Abstract

Protonation of Ph₂SNH 1 with HCl gives [Ph₂SNH₂]Cl 2 which shows strong hydrogen bonding between the sulfimidium NH₂ unit and the chloride anion resulting in a zig-zagged 1-D structure in which stacks of [Ph₂SNH₂]⁺ cations are observed. The analogous bromide, [Ph₂SNH₂]Br, 3 is not isostructural and shows an extended structure with two stacks of cations linked by bridging bromide anions. Reaction of two equivalents of 2 with CuCl₂ gives [Ph₂SNH₂]₂[CuCl₄] 4 in two forms. One of these, 4a, which is formed at ambient temperature, is orange and contains distorted tetrahedral [CuCl₄]²⁻ anions whilst the lower temperature form, 4b, is green and contains both distorted tetrahedral and square planar copper geometries in the same unit-cell. Both structures show extended arrays formed via the hydrogen bonding between the sulfimidium NH₂ unit and chlorides.