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Crystal and electronic structure of thiazolium pentaiodide: an experimental and theoretical study of covalent and non-covalent bonds

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Abstract

Crystal and electronic structures of a newly synthesized thiazolium pentaiodide, C3H4NS(I5), were examined in detail. The title pentaiodide crystallizes in the monoclinic space group P21/m with the unit cell volume of 1289.27(6) Å3. Its crystal structure features branched pentaiodide chains composed of alternating I3− and I2 building units, whereas the chains are further linked into a 3D array by thiazolium cations with the help of (N)H⋅⋅⋅I and S⋅⋅⋅I bonds. The electronic structure and bonding assessed by DFT calculations show that covalent interactions within the I2 and I3− units are supplemented by non-covalent (N)H⋅⋅⋅I and S⋅⋅⋅I interactions, which were revealed by the electron localization function and reduced density gradient analyses.

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Availability of data and materials

Data are available from the authors upon a reasonable request.

Code availability

Details on the crystal structure investigation may be obtained from the Cambridge Crystallographic Data Centre by quoting the CCDC number 2191074.

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Funding

This work was supported by the Russian Foundation for Basic Research, grant no. 21–53-50007. The synthesis and characterization of starting thiazolium thiocyanate were performed during realization of project 21–73-10212 supported by the Russian Science Foundation.

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Authors and Affiliations

  1. Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3 119991, Moscow, Russia

    Tatiana A. Shestimerova, Alexey N. Kuznetsov & Andrei V. Shevelkov

  2. Dmitry Rogachev National Medical Research Center of Pediatric Hematology, Oncology and Immunology, Samory Mashela st. 1, 117997, Moscow, Russia

    Ivan A. Andreev, Nina K. Ratmanova & Igor V. Trushkov

  3. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr. 47, 119334, Moscow, Russia

    Igor V. Trushkov

Authors
  1. Tatiana A. Shestimerova
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  2. Ivan A. Andreev
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  3. Nina K. Ratmanova
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  4. Igor V. Trushkov
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  5. Alexey N. Kuznetsov
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  6. Andrei V. Shevelkov
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Contributions

TAS performed the crystal structure solution and co-wrote the manuscript; IAA, NKR, and IVT performed synthesis and primary characterization and co-wrote the manuscript; ANK performed calculations and co-wrote the manuscript; and AVS supervised the research and co-wrote and edited the manuscript.

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Correspondence to Andrei V. Shevelkov.

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Shestimerova, T.A., Andreev, I.A., Ratmanova, N.K. et al. Crystal and electronic structure of thiazolium pentaiodide: an experimental and theoretical study of covalent and non-covalent bonds. Struct Chem 34, 1557–1564 (2023). https://doi.org/10.1007/s11224-022-02097-6

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