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Chemisorption Synthesis of the Ion-Polymeric Heteronuclear Gold(III)–Bismuth(III) Complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n Based on [Bi2{S2CN(C3H7)2}6]: 13C MAS NMR, Supramolecular Structure, and Thermal Behavior

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Abstract

Chemisorption synthesis on the basis of the binuclear compound [Bi2{S2CN(C3H7)2}6] (I) and preparative isolation of the ion-polymeric heteronuclear gold(III)–bismuth(III) complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n (II) are carried out. Compounds I and II are characterized in comparison by IR spectroscopy and 13C CP-MAS NMR. According to the X-ray diffraction analysis data (CIF file CCDC no. 1407705), the cationic moiety of compound II exhibits an unusually complicated supramolecular structure including six isomeric noncentrosymmetric complex cations [Au{S2CN(C3H7)2}2]+ (hereinafter A–F) and two binuclear anions [Bi2Cl9]3– as conformers. The isomeric gold(III) cations perform various structural functions. Owing to pair secondary interactions Au···S, cations B, C, E, and F form centrosymmetric ([E···E], [F···F]) and noncentrosymmetric ([B···C]) binuclear aggregates [Au2{S2CN(C3H7)2}4]2+, whereas cations A and D are not involved in dimerization. The strongest secondary Au···S bonds are formed between the binuclear and mononuclear cations, resulting in the formation of supramolecular cation-cationic polymer chains of two types: (⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅)n and (D⋅⋅⋅[E⋅⋅⋅E]⋅⋅⋅D⋅⋅⋅[F⋅⋅⋅F]⋅⋅⋅])n. In both chains, the gold atoms of the binuclear cations are characterized by a distorted octahedral coordination [S6], whereas in the mononuclear cations the gold atoms retain the square environment [S4]. The cation-anionic interactions are provided by secondary bonds Cl⋅⋅⋅S involving the terminal chlorine atoms of isomeric [Bi2Cl9]3– and the sulfur atoms of the binuclear cations [Au2{S2CN(C3H7)2}4]2+. The character of the thermal behavior of compounds I and II is studied by simultaneous thermal analysis with the identification of intermediate and final products of the thermal transformations. The thermolysis of compound I at 193–320°C is accompanied by the formation of Bi2S3 with an impurity of reduced metallic bismuth particles. The final products of the thermal transformations of compound II are reduced elemental gold and Bi2O3, and the thermal transformation intermediates are BiCl3 and Bi2S3.

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Notes

  1. The concept of secondary bonds was proposed [34] for the description of interactions characterized by the distances comparable with the sums of the van der Waals radii of the corresponding atoms.

  2. Cation-anionic interactions of this type were observed earlier for the formation of supramolecular structures of the heteronuclear complexes Au(III)–Zn [36] and Au(III)–Fe(III) [37].

  3. The formation of metal sulfides upon the thermolysis of the complexes including the sulfur-containing ligands was substantiated from the thermodynamic point of view [42].

  4. The evaporation of BiCl3 was studied for samples of the compact substance. A significant mass loss begins from sample melting, the evaporation region lies in a range of 234.0–415.0°С, and the maximum rate of mass loss falls on 376.6°С.

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Authors and Affiliations

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

    A. V. Ivanov, A. S. Zaeva & E. V. Novikova

  2. Institute of Chemistry, Far East Branch, Russian Academy of Sciences, 690022, Vladivostok, Russia

    A. V. Gerasimenko

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

    I. V. Egorova & N. A. Rodionova

  4. Luleå University of Technology, SE-97187, Luleå, Sweden

    V. Gowda & O. N. Antzutkin

  5. University of Oulu, P.O. Box 3000, FI-90014, Oulu, Finland

    V. Gowda

  6. Warwick University, CV4 7AL, Coventry, United Kingdom

    O. N. Antzutkin

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  1. A. V. Ivanov
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Translated by E. Yablonskaya

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Ivanov, A.V., Gerasimenko, A.V., Egorova, I.V. et al. Chemisorption Synthesis of the Ion-Polymeric Heteronuclear Gold(III)–Bismuth(III) Complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n Based on [Bi2{S2CN(C3H7)2}6]: 13C MAS NMR, Supramolecular Structure, and Thermal Behavior. Russ J Coord Chem 44, 518–531 (2018). https://doi.org/10.1134/S1070328418080043

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