The preparation and structure of novel sulfimide systems; X-ray crystal structures of 1,4-(PhS{NH})2C6H4 (and dihydrate), 1,2-(PhS{NH})(PhS)C6H4·H2O and of [Ph2SNH] and its hydrate

Abstract

Treatment of 1,4-(PhS)₂C₆H₄ and 1,2-(PhS)₂C₆H₄ with the appropriate amount of O-mesitylsulfonylhydroxylamine (MSH) yields the corresponding protonated sulfimides, both of which may be deprotonated with DBU to give the hydrated free sulfimides 1,4-(PhS{NH})₂C₆H₄·2H₂O 1a and 1-(PhS{NH})-2-(PhS)C₆H₄·H₂O 2a. The X-ray crystal structures of both 1a and 2a, together with that of the well-known sulfimide Ph₂SNH·H₂O 3a, all reveal extended hydrogen-bonded arrays involving the N–H units and the waters of crystallisation. Crystals of 1b, the dehydrated form of 1a, also readily form, while removal of the water from 3ain vacuo followed by slow evaporation of a solution in diethyl ether under anaerobic conditions leads to crystals of Ph₂SNH 3b; the X-ray crystal structures of both 1b and 3b also reveal extended arrays formed from N–H⋯N interactions. In contrast, dehydration of 2a breaks down the extended structure resulting in the formation of an oil.