The role of substituents on configurational isomerism and geometry of adamantane-like [(μ-ER)6(MX)4]2- (E = chalcogen, X = halogen).: Structures of (Me4N)2[(μ-SPh)6(ZnX)4] (X = Cl, Br, I).

The structures of (Me4N)(2)[mu-SPh)(6)(ZnX)(4)] . xMeCN (X = Cl,x = 2 (1); Br, x = 2 (2); I, x = 1.25 (3)) have been determined by single crystal X-ray diffraction techniques. This is the first time a complete family of adamantanoid tetrahalo-anions [(mu(-SPh)(6)(MX)(4)](2-) has been characterized structurally. In each anion the configuration (axial or equatorial) of the phenyl groups in the four six-membered rings is [aae, aae, aee, aee], corresponding to isomer III. The (mu-S)(6)Zn-4 cage is distorted in each case, but there is little systematic effect on dimensions of the cage as the terminal halogen is varied. Such differences as exist may result from a difference between the space group when X = I and that when X = Cl or Br. (C) 1998 Elsevier Science Ltd. All rights reserved.