1070-3284/02/2803- $27.00 © 2002
Russian Journal of Coordination Chemistry, Vol. 28, No. 3, 2002, pp. 175–182. Translated from Koordinatsionnaya Khimiya, Vol. 28, No. 3, 2002, pp. 185–192.
Original Russian Text Copyright © 2002 by Storozhuk, Udovenko, Mirochnik, Petrochenkova, Karasev.
The ions with the electronic conﬁguration of
mercury-like ions, are known to form complexes lumi-
nescing at 77 and 300 K [1–4]. The ﬂuorescence of
these compounds is characterized by a pronounced
temperature decay and is very weak (or even absent) at
room temperature. In connection with this, it is impor-
tant to determine the factors inﬂuencing the sensitiza-
tion and decay of the antimony(III) ion luminescence in
In this work, bis(2-benzylpyridinium) pentachloro-
) and bis(4-benzylpyridinium) pen-
) were synthesized, the crys-
tal structure of complex
was studied, and the lumines-
cent properties of complexes
Synthesis of complexes I and II.
A solution of
2 mol of 2- or 4-benzylpyridine (2-BP or 4-BP) in con-
centrated hydrochloric acid was added to a solution of
1 mol of SbCl
in the similar solvent. The reaction mix-
ture was evaporated on a water bath for several hours;
the crystals formed were ﬁltered off, washed succes-
sively with isoamyl alcohol and diethyl ester, and dried
in air to a constant weight.
The elemental analysis of the compounds obtained
was carried out using the known procedures: C, H, and
N were determined by the semimicroanalytical method;
Sb, by atomic absorption spectroscopy. The content of
chloride ions was determined titrimetrically using the
Folgard method .
X-ray powder diffraction analysis
on a DRON-2.0 diffractometer (ﬁltered
were recorded on a Specord 75IR spec-
trophotometer in the 400–4000 cm
range. The sam-
ples were prepared in the form of a suspension in min-
The luminescence spectra
were taken on a SDL-1
spectrometer at 300 and 77 K. A DRSh-250 mercury
lamp was used for the excitation.
X-ray diffraction analysis.
have the form of very thin extended prisms.
The diffraction data were collected from an edged sin-
gle crystal on a Bruker SMART-1000 CCD diffracto-
meter. The main crystallographic parameters and the
details of structure reﬁnement are summarized in Table 1.
anal. calcd. (%): C, 45.04; H, 3.75; N, 4.38; Cl, 27.76; Sb, 19.08.
Found for I (%): C, 45.41; H, 3.82; N, 4.27; Cl, 28.01; Sb, 19.03; mp 65–66°C
Found for II (%): C, 45.12; H, 3.70; N, 4.15; Cl, 27.35; Sb, 19.45; mp 182–183°C
Antimony(III) Chloride Complexes with Benzylpyridines:
Synthesis and Luminescence. Crystal Structure
of Bis(2-benzylpyridinium) Pentachloroantimonate(III)
T. V. Storozhuk, A. A. Udovenko, A. G. Mirochnik, N. V. Petrochenkova, and V. E. Karasev
Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
Received March 22, 2001
—The antimony(III) chloride complexes with 2- and 4-benzylpyridine were synthesized and studied
using elemental analysis, X-ray diffraction analysis, IR spectroscopy, and luminescence spectroscopy. The
crystal structure of bis(2-benzylpyridinium) pentachloroantimonate(III) was determined. The crystals are tri-
= 99. 216(2)°;
(calcd) = 1.591 g/cm
, space group
= 0.0358. The structure consists of polymeric chains of
cations combined into a framework by the N
H···Cl hydrogen bonds.
The electronic and geometrical factors responsible for a relatively low intensity of the luminescence emitted by
the complexes of antimony(III) chloride with 2- and 4-benzylpyridine at 77 K are discussed.