A New Structural Type of Bismuth(III) Dithiocarbamato-Chlorido Complexes: Preparation, Structural Organization, and Thermal Behavior of Binuclear Compounds [Bi2{S2CN(CH2)6}4(μ2-Cl)2] and [Bi2{S2CN(CH2)6}4(μ2-Cl)2]·2CH2Cl2

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Abstract

Heteroleptic compounds of bismuth(III) adopting a new binuclear structural type: hexamethylenedithiocarbamato(HmDtc)-chloride of [Bi2(S2CNHm)4(μ2-Cl)2] (I) and its solvated form [Bi2(S2CNHm)4(μ2-Cl)2]·2CH2Cl2 (II) have been isolated and studied by X-ray diffraction, IR spectroscopy, and simultaneous thermal analysis. Despite the identical chemical composition, the structure of binuclear molecules in I and II differs significantly. In the first case, the noncentrosymmetric molecule includes two nonequivalent moieties of [Bi(S2CNHm)2Cl], which are combined by μ2-Cl ligands to form the [Bi–(μ2-Cl)2–Bi] metallocycle in the butterfly conformation: Bi(1)–Bi(2) 4.0785(5) Å, Cl(1)–Cl(2) 3.936(2) Å. On the contrary, in the solvated form II, the complex is centrosymmetric and four-membered [Bi2Cl2] ring is stabilized in a rhombic configuration: Bi(1)–Bi(1)a 3.9592(9) Å and Cl(1)–Cl(1)a 4.540(4) Å. According to the microprobe method, the main residual substance after the thermolysis of the complexes is microcrystalline Bi2S3 with inclusions of metallic bismuth particles.

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

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, К.Л. Исаковская, А.В. Иванов