Cobalt(II) and nickel(II) complexes with 1-methyl-2-pyridin-2-yl-1H- and 1-methyl-2-phenyliminomethyl-1H-benzimidazoles and the closo-decaborate anion

Article abstract of DOI:10.1134/S0036023615070037

Synthesis of cobalt(II) and nickel(II) complexes with the closo-decaborate anion and benzimidazole derivatives (L¹ = C₁₃N₃H₁₁, L² = C₁₅N₃H₁₃) of the general formula [ML₃][B₁₀H₁₀] (M = Co, Ni) is described. Complexes have been characterized by elemental analysis, IR and UV spectroscopy. The structure of a [Ni(L¹)₃][B₁₀H₁₀] · 1.797CH₃CN single crystal has been determined by X-ray diffraction. The imidazole and pyridine N atoms of three L¹ molecules, two of which are disordered, form the distorted octahedral environment of the Ni atom. In the crystal, the majority of complexes [Ni(L¹)₃]²⁺ have the meridional configuration. The Ni-N bonds with the imidazole nitrogen atoms (2.010(4)-2.076(3) ?) are shorter than those with the pyridine atoms (2.132(4)-2.179(5) ?). This nonequivalence of the Ni-N bonds is responsible for the low magnetic susceptibility of the compound.

Full text of DOI:10.1134/S0036023615070037

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2015, Vol. 60, No. 7, pp. 817–822. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.V. Avdeeva, I.N. Polyakova, L.V. Goeva, E.A. Malinina, A.P. Zhdanov, K.Yu. Zhizhin, N.T. Kuznetsov, 2015, published in Zhurnal Neorganicheskoi
Khimii, 2015, Vol. 60, No. 7, pp. 901–907.
Cobalt(II) and Nickel(II) Complexes
with 1ꢀMethylꢀ2ꢀPyridinꢀ2ꢀylꢀ1
Hꢀ
and 1ꢀMethylꢀ2ꢀPhenyliminomethylꢀ1 ꢀBenzimidazoles
H
and the closoꢀDecaborate Anion
V. V. Avdeeva, I. N. Polyakova, L. V. Goeva, E. A. Malinina,
A. P. Zhdanov, K. Yu. Zhizhin, and N. T. Kuznetsov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
eꢀmail: avdeeva.varvara@mail.ru
Received February 9, 2015
Abstract—Synthesis of cobalt(II) and nickel(II) complexes with the closoꢀdecaborate anion and benzimidaꢀ
1
2
zole derivatives (L = C N H , L = C N H13) of the general formula [ML ][B H10] (M = Co, Ni) is
13
3
11
15
3
3
10
described. Complexes have been characterized by elemental analysis, IR and UV spectroscopy. The structure
1
of a [Ni(L ) ][B H ] 1.797CH CN single crystal has been determined by Xꢀray diffraction. The imidazole
⋅
3
10 10
3
1
and pyridine N atoms of three
ronment of the Ni atom. In the crystal, the majority of complexes [Ni(L ) ] have the meridional configuꢀ
L molecules, two of which are disordered, form the distorted octahedral enviꢀ
1
2+
3
ration. The Ni–N bonds with the imidazole nitrogen atoms (2.010(4)–2.076(3) Å) are shorter than those
with the pyridine atoms (2.132(4)–2.179(5) Å). This nonequivalence of the Ni–N bonds is responsible for
the low magnetic susceptibility of the compound.
DOI: 10.1134/S0036023615070037
The literature data on nickel(II) complexes with of industry. The development of the optimal condiꢀ
2
–
the boron cluster anions [B H ] (
n
= 10, 12) are few tions for the synthesis of metal complexes with benzꢀ
in number. Structures of two aqua complexes— imidazoleꢀbased organic ligands and boron cluster
Ni(H O) ][B H ] 6H O and anions is a topical problem. Its solution allows one, on
6H O—prepared by one hand, to carry out oneꢀstage syntheses of comꢀ
n
n
[
⋅
2
6
12 12
2
[
Ni(H O) ](H O) [B H ]
⋅
2
6
3
2
12 12 2
2
reaction of nickel(II) carbonate or nickel(II) hydroxꢀ plexes, and, on the other hand, to develop the concept
ide with the (H O) [B H ] acid were determined by of the nature of chemical bond in such compounds
3
2
12 12
Xꢀray crystallography [1, 2]. Complexes [NiL ][B H ] and of the processes of ligand replacement.
