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Crystal Structures of a New Polymorph of N-tert-butyl-2-thioimidazole, and Its 1,4-Diiodotetrafluorobenzene, Tetraiodoethylene, and Iodine Cocrystals

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Abstract

A new polymorph of N-tert-butyl-2-thioimidazole (1), along with its cocrystals with 1,4-diiodotetrafluorobenzene (2), tetraiodoethylene (3), and molecular iodine (4) have been synthesized. Compound 1 is a new polymorph of a previously reported structure. A series of noncovalent N–H⋯S, N–H⋯I, and I⋯S interactions all contribute to the packing. In 1–3, a pair of N–H⋯S contributes to the formation of imidazole dimers, a commonly observed motif for these systems, which are then linked together through C–I⋯S halogen bonding. This halogen bond occurs approximately normal to the imidazole ring plane. In 4, the addition of I2 to the sulfur atom interrupts N–H⋯S dimer formation, with the primary interactions between neighboring imidazole molecules being of the N–H⋯I and C=S⋯I. This variety of intermolecular interactions leads to the formation of double-stranded chains, ribbons, and sheets.

Graphic Abstract

A new polymorph of N-tert-butyl-2-thioimidazole, along with its cocrystals with 1,4-diiodotetrafluorobenzene, tetraiodoethylene, and molecular iodine have been synthesized. A series of noncovalent N–H⋯S, N–H⋯I, and I⋯S all contribute to the packing

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Acknowledgements

AJP acknowledges the United States Air Force Institute of Technology Civilian Institutions program for fellowship support.

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Author notes

  1. Hadi D. Arman

    Present address: Department of Chemistry, The University of Texas at San Antonio, San Antonio, TX, 78249, USA

Authors and Affiliations

  1. Department of Chemistry, Clemson University, Clemson, SC, 29634-0973, USA

    Andrew J. Peloquin, Sarah C. Hill, Hadi D. Arman, Colin D. McMillen & William T. Pennington

  2. Department of Chemistry, The University of North Carolina at Charlotte, Charlotte, NC, 28223, USA

    Daniel Rabinovich

  3. H.L. Hunter Laboratories, Clemson, SC, 29634, USA

    William T. Pennington

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Peloquin, A.J., Hill, S.C., Arman, H.D. et al. Crystal Structures of a New Polymorph of N-tert-butyl-2-thioimidazole, and Its 1,4-Diiodotetrafluorobenzene, Tetraiodoethylene, and Iodine Cocrystals. J Chem Crystallogr 52, 62–72 (2022). https://doi.org/10.1007/s10870-021-00885-2

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