1070-3284/02/2807- $27.00 © 2002
Russian Journal of Coordination Chemistry, Vol. 28, No. 7, 2002, pp. 473–476. Translated from Koordinatsionnaya Khimiya, Vol. 28, No. 7, 2002, pp. 506–509.
Original Russian Text Copyright © 2002 by Sharutin, Pakusina, Nasonova, Fukin, Zakharov.
About 20 compounds of the general formula
have been structurally characterized to
date [1–15]. The SbOSb fragment in these compounds
may be either nearly linear or curved (the SbOSb angle
ranges from 139.0
). Apparently, the geome-
try of this fragment is determined by substituents at the
Sb atoms (in particular, by their steric and electron
effects) or by the molecular packing in the crystal.
In this study, the molecular and crystal structures of
ligands more bulky than phenyl were investigated.
was synthesized as follows. A 31% solu-
(0.15 ml, 1.38 mmol) was added to a mix-
ture of tri-
-tolylantimony (1.00 g, 2.78 mmol) and
aqueous 40% HBr (0.50 ml, 2.72 mmol) in 20 ml of
ether. After 12 h, the colorless crystals that formed were
ﬁltered off and dried. The yield of
was 1.06 g (87%);
X-ray diffraction analysis
out using a Siemens P3/CP four-circle diffractometer
radiation, graphite monochromator,
The crystals of
are triclinic: at
, space group
= 1.626 g/cm
= 3.425 mm
= 4 (two
The structure was solved by the direct method and
reﬁned by the full-matrix least squares method in the
anal. calcd. (%): C, 57.17; H, 4.35; Br, 16.56.
Found (%): C, 57.48; H, 4.53; Br, 16.04.
anisotropic approximation for all non-hydrogen atoms
= 0.1430, and
= 1.016 from 6937
. The H atoms were located
geometrically and reﬁned in the rider model with ﬁxed
All computations were performed with the
SHELX97 programs  using an IBM PC.
Atomic coordinates and equivalent isotropic ther-
mal parameters are given in Table 1. Bond lengths and
angles are presented in Table 2.
RESULTS AND DISCUSSION
It is known that triarylstibine can be oxidized with
hydrogen peroxide in the presence of arenesulfonic
. We found that the use of hydrobromic acid instead
of arenesulfonic acid does not change the reaction
scheme. In this way,
) was obtained from tri-
hydrogen peroxide, and hydrobromic acid:
Sb + 2HBr + 2H
The structural units of crystal
are two types of
crystallographically nonequivalent binuclear Sb(V)
complexes in which two (
are united through the bridging O atom (ﬁgure) lying in
the center of inversion.
The Sb(1) and Sb(2) atoms have a slightly distorted
trigonal-bipyramidal coordination; the equatorial
CSbC angles range from 115.7(3)
Sb(1) and from 119.8(4)
for Sb(2), and
the axial BrSbO angle is equal to 175.52(4)
Synthesis and Structure
V. V. Sharutin, A. P. Pakusina, N. V. Nasonova, G. K. Fukin, and L. N. Zakharov
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
Received March 24, 2001
-tolylantimony] was synthesized by the reaction of tri-
hydrobromic acid in ether in the presence of hydrogen peroxide. The complex was structurally characterized
by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid
with the bromine and the bridging O atoms in the axial positions. The Sb(1)–C(Ph) distances vary from 2.085(9)
to 2.111(8) Å. The Sb(1)–Br(1) and Sb(2)–Br(2) bond lengths are 2.739(2) and 2.735(2) Å, respectively; the
distances measure 1.949(1) Å.