3
n
n
(
(
2
(
n
= 10, 12) with such ligands as benzoyl hydrazine
Bh), metaꢀnitrobenzoyl hydrazine ( ꢀNBh) [3, 4],
,2'ꢀbipyridyle (Bipy), and 1,10ꢀphenanthroline
Phen) [5, 6], as well as complex [Ni(en) ][B H12]
This paper describes the synthesis, structure, and
physical and chemical properties of complex comꢀ
pounds [ML ][B H ] with benzimidazole derivatives
m
3
10 10
1
2
3
12
L = C N H (L ) or C N H (L ).
13 3 11 15 3 13
with ethylenediamine [7], were synthesized. These
compounds were characterized by various physical
and chemical methods; based on indirect analytical
methods, it was assumed that nickel(II) atoms have
the octahedral environment formed by three chelating
EXPERIMENTAL
Triethylammonium decahydroꢀclosoꢀdecaborate
Et NH) [B H ] was synthesized from decaboꢀ
rane(14) through the stage of formation of 1,6ꢀbis(triꢀ
methylamine)decaborane as described in [9].
(
3
2
10 10
2–
ligands, and the [В H ] anions are in the outer
n
n
sphere of the complexes.
1
ꢀMethylꢀ2ꢀ(2ꢀpyridyl)benzimidazole C N H
Among the organic ligands, 2ꢀsubstituted derivaꢀ
tives of benzimidazole with substituents containing a
multiple CN bond are of particular interest for the
chemistry of complex compounds [8]. This is
13 3 11
1
(
L ) was prepared according to the procedure reported
in [8].
1ꢀMethylbenzimidazoꢀ2ꢀylꢀmethyleneaniline C N H
13
1
5
3
explained by the presence of donor nitrogen atoms of (L2) was synthesized through the stage of formation of
different nature in their structures, the potential ability 1ꢀmethylꢀ2ꢀformylbenzimidazole (MFBZ) that was
to act as tridentate ligands, and the pharmacological prepared according to the known procedure [10]
properties that allow one to use complexes prepared (Scheme 1). The yield of MFBZ was 2.18 g (45%)
on their basis in medicine, agriculture, and some fields from 1ꢀmethylbenzimidazole (4.00 g, 30.3 mmol) and
817

818
AVDEEVA et al.
Table 1. Maxima of selected absorption bands in the IR spectra of the benzimidazole derivatives L and complexes
–1
[
ML ][B H ],
ν
, cm
Compound
L = C N H
3
10 10
ν
(C=N)
ν
(C=N) of the benzꢀ
imidazole ring
ν
(C=N) of the pyriꢀ
ν
(BH)
–
of the imine group
dine ring
1
–
–
1566
1571
1573
1590
1585
1585
1590
1602
1601
–
13
3
11
1
[
Co(L ) ][B H ] (
I
)
2438
2435
–
3
10 10
1
[
Ni(L ) ][B H ] (II
)
–
3
10 10
2
L = C N H
13
1630
1604
1616
1
5
3
2
[
Co(L ) ][B H ] (III
)
2454
2453
–
3
10 10
2
[
Ni(L ) ][B H ] (IV
)
–
3
10 10
DMF (4.98 g, 68.2 mmol). MFBZ (2.18 g, tered off, washed with water and hexane. The prodꢀ
3.6 mmol) was dissolved in 15 mL of absolute uct was recrystallized from hot ethanol and dried
1
EtOH, and then aniline (1.33 g, 14.3 mmol) was under vacuum of an oil pump. Obtained: 2.72 g
added. The reaction solution was stirred under dry (85%) of 1ꢀmethylꢀbenzimidazoꢀ2ꢀylꢀmethyleneꢀ
2
argon atmosphere for 72 h. The precipitate was filꢀ aniline (ligand
L
).
CH3
CH3
H2N
CH3
H
O BuLi
CH3
N
N
O
H
N
+
O
N
N
MFBZ
N
N
H C
3
L2
Scheme 1.
For C N H anal. calcd. (%): C, 76.57; H, 5.57;
Found for I (%): C, 58,15; H, 5.38; N 15,62; B,
15
3
13
N, 17.86.
Found L (%): C, 35.13; H, 8.53; N, 13.70.
1H NMR (DMSOꢀd6,
, ppm: 4.12 (s, 3H, СH ); 5.39; N, 15.67; B, 13.44; Ni, 7.29.
13.40; Co, 7.24.
