alfa Aesar. Solvents were used without further purification.
Crystalline powders of compounds 1A–1C and 2A–2B were pre-
pared by stirring the reactants in appropriate solvents at room tem-
perature. The residues of 1B–1C and 2A–2B were filtered off and
washed with ethanol and diethyl ether and dried in air. The result-
ant precipitate of 1A is air sensitive and has to be kept in the
mother liquor. The purity of all compounds was checked by X-
ray powder diffraction (see Figures S16 – S20 in the Supporting
Information) and elemental analysis.
(
1
–1
(w) cm .
Elemental Analysis of the Residues Obtained in the Thermal Decom-
position: These were isolated in the first and second heating step
(
see thermoanalytical investigations) of compound 1A. Calculated
for the ligand-deficient compound 1B: C10 CdN (388.8):
H
8
6 2
S
calcd. C 30.9, H 2.1, N 21.6, S 16.5; found C 30.8, H 2.2, N 21.5,
S 16.4%. Calculated for the ligand-deficient compound 1C:
C H CdN S (308.7): calcd. C 23.4, H 1.3, N 18.2, S 20.8; found
6 4 4 2
C 23.2, H 1.1, N 17.9, S 20.5.
Cd(NCS)
3.5258 g, 10 mmol) were stirred in water (100 mL). The colourless
precipitate of BaSO was filtered off and the water was removed
2 2 2 4 2
: Ba(NCS) ·3H O (3.0755 g, 10 mmol) and CdSO ·8H O
(
4
Single-Crystal Structure Analyses: All investigations were per-
formed with an imaging plate diffraction system from STOE & CIE
from the filtrate by heating. The final product was dried at 80 °C.
The homogeneity of the product was investigated by Xray powder
(
IPDS-1 for 1A, 2A/IPDS-2 for 1B, 1C and 2B) utilising Mo-K
α
diffraction. Cd(NCS)
2
(228.6): calcd. C 10.5, N 12.3, S 28.1; found
radiation. The structure solution was performed with direct meth-
C 10.4, N 12.1, S 27.9.
[
16]
ods using SHELXS-97
and structure refinements were per-
Synthesis of Compound 1A: Cd(NCS)
2
(114 mg, 0.50 mmol) and
2
[16]
formed against F using SHELXL-97.
All non-hydrogen atoms
pyridazine (725 μL, 10.00 mmol) were stirred together in a 3 mL
snap cap vial for 3d. Single crystals suitable for single-crystal X-
ray diffraction were prepared by the same method but with stirring
omitted. IR (KBr): ν˜ = 2061 (m), 1655 (w), 1563 (m), 1444 (w),
were refined with anisotropic displacement parameters. The hydro-
gen atoms were positioned with idealised geometries and were re-
fined with fixed isotropic displacement parameters [Uiso(H) =
–1.2·Ueq(C)] using a riding model. For compound 2A, a pseudo
1
412 (m), 1282 (w), 1182 (m), 1108 (m), 1061 (m), 1023 (m), 961
translation could be found which might indicate that a wrong unit
cell was selected. Therefore, we tried to refine the structure in a
smaller unit cell in which this pseudo translation is absent but this
was unsuccessful because most parts are completely disordered. A
closer look at the structure model clearly shows that this pseudo
translation is only fulfilled for a few atoms. However, even from
Figure 2 it is completely obvious that the torsion of the phenyl
rings is completely different and that no smaller unit can be found.
Details of the structure determination are given in Table 6.
–1
(s), 754 (s), 665 (w), 615 (w) cm . C18
2
H16CdN10S (548.9): calcd.
C 39.4, H 2.9, N 25.5, S 11.7; found C 39.2, H 2.6, N 25.3, S 11.5.
