A New Family of Supramolecular Complexes with 3D Cationic Hg/Z Frameworks, SnX3− Guest Anions (Z = P, As, Sb; X = Cl, Br, I): Crystal Structures and Host−Guest Interactions

Abstract

Five new inorganic supramolecular complexes, [Hg6P4Cl3](SnCl3) (I), [Hg6As4Cl3](SnCl3)Hg0.13 (II), [Hg6As4Br3](SnBr3) (III), [Hg6Sb4I3](SnI3)Hg0.16 (IV), and [Hg7P4Br3](SnBr3) (V), have been prepared and their structures determined by X-ray single crystal experiments. They all crystallize in the cubic space group P213 (No 198) with Z = 4, and unit cell parameters a = 11.865(1) (I), 12.233(1) (II), 12.383(1) (III), 13.285(2) (IV), and 12.490(1) A (V). The crystal structures of these compounds are composed of the 3D positively charged frameworks [Hg6Z4X3]+ (I−IV) or [Hg7P4Br3]+ (V), with SnX3− anions trapped in the larger cavities of the frameworks (X = Cl, Br, I; Z = P, As, Sb). In the structures of II and IV the smaller cavities are partly filled by mercury atoms. The structures of I−V and of previously reported [Hg7As4I3](SnI3) (VI) are discussed with respect to the matching and mutual adjusting of the host frameworks and guest anions. A comparison of the observed and calculated (ab initio, RHF level) geometry of the SnX3− anions is used to analyze the weak host−guest interactions.