2
For C H N B Ni anal. calcd. (%): C, 58.22; H,
39
49
9 10
δ
3
7
.16 (m, 2H, оꢀС ꢀH); 7.27–7.34 (m, 2H, С ꢀH),
Ph BZ
Found for II (%): C, 58.18; H, 5.29; N 15.66; B,
7
.38 (m, 1H, pꢀC ꢀH), 7.45 (m, 2H, С ꢀH); 7.60
Ph BZ
13.30; Ni, 7.15.
(
m, 2H,
t
ꢀС ꢀH); 9.04 (s, 1H, N=CH).
Ph
For C H N B Co anal. calcd. (%): C, 61.21; H,
13
C NMR (DMSOꢀd6,
45 49
9 10
δ
, ppm): 31.69 (СH );
3
5
.59; N, 14.28; B, 12.24; Co, 6.67.
1
1
1
10.67, 118.64, 120.18, 123.90, 125.01, 125.72,
29.61, 139.39, 141.77 (aromatic), 150.22 (N=CH),
51.89, 152.26 (aromatic).
Found for III (%): C, 60.98; H, 5.44; N 14.19; B,
12.18; Co, 6.64.
1
Synthesis of [ML ][B H
]
(L = L = C N H11,
For C H N B Ni anal. calcd. (%): C, 61.23; H,
3
10 10
13
3
45 49
9 10
2
M = Co (I), Ni (II)); L = L = C H N3; M = Co 5.59; N, 14.28; B, 12.25; Ni, 6.65.
15 13
(
III), Ni (IV)). Solid CoCl2 or NiCl2 (1 mmol) was
Found for IV (%): C, 60.50; H, 5.37; N 14.10; B,
2.15; Ni, 6.61.
added to a solution of (Et NH) [B H ] (1 mmol) in
acetonitrile (10 mL) on stirring. The reaction solution
became blue or green upon the dissolution of the metal
3
2
10 10
1
Elemental analysis for carbon, hydrogen, and
1
2
nitrogen was carried out on a Carlo Erba CHNSꢀ3
FA 1108 automated elemental analyzer. Determinaꢀ
tion of boron and metals was performed on an
iCAP 6300 Duo ICP emission spectrometer with
inductively coupled plasma.
chlorides. When a solution of ligand
L or L (3 mmol)
in acetonitrile (5 mL) was added to the reaction soluꢀ
tion, the mixture changed its color to sand or coffee,
respectively. Formation of polycrystalline precipitates
of sand (
after 2–3 h. The yield of I–IV was more than 80%
based on boron. A single crystal of II 1.797CH CN
I or II) or coffee (II or IV) colors was observed
IR spectra of the initial compounds and reaction
products (Table 1) were recorded on a Lumex
Infralum FTꢀ02 Fourierꢀtransform spectrometer in
⋅
3
suitable for Xꢀray crystallography was isolated directly
from the reaction solution.
–1
–1
the range of 4000–600 cm at a resolution of 1 cm .
For C H N B Co anal. calcd. (%): C, 58.20; H, Samples were prepared as Nujol (Aldrich) mulls;
39
43
9 10
5
.57; N, 15.66; B, 13.43; Co, 7.32.
NaCl pellets were used.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

COBALT(II) AND NICKEL(II) COMPLEXES
819
UV spectra of compounds suspended in glycerol Table 2. Crystallographic data, details of data collection, and
characteristics of structure refinement for II 1.797CH CN
⋅
were measured on an SF 103 spectrophotometer in the
visible region 200–800 nm.
3
Molecular formula
FW
C42.59H48.39B N10.80Ni
10
1
13
H and C NMR spectra of a solution of L in
2
878.46
150(2)
6
DMSOꢀ
d
were recorded on a Bruker Avance IIꢀ300
T
, K
radiospectrometer at the operating frequencies of
3
00.3 and 96.32 MHz, respectively, with internal deuꢀ Radiation,
λ
, Å
MoK , 0.71073
α
terium lock; tetramethylsilane was used as an external
standard.
