Synthesis, structure, and thermal properties of benzene-solvated forms of bis(dimethyldithiocarbamato)piperidinezinc and -copper(II)

Article abstract of DOI:10.1134/S1070328410070043

Solvated adducts of zinc and copper(II) dimethyldithiocarbamate complexes with piperidine of the general formula [M{NH(CH₂)₅}{S ₂CN(CH₃)₂}₂] ? C ₆H₆ (M = Zn (I), ⁶³Cu (II)) were isolated on a preparative scale. According to X-ray diffraction data, compound I has a clathrate type structure: the benzene molecules located between the coordinated piperidine rings of neighboring adduct molecules are held by hydrogen bonds. Thermal destruction of I studied by simultaneous thermal analysis includes the desorption steps of benzene solvate molecules and inner-sphere piperidine molecules and thermolysis of the dithiocarbamate part of the adduct to give ZnS as the final product. The triaxial anisotropy pattern of EPR parameters of the isotope-substituted magnetically diluted adduct II indicates that the geometry of the copper coordination polyhedron is intermediate between a tetragonal pyramid (TP) and trigonal bipyramid (TBP). It was shown solvation of the adduct [⁶³Cu{NH(CH₂)₅}{S ₂CN(CH₃)₂}₂] resulting a considerable increase in the contribution of the TBP component.

Full text of DOI:10.1134/S1070328410070043

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2010, Vol. 36, No. 7, pp. 502–508. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © I.A. Lutsenko, A.V. Ivanov, A.S. Zaeva, A.V. Gerasimenko, 2010, published in Koordinatsionnaya Khimiya, 2010, Vol. 36, No. 7, pp. 505–511.
Synthesis, Structure, and Thermal Properties of BenzeneꢀSolvated
Forms of bis(dimethyldithiocarbamato)piperidinezinc and ꢀcopper(II)
I. A. Lutsenkoa, A. V. Ivanova, *, A. S. Zaevaa, and A. V. Gerasimenkob
a Institute of Geology and Natural Management, Far East Division, Russian Academy of Sciences,
Blagoveshchensk, 675000 Russia
b Institute of Chemistry, Far East Division, Russian Academy of Sciences, pr. Stoletiya Vladivostoka 159,
Vladivostok, 690022 Russia
*Eꢀmail: alexander.v.ivanov@chemist.com
Received November 26, 2009
Abstract—Solvated adducts of zinc and copper(II) dimethyldithiocarbamate complexes with piperidine of
the general formula [M{NH(CH2)5}{S2CN(CH3)2}2] · C6H6 (M = Zn (
parative scale. According to Xꢀray diffraction data, compound
molecules located between the coordinated piperidine rings of neighboring adduct molecules are held by
hydrogen bonds. Thermal destruction of studied by simultaneous thermal analysis includes the desorption
I
), 63Cu (II)) were isolated on a preꢀ
has a clathrate type structure: the benzene
I
I
steps of benzene solvate molecules and innerꢀsphere piperidine molecules and thermolysis of the “dithiocarꢀ
bamate part” of the adduct to give ZnS as the final product. The triaxial anisotropy pattern of EPR parameters
of the isotopeꢀsubstituted magnetically diluted adduct II indicates that the geometry of the copper coordinaꢀ
tion polyhedron is intermediate between a tetragonal pyramid (TP) and trigonal bipyramid (TBP). It was
shown solvation of the adduct [63Cu{NH(CH2)5}{S2CN(CH3)2}2] resulting a considerable increase in the
contribution of the TBP component.
DOI: 10.1134/S1070328410070043
Transition and postꢀtransition metal dialkyldithioꢀ
carbamate complexes with open molecular configuraꢀ
tion are characterized by partial coordinative unsaturꢀ
ation of the complexing metal. Therefore, the disꢀ
cussed compounds can reversibly add molecules of
organic donor bases to the axial position, resulting in
the formation of mixedꢀligand complexes of donorꢀ
acceptor nature (generally called adducts). The pracꢀ
tical use of dithiocarbamate complexes and their
adducts with organic Nꢀ, Oꢀ, Sꢀ, and Pꢀbases is quite
diverse [1] including production of metal sulfide films
and powders with semiconductor properties [2, 3],
preconcentration of noble metals from dilute solutions
[4, 5], and so on. It is known that both the adduct forꢀ
The purpose of this work is to prepare and study the
structure and thermal properties (by EPR, Xꢀray difꢀ
fraction, and simultaneous thermal analysis data) of
solvated adducts [М{NH(CH2)5}{S2CN(CH3)2}2]
⋅
C6Н6 (M = Zn (
I
), 63Cu (II)).
