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Abstract
A new air-stable cyclohexasulfur（cyclo-S6）was discovered in the crystal of 3,5-diphenyl-1,2,4-dithiazol-1-ium（dpdti）iodide, formed by cocrystallization. The dpdti was synthesized via an oxidation reaction of thiobenzamide with iodine in benzene. Two kinds of crystal habits—brock-shaped（crystal-A）and needle-shaped（crystal-B）—were obtained following recrystallization from acetonitrile solvent. All molecules in crystal-A and -B were identified through single-crystal X-ray structure analysis using a synchrotron X-ray. The cyclic-S6 molecule in the crystal-A is a self-assembly enclosed by the dpdti cation and iodide anion, and is assumed to contribute to their stability in the crystal, akin to the Sn ring in zeolites and sodalites. In the context of cyclo-S6, cocrystallization is constituted by weak intermolecular effects such as the van der Waals force. Crystal engineering of cocrystals resulted in air-stable cyclo-S6. This study presents a method to turn an unstable molecule into a stable crystalline molecule that maintains its origin structure, with an aim of predicting its stability in future studies.
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