Space group,
Z
P
1, 2
a
, Å
, Å
10.2783(11)
14.5696(16)
15.7379(17)
102.217(2)
90.849(2)
107.341(2)
2191.0(4)
1.332
The static magnetic susceptibility of a polycrystalꢀ
line sample of II was measured in the temperature
range 300–4 K with a Quantum Design PPMSꢀ9
AC/DC instrument.
b
c
, Å
, deg
, deg
, deg
α
Xꢀray crystallography. The set of diffraction reflecꢀ
β
tions for II 1.797CH CN was collected on a Bruker
⋅
3
SMART APEX2 automated diffractometer at the
Shared Facility Center, IGIC RAS. The data were colꢀ
lected and processed with the APEX2, SAINT, and
γ
, Å3
V
ρ
μ
, g/cm3
x
SADABS programs [11]. The structure of II
⋅
, mm–1
0.490
1
.797CH CN was solved by the direct method using
3
Mo
the SIRꢀ92 program [12]. In the structure of
Tmin
(000)
pyridine fragments replace each other. The ratio of site Crystal size, mm
,
Tmax
0.6317, 0.7450
915
1
IV
⋅
1.797CH CN, two L molecules are disordered
over two positions, in which the methylimidazole and
3
F
0.24
×
0.14 × 0.06
occupancy factors is 0.953(3) : 0.047(3) for the N(1)ꢀ
C(13) molecule and 0.797(4) : 0.203(4) for the N(4)ꢀ
C(26) molecule. The acetonitrile molecule N(11)ꢀ
C(43) is incompatible with the poorly occupied posiꢀ
tion of the N(4)ꢀC(26) molecule; therefore, its site
occupancy factor is equal to 0.797(4). The L moleꢀ
cules at the poorly occupied positions were refined by
the leastꢀsquars procedures with restrained geometry
θ
range, deg
2.161–24.275
Number of reflections:
collected
16813
7082 [0.0461]
4653
unique (
with > 2
1, wR2 for No
1, wR2 for
N
) [Rint
]
I
σ
(
I) (No)
R
R
S
0.0626, 0.1468
0.1041, 0.1700
1.034
(
(
SAME instructions) and Ni–N bond lengths
DFIX). The thermal parameters of the minor comꢀ
N
ponent of the N(1)ꢀC(13) molecule were assumed to
be equal to Ueq of the corresponding atoms of the
major component and fixed, and those of the N(4)ꢀ
C(26) molecule were refined isotropically. All other
Δρmax/Δρ , e/Å3
1.097/–0.801
min
nonꢀhydrogen atoms were refined in the anisotropic degree by the nature of substituents. In the present
1
2
approximation. Some of the hydrogen atoms were work, the benzimidazole derivatives
L and L were
located on difference Fourier maps; the positions of used, their structures are presented in Fig. 1.
Complexes [ML ][B H10] (M = Co, Ni; L = L1 or
3 10
the lacking hydrogen atoms were calculated. The H
atoms of the methyl C(41) atom are disordered over L2) were prepared by reaction of triethylammonium
two positions with equal occupancies (0.49(6) : closoꢀdecaborate with cobalt(II) or nickel(II) chloride
0
.51(6)). Hydrogen atoms were refined by the riding and a threefold excess of benzimidazole derivatives L
model. Structure of II
the SHELXLꢀ2013 program [13].
⋅
1.797CH CN was refined using
3
Main crystal data, details of data collection, and
characteristics of structure refinement are listed in
Table 2. The crystallographic data have been deposited
with the Cambridge Structural Database (CCDC
no. 1044931).
M
M
N
N
N
N
N
N
CH3
L1
CH3
L2
RESULTS AND DISCUSSION
Compounds of the imidazole class possess physioꢀ
logical activity; the extent of their physiological action
and its direction are determined to a considerable
Fig. 1. Coordination of ligands L1 and L2 in complexes
ML ][B H10].
[
3
10
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

820
AVDEEVA et al.
C(4)
C(3)
C(5)
C(37)
C(38)
C(6)
C(2)
C(1)
C(36)
C(35)
C(33)
C(8)
C(39)
C(34)
N(2)
C(7)
C(9)
N(8)
C(32)
N(9)
N(1)
C(31)
N(7)
N(3)
Ni(1)
C(27)
C(28)
C(10)
C(15)
C(14)
C(30)
C(26)
C(11)
N(4)
C(29)
C(13)
C(12)
N(6)
C(16)
C(17)
C(20)
C(25)
C(22)
C(23)
C(19)
C(18)
N(5)
C(24)
C(21)
Fig. 2. Fragment of structure II ⋅ 1.797CH CN. Thermal ellipsoids are shown at the 30% probability level.
3
(
Scheme 2). The compounds were formed selectively late rings are formed. The coordination of one moleꢀ
1
and in good yields.
cule of ligand L is schematically presented in Fig. 1.
