Skip to main content
SpringerLink
Log in

Three-Dimensional Polymeric Thallium(I) Morpholinedithiocarbamate [Tl2{S2CN(CH2)4O}2] n and Its Capability of Binding Gold(III) from Solutions: Chemisorption Synthesis of a Heteronuclear Gold(III)–Thallium(III) Complex of the Ionic Type, ([Au{S2CN(CH2)4O}2][TlCl4]) n , the Role of Secondary Interactions Tl…O, Tl…S, and Au…S in the Supramolecular Self-Organization, 13C MAS NMR, and Thermal Behavior

  • Published:
Russian Journal of Coordination Chemistry Aims and scope Submit manuscript

Abstract

Crystalline polymeric thallium(I) morpholinedithiocarbamate [Tl2{S2CN(CH2)4O}2] n (I) and the heteronuclear ion–polymeric gold(III)–thalium(III) complex ([Au{S2CN(CH2)4O}2][TlCl4]) n (II) are preparatively isolated and characterized by X-ray diffraction analysis and 13C MAS NMR spectroscopy. According to the X-ray diffraction data, the main structural units of compounds I and II (CIF files CCDC 1548079 and 1548080) are presented by the binuclear centrosymmetric molecule [Tl2{S2CN(CH2)4O}2], noncentrosymmetric complex cation [Au{S2CN(CH2)4O{2]+, and isomeric complex anions [TlCl4]–. The formation of the three-dimensional polymeric structure (coordination number of Tl is 7), which is not characteristic of thallium(I) dithiocarbamates, is a consequence of the participation of the secondary Tl…O and Tl…S bonds of two types in the supramolecular self-organization of compound I. Nonequivalent secondary interactions of the first type join the binuclear molecules [Tl2{S2CN(CH2)4O}2] into polymer layers, which, in turn, form the three-dimensional polymeric framework due to the secondary bonds Tl…S. The revealed ability of freshly precipitated compound I to the chemisorption of gold(III) from solutions (2 M HCl) makes it possible to obtain heteronuclear supramolecular complex II as an individual form of binding. In the structure of the latter, the pairs of stronger secondary Au…S bonds join the gold(III) cations into dimers [Au2{S2CN(CH2)4O}4]2+ of the angular structure, the structural ordering of which is achieved in the cationcationic polymeric chain ([Au2{S2CN(CH2)4O}4]2+) n of the helical type involving the pairs of less strong Au…S bonds between the adjacent binuclear units. The distorted tetrahedral anions [TlCl4]– are localized between the polymeric chains. The study of the thermal behavior of compounds I and II by simultaneous thermal analysis makes it possible to establish the character of thermal transformations of the substances and to identify Tl2S (I), TlCl, and elemental gold (II) as thermolysis products.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Riley, J.P. and Siddiqui, S.A., Anal. Chim. Acta, 1986, vol. 181, p. 117.

    Article  CAS  Google Scholar 

  2. Elson, C.M. and Albuquerque, C.A.R., Anal. Chim. Acta, 1982, vol. 134, p. 393.

    Article  CAS  Google Scholar 

  3. Nilson, L. and Hesse, R., Acta Chem. Scand., 1963, vol. 23, no. 6, p. 1951.

    Google Scholar 

  4. Jennische, P., Olin, Å., and Hesse, R., Acta Chem. Scand., 1972, vol. 26, no. 7, p. 2799.

    Article  CAS  Google Scholar 

  5. Jennische, P. and Hesse, R., Acta Chem. Scand., 1973, vol. 27, no. 9, p. 3531.

    Article  CAS  Google Scholar 

  6. Anacker-Eickhoff, H., Jennische, P., and Hesse, R., Acta Chem. Scand., Ser. A, 1975, vol. 29, no. 1, p. 51.

    Article  Google Scholar 

  7. Pritzkow, H. and Jennische, P., Acta Chem. Scand., Ser. A, 1975, vol. 29, no. 1, p. 60.

    Article  Google Scholar 

  8. Elfwing, E., Anacker-Eickhoff, H., Jennische, P., and Hesse, R., Acta Chem. Scand., Ser. A, 1976, vol. 30, no. 5, p. 335.

    Article  Google Scholar 

  9. Hong, S.-H. and Jennische, P., Acta Chem. Scand., Ser. A, 1978, vol. 32, no. 4, p. 313.

    Article  Google Scholar 

  10. Alexander, N., Ramalingam, K., and Rizzoli, C., Inorg. Chim. Acta, 2011, vol. 365, no. 1, p. 480.

    Article  CAS  Google Scholar 

  11. Akhbari, K. and Morsali, A., Coord. Chem. Rev., 2010, vol. 254, nos 17–18, p. 1977.

    Article  CAS  Google Scholar 

  12. Ramalingam, K., Rizzoli, C., and Alexander, N., Monatsh. Chem., 2013, vol. 144, no. 9, p. 1329.

    Article  Google Scholar 

  13. Sivagurunathan, G.S., Ramalingam, K., and Rizzoli, C., Polyhedron, 2013, vol. 65, p. 316.

    Article  CAS  Google Scholar 

  14. Gomathi, G., Thirumaran, S., and Ciattini, S., Polyhedron, 2015, vol. 102, p. 424.

    Article  CAS  Google Scholar 

  15. Kumar, V., Singh, V., Gupta, A.N., Drew, M.G.B., and Singh, N., Dalton Trans., 2015, vol. 44, no. 4, p. 1716.

    Article  CAS  Google Scholar 

  16. Ramalingam, K., Rizzoli, C., and Sivagurunathan, G.S., New J. Chem., 2016, vol. 40, no. 3, p. 2489.

    Article  CAS  Google Scholar 

  17. Manar, K.K., Rajput, G., Yadav, M.K., Yadav, C.L., Kumari, K., Drew, M.G.B., and Singh, N., Chem. Select., 2016, vol. 1, no. 18, p. 5733.

