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

E. V. Novikova; Новикова Е. В.; I. V. Egorova; Егорова И. В.; K. L. Isakovskaya; Исаковская К. Л.; A. V. Ivanov; Иванов А. В.

doi:10.31857/S0044457X23600548

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

Authors: Novikova E.V.¹, Egorova I.V.², Isakovskaya K.L.³^,4, Ivanov A.V.¹
Affiliations:
1. Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences
2. Blagoveshchensk State Pedagogical University
3. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
4. Mendeleev University of Chemical Technology of Russia
Issue: Vol 68, No 10 (2023)
Pages: 1433-1446
Section: КООРДИНАЦИОННЫЕ СОЕДИНЕНИЯ
URL: https://rjmseer.com/0044-457X/article/view/666186
DOI: https://doi.org/10.31857/S0044457X23600548
EDN: https://elibrary.ru/NLZMXC
ID: 666186

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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.

Keywords

bismuth(III) compounds, dialkyl dithiocarbamate complexes, supramolecular self-organization, secondary interactions, thermal behavior

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