The participation of the pyridine nitrogen atom in
metal coordination is also confirmed by the shifts of
the absorption band maxima of the pyridine ring in the
[
ML ][B H ] (I– )
IV
L = L = C N H :
3 10 10
1
(
Et NH) [B H ] + 3L
3 2 10 10
L = C N H or
13 3 11
DMF
–1
range 1600–700 cm and the alteration of the ratio of
1
C N H
3 3 11
M = Co (I), Ni (II
)
2
their intensities. The highꢀfrequency shifts of the maxꢀ
ima of the stretching vibrations bands of both CN
bonds upon metal coordination indicate that the cheꢀ
late ring is involved in the system of conjugation of the
ligand.
1
5
3
13
L = L = C N H :
15 3 13
M = Co (III), Ni (IV
Scheme 2.
)
The compositions and structures of complexes I–
IV were determined by elemental analysis, IR, and UV
spectroscopy. In the IR spectra of complexes with
In the IR spectra of complexes III and IV with
1
2
ligand
vibrations of CN bonds
L
(complexes
I
and II), the bands of stretching ligand
L
, the bands of stretching vibrations of C=N
ν
(CN) of both benzimidazole bonds of the imine group and of CN bonds of the benꢀ
and pyridine rings are located at higher frequencies as zimidazole group are observed; the maxima of both
1
compared to the IR spectrum of the initial ligand
L
bands are shifted to the lower frequencies as compared
(
Table 1). This fact indicates that two nitrogen atoms to their position in the IR spectrum of the noncoordiꢀ
1
2
of ligand
L
participate in the coordination of the nated ligand
L (Table 1). These changes in the IR
Co(II) and Ni(II) atoms, so that fiveꢀmembered cheꢀ spectra testify to the bidentate coordination of the
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

COBALT(II) AND NICKEL(II) COMPLEXES
821
a
c
0
b
Fig. 3. Projection of structure II ⋅ 1.797CH CN along the a axis. The H atoms are omitted.
3
benzimidazole derivative L2 through two nitrogen three pyridine nitrogen atoms form a distorted octaheꢀ
1
2+
atoms with the formation of fiveꢀmembered metalloꢀ dral environment around the Ni atom. The [Ni(L ) ]
3
cycles.
1
complexes, in which disordered
L
molecules occupy
In the region of stretching vibrations of BH bonds the main positions, have the meridional configuration.
of the IR spectra of I–IV (Table 1), there is an intense In these complexes, the Ni–N bonds with the imidazole
–
1
ν
(BH) band with the maximum near 2450 cm . The
nitrogen atoms (2.010(4)–2.076(3) Å) are shorter than
those with the pyridine nitrogen atoms (2.132(4)–
–1
absence of bands in the range 2400–2000 cm typical
of (BH)MHB stretching vibrations of coordinated
closoꢀdecaborate anion indicates that the [B H ]
ν
2
.179(5) Å). Molecules C N H are flattened. Torꢀ
2–
13 3 11
10
10
sion
angles
N(1)C(7)C(9)N(3),
anion is located in the outer sphere.
N(4)C(20)C(22)N(6), and N(7)C(33)C(35)N(9)
characterizing the relative rotation of the imidazole
and pyridine rings are –4.9°, –12.7°, and –18.1°,
According to the data of the UV spectra, the energy
of the intramolecular charge transfer in ligand
complexes and II (330 and 335 nm, respectively) is
lower than in the noncoordinated ligand (305 nm). A
similar decrease in the energy with respect to that in
the noncoordinated ligand L (340 nm) is found for
complexes with L (~370 nm for both III and IV).
According to the elemental analysis, the metalꢀtoꢀ
ligand ratio in complexes I–IV is 3 : 1. This allows us
to conclude that the coordination number of Co and
Ni is six due to the metal coordination by three bidenꢀ
tate ligands L.
1
L in
I
respectively. The complex with the minor component
of the N(4)ꢀC(26) molecule and the main component
of the N(1)ꢀC(13) molecule has the facial configuraꢀ
tion. The other combinations of molecules correspond
to the meridional isomer. Note that, in the Cambridge
Structural Database there is only one compound conꢀ
2
2
1
2+
taining complex cation [M(L ) ] with the same
3
ligand, namely, [Fe(C N H ) ](F CSO )
⋅
0.5H O
13
3
11 3
3
3 2
2
2+
[14]. Complex [Fe(C N H ) ] has the meridional
13
3
11 3
configuration. The Fe–N bond lengths with the imiꢀ
dazole and pyridine nitrogen atoms (1.942–2.038 and
Ni(C N H ) ] , the [B H ] anions, and solvate 1.991–2.047 Å, respectively) differ to a smaller extent
According to the Xꢀray diffraction data, crystals of
II
[
⋅
1.797CH CN are built of complex cations
3
2+
2–
13 3 11 3 10 10
acetonitrile molecules (Fig. 2). Three imidazole and than the Ni–N bond lengths in II 1.797CH CN.
