Polymeric Structure of Mercury tert-Butyl Mercury Mercaptide

Abstract

INVESTIGATIONS of metal alkoxides¹ have shown that polymeric molecules [M(OR)_x]_n are generally formed unless the alkyl group (R) is bulky. Work on sulphur analogues known as metal mercaptides M(SR)_x was undertaken in order to compare the structures and properties of metal alkoxides and metal mercaptides. A survey of the work on metal mercaptides showed that the lowest mercaptide, mercury methyl mercaptide Hg(S·CH₃)₂, has quite a compact structure² having weak intermolecular Hg—S bonds. The structure is consistent with the high melting point (185°) and low solubility of this compound. The next higher mercaptide, mercury ethyl mercaptide Hg(S·Et)₂, melts at a low temperature (76°) and as such has essentially a molecular structure³. The structures of most of the higher mercaptides are likely to be molecular since they are volatile and soluble in organic solvents. The properties of mercury tert-butyl mercaptide did not fit into this pattern. This compound has a low solubility and sublimes at a high temperature (135°) under low pressure. An X-ray analysis of this compound was, therefore, undertaken in order to elucidate its crystal structure.