    CAS  Google Scholar 

  18. Ivanov, A.V., Bredyuk, O.A., Gerasimenko, A.V., and Antzutkin, O.N., Dokl. Phys. Chem., 2008, vol. 420, no. 2, p. 130.

    Article  CAS  Google Scholar 

  19. Rodina, T.A., Ivanov, A.V., Bredyuk, O.A., and Gerasimenko, A.V., Russ. J. Coord. Chem., 2009, vol. 35, no. 3, p. 170.

    Article  CAS  Google Scholar 

  20. Ivanov, A.V., Bredyuk, O.A., Gerasimenko, A.V., et al., Russ. J. Coord. Chem., 2006, vol. 32, no. 5, p. 339.

    Article  CAS  Google Scholar 

  21. Ivanov, A.V., Bredyuk, O.A., Loseva, O.V., and Rodina, T.A., Russ. J. Coord. Chem., 2015, vol. 41, no. 2, p. 108.

    Article  CAS  Google Scholar 

  22. Ivanov, A.V., Bredyuk, O.A., Loseva, O.V., and Antzutkin, O.N., Russ. J. Inorg. Chem., 2016, vol. 61, no. 6, p. 755.

    Article  CAS  Google Scholar 

  23. Byr’ko, V.M. Ditiokarbamaty, Moscow: Nauka, 1984.

    Google Scholar 

  24. Pines, A., Gibby, M.G., and Waugh, J.S., J. Chem. Phys., 1972, vol. 56, no. 4, p. 1776.

    Article  CAS  Google Scholar 

  25. Bruker, APEX2 (version 1.08), SAINT (version 7.03), SADABS (version 2.11), SHELXTL (version 6.12), Madison: Bruker AXS Inc., 2004.

  26. Khimicheskaya entsiklopediya (Chemical Encyclopedia), Zefirov, N.S., Ed., Moscow: Bolshaya Rossiiskaya Entsiklopediya, 1995.

  27. Pauling, L., The Nature of the Chemical Bond and the Structure of Molecules and Crystals, London: Cornell Univ., 1960.

    Google Scholar 

  28. Bondi, A., J. Phys. Chem., 1964, vol. 68, no. 3, p. 441.

    Article  CAS  Google Scholar 

  29. Bondi, A., J. Phys. Chem., 1966, vol. 70, no. 9, p. 3006.

    Article  CAS  Google Scholar 

  30. Alcock, N.W., Adv. Inorg. Chem. Radiochem., 1972, vol. 15, no. 1, p. 1.

    CAS  Google Scholar 

  31. Urusov V.S. Teoreticheskaya kristallokhimiya (Theoretical Crystal Chemistry), Moscow: Izd. MGU, 1987.

  32. Lidin, R.A., Molochko, V.A., and Andreeva, L.L. Khimicheskie svoistva neorganicheskikh veshchestv (Chemical Properties of Inorganic Substances) Moscow: Khimiya, 2000.

  33. Ivanov, A.V., Loseva, O.V., Rodina, T.A., et al., Russ. J. Coord. Chem., 2016, vol. 42, no. 2, p. 104.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

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

    O. A. Bredyuk, O. V. Loseva & A. V. Ivanov

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

    V. Gowda & O. N. Antzutkin

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

    V. Gowda

  4. Warwick University, Coventry, CV4 7AL, UK

    O. N. Antzutkin

Authors
  1. O. A. Bredyuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. O. V. Loseva
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. V. Ivanov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. V. Gowda
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. O. N. Antzutkin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. V. Ivanov.

Additional information

Original Russian Text © O.A. Bredyuk, O.V. Loseva, A.V. Ivanov, V. Gowda, O.N. Antzutkin, 2017, published in Koordinatsionnaya Khimiya, 2017, Vol. 43, No. 10, pp. 602–616.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Bredyuk, O.A., Loseva, O.V., Ivanov, A.V. et al. Three-Dimensional Polymeric Thallium(I) Morpholinedithiocarbamate [Tl2{S2CN(CH2)4O}2] n and Its Capability of Binding Gold(III) from Solutions: Chemisorption Synthesis of a Heteronuclear Gold(III)–Thallium(III) Complex of the Ionic Type, ([Au{S2CN(CH2)4O}2][TlCl4]) n , the Role of Secondary Interactions Tl…O, Tl…S, and Au…S in the Supramolecular Self-Organization, 13C MAS NMR, and Thermal Behavior. Russ J Coord Chem 43, 638–651 (2017). https://doi.org/10.1134/S1070328417100013

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1070328417100013

Keywords

Search

Navigation