EXPERIMENTAL
Synthesis. The solvated adduct
I
was prepared by
dissolving binuclear [Zn2{S2CN(CH3)2}4] [8] (0.50 g,
0.80 mmol) in benzene (5 ml) containing a 10% excess
of piperidine (0.178 ml, 1.76 mmol). The single crysꢀ
tals of I were grown from the obtained solution at room
temperature, separated from the mother solution, colꢀ
lected on a filter, and dried in air until loose. Yield
mation and solvation of the adducts can be used to 73%.
successively shift the range of thermal destruction of
the “dithiocarbamate fragment” of the compounds to
lower temperature (with respect to the initial dialkyꢀ
ldithiocarbamate complexes) [6].
Adduct II was prepared similarly to I but as an isoꢀ
topically substituted compound. To this end, copꢀ
per(II) salt with the 63Cu nuclide concentration of
99.3(1) at % was used. To increase the resolution of the
EPR spectra, the sample of II was obtained in the
magnetically dilute state (Cu : Zn = 1 : 1000). The
completeness of conversion of the starting complex to
the adduct was checked by gravimetry and EPR specꢀ
Previously [7], we obtained adducts of zinc and
copper(II) dimethyldithiocarbamate (MDtc) comꢀ
plexes with piperidine of the general formula
[
M{NH(CH2)5}{S2CN(CH3)2}2] and studied them by
tra. The obtained samples if
I and II were stored in
EPR, MAS NMR (13C, 15N), and Xꢀray diffraction. sealed tubes.
For each adduct, the possibility for existence of two
isomers was established.
The EPR spectra of magnetically dilute complex II
were measured on a 70ꢀ02 XD/1 radiospectrometer
502

SYNTHESIS, STRUCTURE, AND THERMAL PROPERTIES
503
Table 1. Crystal data, experiment and structure refinement
details for structure I
operating at ~9.5 GHz at room temperature. The
working frequency was measured by a ChZꢀ46 microꢀ
wave frequency meter. The
with respect to DPPH. The error in determination of
value was 0.002; that for the hyperfine structure
constants (HFS, measured in Oersted) was 2%. The
EPR spectra were simulated in terms of the second
approximation of perturbation theory using the WINꢀ
EPR SimFonia program, version 1.2 (Bruker softꢀ
ware). The simulated spectra were approximated to
g value were calculated
Parameter
Molecular formula
Value
C11H23N3S4Zn
469.04
⋅
C6H6
g
М
System
Space group
Monoclinic
2/
С
c
a
,
Å
Å
Å
8.1172(9)
23.249(3)
12.4801(14)
108.809(2)
2229.4(5)
4
b,
experimental ones by varying the
g value, HFS conꢀ
stants, resonance line widths, and the contributions of
Lorentzian and Gaussian components to the line
shape.
c,
β
, deg
Å3
V,
The thermal properties of I were studied by simulꢀ
Z
ρ(calcd.), g/cm3
, mm–1
(000)
1.397
taneous thermal analysis (STA) comprising simultaꢀ
neous recording of thermogravimetry (TG) and differꢀ
ential scanning calorimetry (DSC) curves. The meaꢀ
surements were carried out on an STA 449C
NETZSCH instrument in corundum crucibles under
a lid with a hole providing a vapor pressure of 1 atm
during the thermal decomposition of the sample.
μ
1.482
F
984
Crystal shape (size, mm)
Prism
(0.40
1.75–30.00
–5 11,
–32
–17
8155
int = 0.0190)
×
0.33
×
0.25)
Data collection range, θ, deg
Heating to 400 С was performed at a rate of 5°C/min
°
Range of reflection indices
≤ h ≤
under argon. The sample weight was 4.46–6.35 mg.
The accuracy of temperature measurement was
≤
k
≤
32,
17
≤ l ≤
0.7
°
С
, that of weight measurement was
1
10–2 mg.
