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C=S⋯I halogen bonding interactions in crystalline iodinated dithiole-2-thiones and thiazole-2-thiones

Abstract : The propensity of the sp2 sulfur atom in thiones to act as a halogen bond (XB) acceptor is well established with dihalides (I2, IBr or ICl) as XB donors, but has been more rarely explored with organic XB donors. The crystal structures of four iodinated heterocycles, namely, the mono- and diiodo derivatives of 1,3-dithiole-2-thione and N-ethylthiazole-2-thione, offer an opportunity to evaluate the strength and directionality of such C-I⋯S interactions. We describe here the original synthesis of 3-ethyl-5-iodothiazole-2(3H)-thione and 3-ethyl-4,5-diiodothiazole-2(3H)-thione and the solid state structures of the four compounds, with specific attention to the halogen bonds (C-I⋯SC) and hydrogen bonds (C-H⋯I,S) taking place in the crystals, in connection with the peculiarities of the calculated electrostatic surface potential (ESP) of the four molecules. The thione sulfur atoms in thiazole-2-thiones appear as better XB acceptors than in dithiole-2-thiones, with a notable deformation of the charge concentration area. The mono-iodinated derivatives, 4-iodo-1,3-dithiole-2-thione and 3-ethyl-5-iodothiazole-2-thione, are characterized by hydrogen atoms with positive extremum of the electrostatic surface potential comparable to those of the neighboring iodine atoms, illustrating the parallelism between C-I⋯S halogen bonds and the so-called weak C-H⋯I,S hydrogen bonds. © The Royal Society of Chemistry 2016.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01367188
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Submitted on : Thursday, September 15, 2016 - 5:16:15 PM
Last modification on : Friday, July 10, 2020 - 4:26:25 PM

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Y. Le Gal, D. Lorcy, O. Jeannin, F. Barrière, V. Dorcet, et al.. C=S⋯I halogen bonding interactions in crystalline iodinated dithiole-2-thiones and thiazole-2-thiones. CrystEngComm, Royal Society of Chemistry, 2016, 18 (29), pp.5474--5481. ⟨10.1039/c6ce00822d⟩. ⟨hal-01367188⟩

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