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Synthesis of Thiosemicarbazones and Their Organoiodine Cocrystals: Cooperative Effects of Halogen and Hydrogen Bonding

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Abstract

Utilizing the facile addition–elimination reaction of thiosemicarbazide with acetone or aldehydes, nine thiosemicarbazones were synthesized. Aldehydes were chosen which contain additional heteroatoms to increase the diversity of possible intermolecular interactions. Further, the thiosemicarbazone synthesis was conducted in situ with one of the common halogen bond donors 1,2-, 1,3-, or 1,4-diiodotetrafluorobenzene, 1,3,5-trifluoro-2,4,6-triiodobenzene, or tetraiodoethylene. These reactions resulted in the characterization of 12 new cocrystals showcasing halogen bonding. The dimerization of two thiosemicarbazone units through a pair of N‒H···S hydrogen bonds was a universal feature of the solid-state structures in this series, with the hydrogen bond network often extending these motifs into chains. The organoiodines serve to link chains through either I···S or I···N halogen bonding, or less commonly, S···I chalcogen bonding. This variety of intermolecular interactions leads to the formation of double-stranded chains, ribbons, and sheets.

Graphical Abstract

Utilizing the facile addition–elimination reaction of thiosemicarbazide with acetone or aldehydes, nine thiosemicarbazones were synthesized, seven of which were isolated as cocrystals with common halogen bond donors. Significant N–H···S hydrogen bonding was observed in all, with S···I halogen and chalcogen bonding contributing to the long-range packing in the cocrystals.

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Data Availability

The crystallographic data including CIF and fcf files have been deposited into Cambridge Crystallographic Data Centre. CCDC 2,117,350 through 2,117,363 contain the crystallographic data. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.

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Acknowledgements

AJP acknowledges the United States Air Force Institute of Technology Civilian Institutions program and the Air Force Office of Scientific Research for fellowship support. The authors thank the NSF grants CHE-1560300 and CHE-2050042 for supporting this work.

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  1. H.L. Hunter Laboratories, Department of Chemistry, Clemson University, Clemson, SC, 29634-0973, USA

    Andrew J. Peloquin, Arianna C. Ragusa, Hadi D. Arman, Colin D. McMillen & William T. Pennington

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Correspondence to Colin D. McMillen or William T. Pennington.

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WTP is the Editor-in-Chief of the Journal of Chemical Crystallography. CDM is an Associate Editor with the Journal of Chemical Crystallography. They have been excluded from the peer review process.

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Peloquin, A.J., Ragusa, A.C., Arman, H.D. et al. Synthesis of Thiosemicarbazones and Their Organoiodine Cocrystals: Cooperative Effects of Halogen and Hydrogen Bonding. J Chem Crystallogr 52, 512–524 (2022). https://doi.org/10.1007/s10870-022-00931-7

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