×
The number of reflections
The TG and DSC curves were recorded using a correcꢀ
tion file and calibration on temperature and sensitivity
for the specified temperature program and heating
rate. An independent determination of the melting
The number of independent
reflections
3168 (R
The number of reflections
2547
with
I
> 2σ(I)
point of
I was carried out on a PTP(M) instrument
The number of refinement variables
GООF
Rꢀfactors on F2 > 2
172
(OJSC Himlaborpribor).
1.018
XꢀRay diffraction analysis of
Bruker Smart 1000 CCD diffractometer (Mo
I
was carried out on a
radiaꢀ
σ(
F2
)
R
1 = 0.0289, wR2 = 0.0657
1 = 0.0414, wR2 = 0.0717
–0.438/0.401
K
α
tion,
λ
= 0.71073 Å, graphite monochromator) at Rꢀfactors for all reflections
R
203(2) K. The data were collected in the hemisphere
region by a standard procedure [9]; the crystal–detecꢀ
tor distance was 45 mm. The absorption corrections
were based on equivalent reflections. The structure
was solved by the direct method and refined by the
fullꢀmatrix leastꢀsquares method (on F2) in the anisoꢀ
tropic approximation for nonꢀhydrogen atoms. The
positions of hydrogen atoms were calcsulated geometꢀ
rically and included in the refinement by the “riding”
model.
Residual electron density
(min/max),
Å–3
e
Centre (no. 752924; deposit@ccdc.cam.ac.uk or
http:// www.ccdc.cam.ac.uk).
RESULTS AND DISCUSSION
The EPR spectrum of compound II (Fig. 1, curve
The data were collected and edited and the unit cell exhibits two quartets, of some nonequidistant HFS
parameters were refined by the SMART [9] and components of the 63Cu nucleus (
= 3/2), and two
a)
I
SAINT [10] program packages. All calculations for intense peaks of “extra features” [12, 13] in the highꢀ
structure solution and refinement were carried out field region. In addition, computer simulation of the
using the SHELXTL/PC program package [11]. spectrum revealed one more orientation (g3 = 2.018)
Selected crystal data and structure refinement details in the highꢀfield region. The simulation was carried
for structure
I are summarized in Table 1, while the out in two stages. The first stage included the construcꢀ
bond lengths and bond angles are in Table 2. The atom tion of the first derivatives of the EPR spectra. This was
coordinates, the bond lengths, and the bond angles are followed by double differentiation of the experimental
deposited with the Cambridge Crystallographic Data spectra, resulting in crucial narrowing of the HFS
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
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504
LUTSENKO et al.
Table 2. Selected bond lengths and bond (ω) and torsion (ϕ) angles in structure I*
Bond Bond
N(2)
d
,
Å
d, Å
Zn
Zn
Zn
−
−
−
2.0863(13)
2.6115(4)
2.3488(3)
1.7113(9)
1.7320(10)
1.3288(11)
1.4642(13)
N(1)
N(2)
N(2)
−
C(3)
C(4)
C(8)
1.4611(13)
1.452(2)
1.492(3)
1.573(3)
1.465(4)
1.572(3)
1.475(3)
S(1)
S(2)
−
−
S(1)
−
C(1)
C(1)
C(4)
C(5)
C(6)
C(7)
−
C(5)
C(6)
C(7)
C(8)
S(2)
−
−
−
−
N(1)
N(1)
−
C(1)
−
C(2)
Angle
ω
, deg
Angle
ω
, deg
N(2)ZnS(1)
N(2)ZnS(1)a
N(2)ZnS(2)
N(2)ZnS(2)a
S(1)ZnS(2)
S(1)ZnS(1)a
S(1)ZnS(2)a
S(2)ZnS(2)a
C(1)S(1)Zn
C(1)S(2)Zn
S(1)C(1)S(2)
N(1)C(1)S(1)
92.05(4)
102.66(4)
125.99(3)
111.17(3)
72.912(11)
165.096(12)
99.709(11)
122.28(2)
80.37(3)
N(1)C(1)S(2)
C(1)N(1)C(2)
C(1)N(1)C(3)
C(3)N(1)C(2)
C(4)N(2)Zn
119.60(7)
121.54(8)
121.92(8)
116.54(7)
109.60(11)
115.73(13)
111.0(2)
110.7(2)
111.6(2)
109.1(2)
109.8(2)
114.7(2)
C(8)N(2)Zn
C(4)N(2)C(8)
N(2)C(4)C(5)
C(4)C(5)C(6)
C(5)C(6)C(7)
C(6)C(7)C(8)
C(7)C(8)N(2)
