期刊
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 -, 页码 -出版社
MAIK NAUKA/INTERPERIODICA/SPRINGER
DOI: 10.1134/S0036023623601381
关键词
bismuth(III) compounds; dialkyl dithiocarbamate complexes; supramolecular self-organization; secondary interactions; thermal behavior
Bismuth(III) hexamethylenedithiocarbamate and its solvated form have been synthesized and their crystal structures analyzed. The compounds exhibit unusual isomeric pseudo-binuclear and pseudo-dimer structures, with the ligands coordinating in an S,S'-anisobidentate mode.
Bismuth(III) hexamethylenedithiocarbamate (HmDtc) [Bi-2{S2CN(CH2)(6)}(6)] (I) and its solvated with dimethyl sulfoxide form [Bi-2(S(2)CNHm)(6)]& sdot;2(CH3)(2)SO (II) have been obtained. The crystal structure of compound I shows an unusual alternation of two unsymmetrical isomeric pseudo-binuclear [Bi-1/1B(HmDtc)(3)Bi-1A/1C(HmDtc)(3)] molecules, each of which involves two non-equivalent mononuclear moieties combined by secondary BiS 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-HO 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 Bi-0.
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