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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.

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Notes

  1. Position of absorption bands of N–CH2 groups was revealed by comparative analysis of IR spectra of complexes I and II and hexamethylenimine C6H12NH [27] and cycloheptane C7H14 [28].

  2. To register IR spectrum of DMSO (νas(CH3) 2997, νs(CH3) 2913, ν(S=O) 1047, νas(C–S) 702, νs(C–S) 670 cm–1), we used thin film method [30].

  3. The concept of secondary bonds was proposed to characterize interactions between atoms located at distances comparable with the sum of their Van der Waals radii [34].

  4. The values of Van der Waals radius for bismuth atom given in certain literature sources—2.3 [35], 2.07 [36], 2.38 [37], and 2.54 Å [38]—differ considerably.

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ACKNOWLEDGMENTS

X-ray diffraction study was performed using equipment of the Center for Molecular Structure Studies of the Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, under support of the Ministry of Science and Higher Education of the Russian Federation (State Assignment no. 075-03-2023-642). Electron microscopy and EDX spectral experiments were performed in the User Facilities Center, Amur Center for Mineral and Geochemical Studies (Laboratory of Microscopy and Molecular Structure Studies), Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences.

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Authors and Affiliations

  1. Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences, 675000, Blagoveshchensk, Russia

    E. V. Novikova & A. V. Ivanov

  2. Blagoveshchensk State Pedagogical University, 675000, Blagoveshchensk, Russia

    I. V. Egorova

  3. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Moscow, Russia

    K. L. Isakovskaya

  4. Mendeleev University of Chemical Technology of Russia, 125047, Moscow, Russia

    K. L. Isakovskaya

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  3. K. L. Isakovskaya
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Correspondence to A. V. Ivanov.

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Translated by I. Kudryavtsev

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Novikova, E.V., Egorova, I.V., Isakovskaya, K.L. et al. 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. Russ. J. Inorg. Chem. 68, 1425–1438 (2023). https://doi.org/10.1134/S0036023623601381

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