88.14(3)
118.23(5)
122.17(8)
Angle
ϕ, deg
Angle
ϕ, deg
C(1)S(1)S(2)Zn
S(2)ZnC(1)S(1)
S(1)C(1)N(1)C(2)
173.03(5)
174.21(4)
177.13(7)
S(1)C(1)N(1)C(3)
S(2)C(1)N(1)C(2)
S(2)C(1)N(1)C(3)
–3.45(11)
–2.53(11)
176.89(6)
Benzene molecules
Bond
d,
Å
Bond
d, Å
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
1.378(2)
1.378(2)
1.371(2)
C(13)–C(14)
C(13)–C(13)b
C(14)–C(15)
C(15)–C(15)b
1.368(5)
1.380(5)
1.379(5)
1.373(5)
Angle
ω
, deg
Angle
ω
, deg
C(9)C(10)C(11)
C(10)C(9)C(10)b
C(10)C(11)C(12)
C(11)C(12)C(11)b
119.6(2)
120.7(2)
119.3(2)
121.5(2)
C(13)C(14)C(15)
C(14)C(13)C(13)b
C(14)C(15)C(15)b
122.0(4)
119.0(2)
118.9(2)
a
b
* The symmetry operation codes: −x + 2, y, −z + 3/2; −x + 1, y, −z + 3/2.
components and increase in the resolution level. The
The results of computer simulation attest to the
individual character of the spectral pattern of solvated
adduct II (Fig. 1, curve ). The simulated spectrum
bearing a high degree of similarity reflects with high
accuracy the position and the relative intensity of the
HFS components in all three orientations and peaks of
“extra features” that are not specified parametrically
second stage consisted of attaining of the highest posꢀ
sible approximation of the third derivatives of the simꢀ
ulated spectra to the experimental ones. The results of
b
best approximation are presented in Fig. 1, curve
and Table 3.
b
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SYNTHESIS, STRUCTURE, AND THERMAL PROPERTIES
505
It was shown previously [16] that an increase in the
TBP contribution to the geometry of the copper polyꢀ
DPPH
hedron results in an antiparallel change in the AC1 u and
AC2 u values such that the HFS constants of lowꢀfield
orientation decrease and those of the intermediate oriꢀ
entation increase. Therefore, the difference between
а
b
50 Oe
the AC1 u and AC2 u constants (the
Δ
parameter) can be
used to estimate the TBP contribution to the geometry
of the copper polyhedron. It was found that the lower
the
case, the
43 Oe compared to the isomeric forms of nonꢀsolvated
adduct ( = 94 and 112 Oe). Thus it is clear that solvaꢀ
Δ
value, the higher the TBP contribution. In our
Δ
value for the solvated adduct II decreases to
Δ
tion of the adduct [Cu{NH(CH2)5}{S2CN(CH3)2}2] is
accompanied by increase in the TBP contribution to
the geometry of the copper polyhedron.
The structural units of the crystal
I are the adduct
molecules and the benzene solvate molecules (Fig. 2). In
the adduct molecules, [Zn{NH(CH2)5}{S2CN(CH3)2}2],
the central atom coordinates S,S'ꢀbidentately two
structurally equivalent MDtc ligands and a piperidine
Fig.
1.
EPR
spectra
of
63
[
Cu{NH(CH ) }{S CN(CH ) } ] · C H : (a) experiꢀ
2 5 2 3 2 2 6 6
mental and (b) simulated.
molecule to give the chromophore
[ZnS4N]
during simulation. The type of thriaxial anisotropy of (C.N.(Zn) = 5). The dithiocarbamate ligands show an
anisobidentate coordination mode: the Zn–S(2) bond
the EPR parameters of adduct II (Table 3) indicates an
essential rhombicity of the local environment of the
metal. For copper(II) complexes with C.N. 5, this
condition is met for the polyhedra with an intermediꢀ
ate geometry between tetragonal pyramid (TP) and
trigonal bipyramid (TBP) and the ground state of the
unpaired electron is formed upon mixing of copper(II)
(
(
2.349 Å) is much stronger than the Zn–S(1) bond
2.612 Å). The strength of binding of the piperidine
molecule in solvated adduct I is somewhat lower (Zn–N,
2.0863 Å) than in the nonꢀsolvated form (Zn–N,
2.0743 Å) [7].