⋅
3
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015

822
AVDEEVA et al.
[
Ni(C N H ) ][B H ]
⋅
1.797CH CN was deterꢀ
3
µ
eff,
µ
13
3
11 3
10 10
B
mined by Xꢀray crystallography. The distorted octaheꢀ
dral environment formed by the imidazole and pyriꢀ
dine nitrogen atoms of three ligand molecules is
responsible for the low magnetic moment of the comꢀ
plex. The complexes are promising for application in
various fields of science and technology owing to the
combination of properties of the metals, benzimidaꢀ
zoles, and boron clusters composing them.
3.0
2.5
2.0
µ
(300 K) = 3.14
µ
B
ACKNOWLEDGMENTS
µ
(2 K) = 2.06
µ
B
This study was supported by the Russian Science
Foundation (project no. 14ꢀ13ꢀ01115).
0
50 100 150 200 250 300
, K
T
REFERENCES
1
. I. Tiritiris, Ng.ꢀD. Van, and Th. Schleid, Z. Anorg.
Allg. Chem. 630, 1763 (2004).
Fig. 4. Temperature dependence of the magnetic susceptiꢀ
bility of complex II 1.797CH CN
⋅
.
3
2. N.ꢀD. Van, New SaltꢀLike DodecahydroꢀclosoꢀDodeꢀ
caborates and Efforts for the Partial Hydroxylation of of
2–
[
B H ] Anions (Inst. Anorg. Chem. der Univ. Stutꢀ
12 12
1
2+
In crystal II
cations are packed into wavy layers parallel to the ac
plane (Fig. 3). Channels extended along the axis, in
which B H anions and acetonitrile molecules are
⋅
1.797CH CN
,
[Ni(L ) ] complex
tgart, Stuttgart, 2009).
3. A. D. Kayumov, K. A. Solntsev, N. T. Kuznetsov, et al.,
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Russ. J. Coord. Chem. 36, 906 (2010).
. H. C. Miller, N. E. Miller, and E. L. Muetterties, J. Am.
Chem. Soc. 85, 3885 (1963).
3
3
a
2
10
−
4
5
6
7
8
9
1
0
located, are formed between neighboring layers. The
shortest contacts between ten independent H atoms of
the borohydride anion and H atoms of ligand
tonitrile fall in the range of 2.28–2.56 Å. The splitting of
absorption bands usually observed in the IR spectra of
compounds with specific B–H⋅⋅⋅H–N interactions is
1
L
or aceꢀ
not found in the IR spectrum of II
The values of the magnetic moment for octahedral
nickel(II) complexes vary in the range of 3.0–3.4 B.
⋅
1.797CH CN.
3
μ
Figure 4 shows the plot of the magnetic moment of
compound II versus temperature. The magnetic
1
0. M. J. Plater, P. Barnes, L. K. McDonald, et al., Org.
Biomol. Chem. , 1633 (2009).
1. APEX2 (V. 2009, 5ꢀ1), SAINT (V7.60A), and SADABS
2008/1) (Bruker, Madison, Wisconsin, USA, 2008ꢀ
009).
moment of complex II equal to 3.14 B corresponds
μ
7
to a distorted octahedral environment because of the
nonequivalence of the Ni–N bonds in the complex.
1
(
2
Thus, we have developed the method to synthesize
cobalt(II) and nickel(II) complexes with 1ꢀmethylꢀ2ꢀ 12. A. Altomare, G. Cascarano, C. Giacovazzo, et al.,
J. Appl. Crystallogr. 26, 343 (1993).
ꢀbenzimidazoles and the closoꢀdecaborate 13. G. M. Sheldrick, Acta Crystallogr., Sect. A 64, 112
2008).
C N H13). The complexes were isolated selectively in 14. J. S. Pap, A. Draksharapu, M. Giorgi, et al., Chem.
pyridinꢀ2ꢀylꢀ1
thylꢀ1
anion [ML ][B H10] (M = Co, Ni; L = C N H or
Hꢀ and 1ꢀmethylꢀ2ꢀphenyliminomeꢀ
H
(
3
10
13
3
11
1
5
3
Commun. 50, 1326 (2014).
a good yield and characterized by elemental analysis,
IR, and UV spectroscopy. The structure of complex
Translated by V. Avdeeva
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 7 2015