Polymorphism,Halogen Bonding,and Chalcogen Bonding in the Diiodine Adducts of 1,3- and 1,4-Dithiane |
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| Authors: | Andrew J Peloquin Srikar Alapati Colin D McMillen Timothy W Hanks William T Pennington |
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| Institution: | 1.Department of Chemistry, Clemson University, Clemson, SC 29634, USA; (A.J.P.); (C.D.M.);2.Department of Chemistry, Furman University, Greenville, SC 29613, USA; (S.A.); (T.W.H.) |
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| Abstract: | Through variations in reaction solvent and stoichiometry, a series of S-diiodine adducts of 1,3- and 1,4-dithiane were isolated by direct reaction of the dithianes with molecular diiodine in solution. In the case of 1,3-dithiane, variations in reaction solvent yielded both the equatorial and the axial isomers of S-diiodo-1,3-dithiane, and their solution thermodynamics were further studied via DFT. Additionally, S,S’-bis(diiodo)-1,3-dithiane was also isolated. The 1:1 cocrystal, (1,4-dithiane)·(I2) was further isolated, as well as a new polymorph of S,S’-bis(diiodo)-1,4-dithiane. Each structure showed significant S···I halogen and chalcogen bonding interactions. Further, the product of the diiodine-promoted oxidative addition of acetone to 1,4-dithiane, as well as two new cocrystals of 1,4-dithiane-1,4-dioxide involving hydronium, bromide, and tribromide ions, was isolated. |
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| Keywords: | crystal engineering chalcogen bonding halogen bonding polymorphism X-ray diffraction |
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