Binding of gold(III) using bismuth hexamethylenedithiocarbamate: the double complexes of [Au(S2CNHm)2][Bi(S2CNHm)2Cl2] and [Au(S2CNHm)2]2[Bi2(S2CNHm)2Cl6] (preparation, crystal structure, thermal behavior and anti-mycobacterial activity)

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Abstract

It was established that during the interaction of bismuth hexamethylenedithiocarbamate (HmDtc) with a H[AuCl4]/2M HCl solution, the individual forms of gold(III) binding in the solid phase are double complexes of [Au(S2CNHm)2][Bi(S2CNHm)2Cl2] (I) and [Au(S2CNHm)2]2[Bi2(S2CNHm)2Cl6] (II). The structures of the obtained compounds include centrosymmetric/non-centrosymmetric (in I/II) complex cations of Au(III), as well as heteroleptic bismuth anions: both the mononuclear and binuclear, whose the ratio Bi : Dtc : Cl = = 1:2:2/2:2:6 (I/II). The secondary S∙∙∙S and S∙∙∙Cl interactions that arise between these ionic structural units lead to the formation of three-dimensional supramolecular architectures. In the IR spectra of the compounds, the absorption bands of N–C(S)S bonds were assigned to HmDtc ligands in the inner sphere of Au(III) complex cations and Bi(III) anions. Thermal behavior of I and II was studied using the STA technique. The residual substance obtained after thermolysis of the samples is represented by metallic particles of a solid solution of bismuth in gold, coated with a layer of Bi2O3. For complex I, a high level of anti-mycobacterial activity in vitro was revealed against the non-pathogenic strain Mycolicibacterium smegmatis.

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About the authors

E. V. Novikova

Institute of Geology and Nature Management, Far Eastern Branch of the Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
Russian Federation, Blagoveshchensk, 675000

I. A. Lutsenko

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences; Peoples' Friendship University of Russia named after Patrice Lumumba

Email: alexander.v.ivanov@chemist.com
Russian Federation, Moscow, 119991; Moscow, 117198

O. B. Bekker

Vavilov Institute of General Genetics, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
Russian Federation, Moscow, 119333

Yu. V. Nelyubina

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
Russian Federation, Moscow, 119334

A. V. Ivanov

Institute of Geology and Nature Management, Far Eastern Branch of the Russian Academy of Sciences

Author for correspondence.
Email: alexander.v.ivanov@chemist.com
Russian Federation, Blagoveshchensk, 675000

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Supplementary files

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1. JATS XML
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2. Fig. 1. Projections of the crystal structure of I on the ab (a) and bc (b) planes. The dotted lines show the interionic secondary bonds S···S.

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3. Fig. 2. Projection of the crystal structure of II onto the bc plane. The dotted lines show the interionic secondary bonds Cl···S.

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4. Fig. 3. Structure of ionic structural units of complex I. Ellipsoids of 50% probability are shown, hydrogen atoms are not shown.

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5. Fig. 4. Structure of ionic structural units of complex II. Ellipsoids of 50% probability are shown, hydrogen atoms are not shown. The dotted lines show bonds between atoms of the minor component of the ligands, disordered between two positions with occupancies of 0.520(6) and 0.480(6)/0.507(3) and 0.493(3) in [Au(S2CNHm)2]+, as well as 0.514(6) and 0.486(6) in [Bi2(S2CNHm)2Cl6]2–.

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6. Fig. 5. Polyhedral representation of the structure of the inner sphere of bismuth(III) in anions: a – [Bi(S2CNHm)2Cl2]– (I); b – [Bi2(S2CNHm)2Cl6]2– (II).

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7. Fig. 6. Method of constructing cation-anionic pseudopolymer chains in structure I; secondary S···S bonds are shown by dotted lines.

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8. Fig. 7. TG (a) and DSC (b) curves of complex I. The inset shows a close-up view of the crucible bottom after completion of thermolysis (c).

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9. Fig. 8. TG (a) and DSC (b) curves of complex II. The inset shows a close-up view of the crucible bottom after completion of thermolysis (c).

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10. Fig. 9. Size, shape of particles (a, b) and energy-dispersive spectra (c, d) of the residual substance (after thermolysis of complex I), reflecting the predominance of Au (c) and Bi2O3 (d).

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11. Fig. 10. Size, shape of particles (a, b) and energy-dispersive spectra (c, d) of the residual substance (after thermolysis of complex II) with a predominance of Au (c) and Bi2O3 (d).

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12. Table
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