Isomeric Molecular Forms of Pseudo-Binuclear Bismuth(III) Dithiocarbamate [Bi2{S2CN(CH2)6}6]: Preparation, Thermal Behavior, and Structural Effect of Its Solvation with DMSO, [Bi2{S2CN(CH2)6}6]⋅2(CH3)2SO

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Abstract

Bismuth(III) hexamethylenedithiocarbamate (HmDtc) [Bi2{S2CN(CH2)6}6] (I) and its solvated with dimethyl sulfoxide form [Bi2(S2CNHm)6]⋅2(CH3)2SO (II) have been obtained. The crystal structure of compound I shows an unusual alternation of two unsymmetrical isomeric pseudo-binuclear [Bi1/1B(HmDtc)3···Bi1A/1C(HmDtc)3] molecules, each of which involves two non-equivalent mononuclear moieties combined by secondary Bi···S bonds. The solvation of complex I leads to the structural unification of isomeric [Bi(HmDtc)3] molecules followed by their self-organization into centrosymmetric pseudo-dimers in the structure of compound II. All HmDtc ligands coordinate in S,S'-anisobidentate mode to form four isomeric (in I) or structurally unique [Bi(HmDtc)3] molecules (in II), whose distorted polyhedra can be approximated by pentagonal pyramid or octahedron. Solvating DMSO molecules are retained in the structure II by C–H···O hydrogen bonds. The analysis of energy dispersive X-ray spectra allowed one to identify the residual matter obtained by thermolysis of the complexes as Bi2S3 with admixture of Bi0.

About the authors

E. V. Novikova

Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
675000, Blagoveshchensk, Russia

I. V. Egorova

Blagoveshchensk State Pedagogical University

Email: alexander.v.ivanov@chemist.com
675000, Blagoveshchensk, Russia

K. L. Isakovskaya

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences; Mendeleev University of Chemical Technology of Russia

Email: alexander.v.ivanov@chemist.com
119991, Moscow, Russia; 125047, Moscow, Russia

A. V. Ivanov

Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences

Author for correspondence.
Email: alexander.v.ivanov@chemist.com
675000, Blagoveshchensk, Russia

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Copyright (c) 2023 Е.В. Новикова, И.В. Егорова, К.Л. Исаковская, А.В. Иванов

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