ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2008, Vol. 34, No. 3, pp. 175–178. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.V. Sharutin, A.P. Pakusina, I.V. Egorova, O.K. Sharutina, M.A. Pushilin, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 3, pp. 181–184.
New Crystalline Modification
of m-Oxo-bis(bromotriphenylantimony)
V. V. Sharutina, A. P. Pakusinaa, I. V. Egorovaa, O. K. Sharutinaa, and M. A. Pushilinb
a Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
b Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
E-mail: vvsharutin@rambler.ru
Received February 14, 2007
Abstract—The triclinic crystalline modification of µ-oxo-bis(bromotriphenylantimony) has been synthesized
by the reaction of triphenylantimmony dibromide with water in benzene. The Sb atoms have distorted trigonal
bipyramidal coordination with the bromine atoms and bridging oxygen atoms in the axial positions. The dis-
tances are Sb–C 2.104(2)–2.123(2), Sb(1)–Br(1) 2.7492(2), Sb(2)–Br(2) 2.7235(2), Sb(1)–O 1.986(1), and
Sb(2)–O 1.987(1) Å, and the Sb(1)OSb(2) angle is 138.19(6)°.
DOI: 10.1134/S1070328408030044
INTRODUCTION
The IR spectrum of isomer II was recorded on a Shi-
madzu spectrometer in Nujol (KBr plates). IR (ν, cm−1):
418.55, 451.34, 688.59, 736.81, 777.31, 848.68,
896.90, 937.40, 970.19, 997.20, 1020.34, 1066.64,
1089.78, 1157.29, 1180.44, 1271.09, 1305.81,
1330.88, 1435.04, 1573.91, 2852.72, 2922.16,
2951.09.
X-ray diffraction study of crystals II was carried
out on a SMART-1000 CCD diffractometer (MoKα
radiation, λ = 0.71073 Å, graphite monochromator).
The structure was solved by the direct method and
refined by the least-squares calculation in the anisotro-
pic approximation for non-hydrogen atoms. The posi-
tions of the hydrogen atoms were calculated geometri-
cally and included into the refinement in the riding
model.
It is known that the crystallization conditions some-
times influence the type of the crystal lattice and geo-
metric parameters of the molecules in a crystal. For
instance, the recrystallization of µ-oxo-bis(iodotriphe-
nylantimony) from acetonitrile affords yellow crystals
containing molecules with the bent SbOSb fragment,
while in dichloromethane, colorless crystals with the
linear SbOSb group are formed [1].
In this paper, we report the synthesis of structural
isomers of µ-oxo-bis(bromotriphenylstibium) (I, II)
and the results of X-ray diffraction analysis of triclinic
modification II.
EXPERIMENTAL
The data were collected and edited and the unit cell
parameters were refined using the SMART and SAINT-
Plus programs [4]. All calculations for the structure
determination and refinement were performed using the
SHELXTL/PC program packages [5].
The main crystallographic data and results of refine-
ment of structure II are listed in Table 1, coordinates
and temperature factors of atoms are summarized in
Table 2, and bond lengths and bond angles are pre-
sented in Table 3.
Synthesis of the monoclinic modification of m-
oxo-bis(bromotriphenylantimony) (I). Water (1 ml)
was added to a solution of triphenylantimony dibro-
mide (1.03 g, 1.0 mmol) in acetone (50 ml), and the
mixture was refluxed for 1 h. After acetone evaporated,
colorless crystals of compound I were obtained as rect-
angular plates with mp 247°ë (mp 247°ë) [2, 3]. The
yield was 0.73 g (83%).
Synthesis of triclinic modification II. A mixture of
triphenylantimony dibromide (1.03 g, 1.0 mmol) and
water (1 ml) in benzene (100 ml) was refluxed for 1 h.
Heptane (10 ml) was added to the cooled solution, and
the solvent was evaporated slowly. Large pale yellow
crystals of isomer II with mp 247°ë were obtained. The
yield was 0.60 g (68%).
RESULTS AND DISCUSSION
The geometries of the molecules of compounds
(Ar3SbX)2O with trigonal bipyramidal coordination of
175
Sharutin