The bidentate coordination of MDtc ligands gives
rise to smallꢀsized fourꢀmembered metallocycles
3dx
ꢀ
and 3dz2ꢀАО [14, 15].
2 – y2
[
ZnS2C] with rather short Zn⋅⋅⋅C and S⋅⋅⋅S distances
0
y
x
z
Fig. 2. Projection of the crystal structure of
I
on the yz plane.
2010
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36 No. 7

506
LUTSENKO et al.
a
C(6)
a
C(6)
a
C(5)
C(7)
C(7)
C(12)
C(5)
C(8)
b
b
C(15)
C(15)
a
C(8)
C(11)
C(14)
C(11)
C(14)
a
C(4)
C(4)
b
C
g
H(2)
b
a
N(2)
H(2)
N(1)
b
C(10)
C(13)
C(10)
C(13)
b
C(9)
S(1)
a
Zn
S(1)
a
S(2)
S(2)
C(2)
C(1)
C(3)
N(1)
Fig. 3. Alternation of the adduct molecules and benzene solvate molecules in structure I. The dashed lines show the hydrogen
bonds.
(2.873 and 2.955 Å, respectively). The CSSZn and
SZnCS torsion angles (173.0 and 174.2 ) attest to the
deviation of atoms in these rings from the plane. The
CNCS torsion angles (Table 2) point to a planar conꢀ
figuration of the C2NCS2 groups. The mesomeric
effect in the dithiocarbamate groups results in the
N⎯C(S)S bond(1.329 Å) being much shorter than the
N–CH3 bonds (1.461–1.464 Å), which reflects the
considerable contribution of double bonding to the
formally single bond and admixing of sp2ꢀ to the sp3 165.1
The geometry of the zinc polyhedron [ZnNS4] is interꢀ
mediate between TP and TBP. For quantitative description
of the metal polyhedra in pentacoordinate complexes, it is
convenient to use the parameter τ = (α − β)/60 [17] (in
°
°
this case,
α > β). For a regular TP,
a regular TBP (
equatorial angle
α
and
β
are the two largest LZnL angles,
C4v = 0, because . In
3v), the axial angle = 180 and the
= 120 = 1. The parameter in the
(
)
τ
α
=
β
C
β
α
°
°
;
τ
τ
range of 0–1 defines the polyhedra with intermediate
geometry. For compound angles
, S(1)ZnS(1)a, is
and , N(2)ZnS(2), is 126.0 . Hence, = 0.65,
I
α
°
β
°
τ
which implies a TBP contribution of 65% (in the iniꢀ
tial nonꢀsolvated adduct, this contribution is only ~4%
[7]). Thus, a direct consequence of the solvation of
initial adduct is an essential deviation of the TP geomꢀ
etry of the zinc polyhedron toward TBP. The equatoꢀ
rial plane of the TBP is formed by the piperidine nitroꢀ
gen atom and two most strongly bonded sulfur atoms.
The less strongly bound sulfur atoms occupy axial
positions.
hybrid state of the nitrogen and carbon atoms in the
=NC(S)S– group.
b
C(14)
b
C(10)
b
C(11)
b
C(13)
In the coordinated piperidine molecule, all atoms
are disordered between two structural positions (with
equal occupancy of 0.5) with respect to the twofold
b
C(15)
C(9)
C(12)
rotation axis passing through the zinc atom along the
axis (i.e., the presence of adduct molecules rotated
through 180 with respect to each other is equally
y
°
C(15)
C(13)
probable in each position) (Fig. 3). The outerꢀsphere
benzene solvate molecules are located strictly between
the coordinated piperidine molecules and are held by
hydrogen bonds N(2)a–H(2)a⋅⋅⋅Cg with the piperidine
C(10)
C(11)
C(14)
NH groups (
NHC, 166 ). According to the topological relationship
between the host and guest molecules, compound
N⋅⋅⋅C 3.690(2), N–H 0.92, H⋅⋅⋅C 2.79 Å;
°
I
refers to the lattice clathrate class with features of
sandwich structure [18]. All carbon atoms of the benꢀ
Fig. 4. Mutual spatial orientation of the planes of disorꢀ
dered benzene solvate molecule
zene molecule in
I are also disordered between two
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SYNTHESIS, STRUCTURE, AND THERMAL PROPERTIES
507
TG, %
DSC, mW/mg
100
90
80
70
60
50
40
30
–9.93%
–16.29%
а
2.0
296.2°C
–18.67%
360.6°C
1.5
1.0
0.5
0
326.8°C
216.9°C
178.1°C
b
22.02%
127.5°C
334.0°C
T, °C
50
100
150
200
250
300
350
Fig. 5. (a) TG curves and (b) DSC curves of compound I.
