Russian Journal of Coordination Chemistry, Vol. 31, No. 1, 2005, pp. 40–44. Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 43–47.
Original Russian Text Copyright © 2005 by Panasyuk, Ranskii, Aliev.
Synthesis and X-ray Diffraction Analysis
of {Perchlorato-bis[benzimidazole-2-N-(4-
methoxyphenyl)carbothioamidato]copper(III)}
Hydroperchlorate
A. G. Panasyuk*, A. P. Ranskii*, and Z. G. Aliev**
* Ukrainian State University of Chemical Technology, pr. Gagarina 8, Dnepropetrovsk, 320640 Ukraine
** Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia
Received January 28, 2004
Abstract—Conditions for the formation of the complex [CuL2(ClO4)] · HClO4 (where L is the deprotonated
molecule of benzimidazole-2-N-(4-methoxyphenyl)carbothioamide) are determined and its crystal and molec-
ular structures are studied by X-ray diffraction analysis.
INTRODUCTION
in anhydrous EtOH (70 ml) and Cu(ClCH2COO)2 ·
2H2O (0.72 g, 2.5 mmol) in anhydrous CH3OH (30 ml).
A solution of anhydrous HClO4 was obtained from
69% HClO4 (2.63 ml), HOAc (6 ml), and ÄÒ2é (8 ml)
and added to the suspension of CuL2. As a result, the
reaction mixture became very hot and the CuL2 precip-
itate dissolved. A yellow–green solution that formed
was heated for another 10 min, slowly cooled to room
temperature, and allowed to stand for 2 h. Black crys-
tals precipitated were filtered off, washed several times
with ethanol to pH ~ 7, and dried in air. The yield was
1.70 g (82%), and the explosion temperature was
235°C.
An interest in organic compounds containing N,S-
donor sites has considerably increased recently. Com-
plexes containing these sites are of great significance in
modern bioinorganic chemistry, since they can be used
to obtain stereochemically fixed structures and models
of active sites of non-heme metalloproteins [1, 2]. For
instance, the polynuclear complexes of trivalent copper,
which can be used also as the functional model systems
of allosteric metalloenzymes, were studied in detail [3].
We have previously obtained complexes CuL2 and
[Cu(HL)X2] based on arylamides of benzimidazole-2-
thiocarboxylic acid (HL) [4]. However, the synthesis of
the aforementioned complexes using perchloric acid in
an anhydrous alcohol medium gave trivalent copper
complexes instead of the expected copper(II) com-
plexes. The synthesis of such complexes is not
described in the literature. This work deals with the
synthesis and X-ray diffraction analysis of the complex
[CuL2(ClO4)] · HClO4 (I) prepared by the oxidation of
the CuL2 chelate (II) with air oxygen on heating in an
anhydrous alcohol medium in the presence of excess
HClO4.A possible specific bioactivity of the complex is
also studied.
For C30H25Cl2N6O10S2Cu
anal. calcd. (%): N, 10.15;
Found (%): N, 10.52;
S, 7.74;
S, 7.48;
Cu, 7.76.
Cu, 7.52.
X-ray diffraction analysis. Black, well faced crys-
tals of compound I belong to the triclinic crystal sys-
tem: a = 12.710(3), b = 16.370(3), c = 8.498(2) Å, α =
100.34(3)°, β = 91.43(3)°, γ = 104.50(3)°, V =
1679.5(6) Å3, M = 828.12, ρ(calcd.) = 1.638 g/cm3, Z =
2, space group P1 .
A set of experimental reflections was obtained on an
automated four-circle KM-4 (KUMA Diffraction) dif-
fractometer with χ geometry using the ω/2θ scan mode
with the monochromatized MoKα radiation (2θ ≤ 50°).
The total number of independent reflections measured
was 5945. No correction for absorption was applied
(µ = 1.001 mm–1).
EXPERIMENTAL
The starting thioamide HL was synthesized accord-
ing to a known procedure [5]. Anhydrous HClO4 was
synthesized by the procedure described in [6]. Cop-
per(II) monochloroacetate dihydrate (high-purity
grade) was used in the synthesis.
Synthesis of {perchlorato-bis[benzimidazole-2-
(4-methoxyphenyl)carbothioamidato]copper(III)}
The structure was solved by the direct method fol-
lowed by a series of electron density syntheses. Hydro-
hydroperchlorate (I). A suspension of CuL2 was pre- gen atoms of the methyl groups were specified geomet-
pared by reacting hot solutions of HL (1.41 g, 5 mmol) rically. The full-matrix anisotropic refinement of non-
1070-3284/05/3101-0040 © 2005 Pleiades Publishing, Inc.
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