ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2011, Vol. 56, No. 10, pp. 1561–1564. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.V. Sharutin, V.S. Senchurin, O.K. Sharutina, O.V. Chagarova, 2011, published in Zhurnal Neorganicheskoi Khimii, 2011, Vol. 56, No. 10, pp. 1640–1643.
COORDINATION
COMPOUNDS
Synthesis of New Antimony(III) and Bismuth(III) Aryl Compounds:
Crystal and Molecular Structure of Tris(5ꢀbromoꢀ2ꢀ
methoxyphenyl)antimony
V. V. Sharutin, V. S. Senchurin, O. K. Sharutina, and O. V. Chagarova
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia.
eꢀmail: vvsharutin@ramler.ru
Received November 26, 2009
Abstract—Tris(5ꢀbromoꢀ2ꢀmethoxyphenyl)antimony (
nyl)bismuth (II) (yield, 81%) were obtained by reacting 5ꢀbromoꢀ2ꢀmethoxyphenyllithium with antiꢀ
mony(III) chloride and bismuth(III) chloride, respectively. According to Xꢀray diffraction data, the antiꢀ
mony atom in is highly coordinated. The Sb–C bonds lengths are 2.160(1) Å, 2.163(1) Å, and 2.157(2) Å;
the Sb···O distances are 2.985(1) Å, 3.051(1) Å, and 3.052(1) Å. The CSbC bond angles vary in the range of
2.19(6)°–94.52(6)°. Molecules of are linked via Sb(A)···Br(B) intermolecular contacts (3.742(2) Å) to
form polymer chains.
I) (yield, 85%) and tris(5ꢀbromoꢀ2ꢀmethoxypheꢀ
I
9
I
DOI: 10.1134/S0036023611100196
Triorganylantimony and ꢀbismuth molecules carefully decomposed with cool water (2 mL); the solꢀ
where the electronic configuration of the base state of vent was removed; and the residue was recrystallized
(
2
3
the atoms is ns np ) are, as a rule, trigonal bipyramids from benzene. As a result, colorless crystals of
I were
with a lone electron pair of the central atom located in obtained. Yield, 10.42 g (85%); = 198°C.
T
m
–
1
the apex. However, antimony and bismuth atoms have
free orbitals, whose low energy gives a possibility of
IR (cm ): 2933, 2834, 1563, 1488, 1425, 1371,
283, 1261, 1234, 1177, 1136, 1088, 1073, 1042, 1017,
easily accepting electron pairs of various donor atoms 890, 826, 805, 767, 744, 615, 540, 443.
d
1
to form both intraꢀ and intermolecular additional
For C H SbBr O anal. calcd. (%): C, 42.74; H,
27
24
3
3
bonds. Large atomic radii of antimony and bismuth
are also in favor of this; their coordination spheres
remain unsaturated after formation of three covalent
bonds. Triaryl compounds of antimony and bismuth
are known, which have potential coordination centers
in aryl ligands (see, e.g., [1, 2]). Xꢀray diffraction studꢀ
ies have shown that, in case of the spatial accessibility
of potential coordination sites, the coordination numꢀ
3
.17. Found (%): C, 42.12; H, 3.07.
The benzene solvate of II was obtained analoꢀ
gously. Yield, 81%; Tm = 203°C.
–1
IR (cm ): 2934, 2833, 1560, 1488, 1457, 1434,
372, 1295, 1260, 1234, 1175, 1142, 1084, 1036, 1013,
80, 829, 800, 613, 528, 434.
1
8
For C H BiBr O anal. calcd. (%): C, 38.34; H,
27
24
3
3
ber of the central atom in these compounds increases. 2.84. Found (%): C, 38.06; H, 2.93.
IR spectra were recorded as KBr pellets on an FSM
201 FTꢀIR spectrophotometer.
In this work, aimed at further studying highly coorꢀ
dinated antimony and bismuth compounds, we have
synthesized for the first time tris(5ꢀbromoꢀ2ꢀmethoxyꢀ
1
Xꢀray singleꢀcrystal diffraction of compound
I ·
phenyl)antimony (
I) and tris(5ꢀbromoꢀ2ꢀmethoxyꢀ C H6 was carried out on a BrukerꢀNonius X8Apex
6
phenyl)bismuth (II) and studied the crystal and fourꢀcircle diffractometer (CCD area detector, Мо
К
α
molecular structure of
I.
radiation,
The experimental intensity array was collected by
scans of narrow frames (0.5 ) to = 50 . The correcꢀ
tion for absorption was applied empirically (SADABS)
3]. The structure was solved by direct methods and
λ
= 0.71073 Å, graphite monochromator).
ϕ
°
2θ
°
EXPERIMENTAL
[
Synthesis of a benzene solvate of complex I. To a
solution of 28.95 g (50.0 mmol) of 5ꢀbromoꢀ2ꢀmethꢀ
oxyphenyllithium obtained by metalation of 28.05 g of
refined by the fullꢀmatrix leastꢀsquares in the anisoꢀ
tropic approximation for nonꢀhydrogen atoms
SHELXꢀ97) [4].
(
pꢀbromoanisole with phenyllithium in ether, a soluꢀ
tion of 3.65 g (16.0 mmol) of antimony(III) chloride
Selected crystal data and refinement parameters
in 20 mL of diethyl ether was added; and the mixture for structure
I are compiled in Table 1; atomic coordiꢀ
was stirred and kept overnight. Then, the mixture was nates and thermal parameters are presented in Table 2;
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