positions (with 0.5 occupancy of each position and endotherm is caused by sample melting (extrapolated
with displacement of the С6 planes with respect to one
another by 30 (Fig. 4)). The benzene molecules in
mp =119.1
The subsequent section of the TG curve (above
180 C) reflects desorption of the innerꢀsphere piperiꢀ
dine molecules. The extrapolated temperature of the
end of piperidine desorption and the start of the third
(final) stage of the thermal destruction occurs at
°C).
°
each orientation have a twofold rotation axis but in
one of them, the axis passes through the C(9) and
C(12) atoms and in the other, through the midpoints
of the C(13)–C(13)b and C(15)–C(15)b bonds (Table 2).
°
The behavior of I during the TG experiment (under
297°C. The weight loss in the range of 180–297°C
inert argon atmosphere) is fairly similar to the behavꢀ
ior of other solvated adducts we studied previously [6,
19, 20]. The first step of weight loss in the TG curve
equals 18.67% (the theoretical value is 18.15%). Thus,
the overall weight loss caused by benzene and piperiꢀ
dine desorption is 34.96% (the theoretical value is
34.80%). The steeply descending section of the TG
curve in the highꢀtemperature region is related to the
thermal destruction of the dithiocarbamate fragment
of the complex. The experimental/theoretical weight
loss at the final stage is 42.51/44.42%. In the correꢀ
sponding sections of the DSC curve, the slightly proꢀ
(Fig. 5, curve a) recorded at 70–180°C is due to the
desorption of benzene solvate molecules. The weight
loss is 16.29% (the theoretical value is 16.65%). This
region of TG curve contains an additional intermediꢀ
ate inflection (with transition to a smoother section)
corresponding approximately to half of the benzene
weight loss (since the inflection points in the TG curve
were poorly visible, differentiation was used). This
may imply the possibility of existence of a solvated
adduct with halved number of benzene molecules. The
nounced endotherm with an extremum at 216.9
be related to desorption of piperidine, while the symꢀ
metric endotherm at 326.8 C reflects the complex
°C can
°
pattern of thermolysis of dithiocarbamate complexes
to give metal sulfides [21, 22]. The thermodynamic
DSC curve (Fig. 5, curve
this temperature range with an extremum at 127.5
b
) shows an endotherm in
C.
°
It was found by independent measurements that this substantiation of the formation of metal sulfides upon
Table 3. EPR parameters of compound II and its nonꢀsolvated form
AC1 u
,
Oe*
AC2 u
,
Oe*
AC3 u
, Oe*
g1
g2
g3
Complex
[63Cu{NH(CH2)5}{S2CN(CH3)2}2]
⋅
С6Н6 (II
)
2.117
2.126
2.132
109
128
130
2.085
2.054
2.041
66
34
18
2.018
2.028
2.029
42
3.0
2.5
[63Cu{NH(CH2)5}{S2CN(CH3)2}2] [7]**
63
* The HFS constants are given for Cu.
** Data are given for two isomeric adduct forms.
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508
LUTSENKO et al.
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thermolysis of metal complexes with sulfurꢀcontainꢀ
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The weight of the residue formed upon thermolysis
of I is 22.02% (the theoretical value is 20.78%), indiꢀ
cating the formation of ZnS (with the wurtzite strucꢀ
ture [24]) contaminated by thermolysis products (usuꢀ
ally, under inert atmosphere carbon is also formed).
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ACKNOWLEDGMENTS
The authors are grateful to Bruker company for
providing free use of WINꢀEPR SimFonia software.
14. Arriortua, M.A., Mesa, J.L., Rojo, T., et al., Inorg.
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This work was supported by the Russian Foundaꢀ
tion for Basic Research (project no. 08ꢀ03ꢀ00068ꢀa)
and Presidium of the Far East Division of the RAS
(project no. 09ꢀIIIꢀB ꢀ04ꢀ103, Program on the Funꢀ
damental and Applied Research of Young Scientists).
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