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

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

doi:10.31857/S0044457X22601882

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

Authors: Novikova E.V.¹, Isakovskaya K.L.²^,3, Ivanov A.V.¹
Affiliations:
1. Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences
2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
3. Mendeleev University of Chemical Technology of Russia
Issue: Vol 68, No 4 (2023)
Pages: 471-481
Section: КООРДИНАЦИОННЫЕ СОЕДИНЕНИЯ
URL: https://rjmseer.com/0044-457X/article/view/665269
DOI: https://doi.org/10.31857/S0044457X22601882
EDN: https://elibrary.ru/FLTIUR
ID: 665269

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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.

Keywords

bismuth(III) dithiocarbamato-chlorido complexes, binuclear molecular structures, IR spectroscopy, thermal transformations of substances

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