Preparation of a range of copper complexes of diphenylsulfimide:: X-ray crystal structures of [Cu(Ph2SNH)4]Cl2 and [Cu4(μ4-O)(μ-Cl)6(Ph2SNH)4]

Reaction of Ph2SNH 1 with CuCl2 (molar ratio 2:1) in acetonitrile gives trans-[CuCl2(Ph2SNH)(2)] 2a which may be isolated as blue crystals (square planar form) by crystallisation from hot MeCN or as green needles (pseudo-tetrahedral form) by slow evaporation of a CH2Cl2/petroleum ether solution. In contrast, [CuBr2(Ph2SNH)(2)] 2b, most efficiently prepared by reaction of [Cu(Ph2SNH)(4)]Br-2 with CuBr2, appears to only exist in a dark green, pseudo-tetrahedral form. When 1.5 equivalents of 1 are reacted with CuX2 in air, [Cu-4(mu(4)-O)(mu-X)(6)(Ph2SNH)(4)] (X = Cl 3a or Br 3b) forms as orange crystals. X-ray crystallography reveals 3a to have the expected tetrahedral arrangement of Cu atoms within an oxo-centered Cu4Cl6O core. Four equivalents of 1 react with CuX2 to give purple [Cu(Ph2SNH)(4)]X-2 (X = Cl 4a or Br 4b); the X-ray crystal structure of 4a reveals a square planar structure exhibiting strong hydrogen bonding interactions between the ligands and the counterions. Even in the presence of excess 1, no more than four of the Ligands may be added to a copper centre. (C) 1999 Elsevier Science Ltd. All rights reserved.