Synthesis of Compound 1B: Cd(NCS) (114 mg, 0.50 mmol) and
pyridazine (160 μL, 2.00 mmol) were stirred together in acetonitrile
2 mL) at room temp. in a 3 mL snap cap vial for 3 d. Single crys-
tals suitable for single-crystal X-ray diffraction were prepared by
the reaction of Cd(NCS) (57 mg, 0.25 mmol) and pyridazine
36 μL, 0.50 mmol) in acetonitrile (2 mL) and heating to 120 °C for
d. C10 CdN (388.8): calcd. C 30.9, H 2.1, N 21.6, S 16.5;
found C 30.6, H 2.0, N 21.4, S 16.3. IR (KBr): ν˜ = 2121 (s), 2100
2
(
2
(
4
H
8
6 2
S
CCDC-835853 (for 1A), -835852 (for 1B), -835854 (for 1C),
-
835855 (for 2A) and -835856 (for 2B) contain the supplementary
(
s), 1570 (m), 1450 (w), 1414 (m), 1396 (w), 1288 (w), 1182 (w),
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/data_request/cif.
–
1
1
071 (m), 970 (m), 931 (w), 914 (w), 763 (m), 746 (m), 668 (w) cm .
(114 mg, 0.50 mmol) and
pyridazine (36 μL, 0.50 mmol) were stirred together in acetonitrile
2 mL) in a 3 mL snap cap vial at room temp. for 3 d. Single crys-
tals suitable for single-crystal X-ray diffraction were prepared by
the reaction of Cd(NCS) (114 mg, 0.50 mmol) and pyridazine
36 μL, 0.50 mmol) in acetonitrile (2 mL) and heating to 130 °C.
After 4 d colourless needles were obtained in a mixture with com-
pound 1B. C CdN (308.7): calcd. C 23.4, H 1.3, N 18.2, S
0.8; found C 23.4, H 1.3, N 18.1, S 20.7. IR (KBr): ν˜ = 2128 (s),
Synthesis of Compound 1C: Cd(NCS)
2
Spectroscopy: Fourier transform IR spectra were recorded on a
Genesis series FTIR spectrometer from ATI Mattson in KBr pel-
lets as well on an Alpha IR spectrometer from Bruker equipped
(
2
with a Platinum ATR QuickSnap™ sampling module between
(
–1
4
000–375 cm . Raman spectra were recorded using a Bruker
–1
ISF66 FRA106 between 3500–100 cm .
6
H
4
4 2
S
2
2
1
Elemental Analysis: CHNS analyses were performed using an
EURO EA elemental analyser manufactured by EURO VECTOR
Instruments and Software.
106 (s), 2100 (s), 2093 (s), 1985 (s), 1937 (w), 1576 (m), 1455 (w),
420 (m), 1400 (w), 1296 (w), 1073 (m), 984 (m), 770 (m), 670
–1
(w) cm .
X-Ray Powder Diffraction (XRPD): XRPD experiments were per-
Synthesis of Compound 2A: Cd(NO
3
)
2
·4H
2
O (77 mg, 0.25 mmol),
formed using a STOE Transmission Powder Diffraction System
KNCSe (65 mg, 0.45 mmol) and pyridazine (400 μL, 5.00 mmol)
α
(STADI P) with Cu-K radiation (λ = 154.0598 pm) and equipped
were stirred together in a 3 mL snap cap vial at room temp. for
with a linear position-sensitive detector (Delta 2θ = 6.5–7° simulta-
neous; scan range overall: 2–130°) from STOE & CIE and an Image
Plate Detector (scan range overall: 0–127°).
3
d. Single crystals suitable for single-crystal X-ray diffraction were
prepared by the same method but without stirring. C14 12CdN Se
562.6): calcd. C 29.8, H 2.1, N 19.9; found C 29.6, H 2.1, N 19.8.
IR (KBr): ν˜ = 2113 (s), 2062 (s), 1568 (m), 1448 (w), 1414 (s), 1385
H
8
2
(
Differential Thermal Analysis and Thermogravimetry: The DTA-TG
measurements were performed in a nitrogen atmosphere (purity:
–
1
(w), 1291 (w), 1285 (w), 965 (s), 759 (s), 741 (s), 667 (m) cm .
5.0) in Al
2 3
O crucibles using a STA-409CD thermobalance from
Synthesis of Compound 2B: Cd(NO ·4H O (154 mg, 0.50 mmol),
KNCSe (144 mg, 1.00 mmol) and pyridazine (72.4 μL, 1.00 mmol)
were stirred together in a 3 mL snap cap vial in water (2.9 mL) at
3
)
2
2
Netzsch. All measurements were performed with a flow rate of
75 mLmin and were corrected for buoyancy and current effects.
The instrument was calibrated using standard reference materials.
–
1
Eur. J. Inorg. Chem. 2011, 5502–5511
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5509

J. Boeckmann, I. Jeß, T. Reinert, C. Näther
FULL PAPER
Table 6. Selected crystal data and details on the structure determinations for compounds 1A–1C and 2A–2B.
1A
1B 1C 2A
2B
Formula
C
548.93
triclinic
P1
8.0308(8)
8.7489(8)
8.9443(9)
84.641(11)
67.701(11)
75.313(11)
562.44(9)
170
18
H
16CdN10
S
2
C
388.74
10
H
8
CdN
6
S
2
C
6
H
4
CdN
308.65
monoclinic
P2 /n
4
S
2
C
562.64
triclinic
P1
12.4219(9)
12.9662(9)
13.2628(10)
62.037(8)
87.134(9)
85.820(9)
1881.5(2)
200
14
H
12CdN
8
Se
2
C
482.54
10
H
8
CdN
6 2
Se
–1
MW [gmol ]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
orthorhombic
Pnma
11.6044(8)
15.0009(15)
7.9160(5)
90.0
90.0
90.0
1377.99(19)
293
orthorhombic
Pnma
11.8634(5)
15.0230(6)
8.1861(3)
90.0
90.0
90.0
1458.96(10)
293
¯
¯
1
9.6590(6)
15.6860(9)
13.3289(9)
90.0
101.152
90.0
α [°]
β [°]
γ [°] 3
V [Å ]
T [K]
1981.3(2)
293
Z
D
1
4
8
4
4
–3
calcd. [gcm ]
1.621
1.184
1.874
1.881
2.069
2.582
1.986
5.044
2.197
6.481
–1
μ [mm ]
θmax. [°]
27.98
25.98
25.00
27.00
28.00
Measured reflections
5123
0.0556
2640
4654
0.0436
1403
15379
0.0612
3492
21455
0.0404
8025
18136
0.0325
1806
R
int
Unique reflections
Reflections [F
Parameters
o
Ͼ 4σ(F
o
)]
2396
143
1119
97
2671
235
6002
455
1675
97
R
wR
1
[F
[all data]
GOF
o
Ͼ 4σ(F
o
)]
0.0356
0.0904
0.986
0.0362
0.0624
1.105
0.0602
0.0767
1.268
0.0335
0.0878
1.024
0.0377
0.0754
1.231
2
–3
Δρmax./min. [eÅ ]
0.791/–1.045
0.426/–0.575
0.451/–0.628
0.888/–1.308
0.846/–0.705
Supporting Information (see footnote on the first page of this arti-
cle): ORTEP plots, Infrared and Raman spectra and experimental
and calculated XRPD patterns for compounds 1A–1C and 2A–2B.
J. 2009, 15, 1757–1764; L. M. Toma, R. Lescouëzec, J. Pasan,
C. Ruiz-Perez, J. Vaissermann, J. Cano, R. Carrasco, W.
Wernsdorfer, F. Lloret, M. Julve, J. Am. Chem. Soc. 2006, 128,
4842–4853; J. H. Yoon, D. W. Ryu, H. C. Kim, S. W. Yoon, B.
Suh, C. Hong, Chem. Eur. J. 2009, 15, 3661–3665.
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[
Acknowledgments
1
7
1026; J. Boeckmann, C. Näther, Chem. Commun. 2011, 47,
104–7106.
This project was supported by the Deutsche Forschungsgemein-
schaft (DFG) (project number NA 720/3-1) and the State of Schles-
wig-Holstein. We thank Professor Dr. Wolfgang Bensch for access
to his experimental facility.
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