Structural Studies of RSHg^II Complexes Containing (-Hg-SR-)_nRings and Chains

Crystals of acetato(methanethio1ato)-γ-picolinemercury(II), MeSHgO₂CMe, C₆H₇N (1), are mono-clinic, P2₁/a, a 16.617(9), b 7.271(3), c 20.476(2) Å β 113.31(5)°, Z 8. The structure resembles that of its pyridine analogue, being based on a polymeric (-Hg-SMe-), chain with acetate and picoline groups coordinated at each mercury; a similar structure is found for EtSHgO₂CMe, C₅H₅N (2), monoclinic, P2₁/c, a 9.344(2), b 17.917(9), c 7.179(2) Å, ß 106.24(3)°, Z 4. The structure of tetrachlorotetra(2-methylpropane-2-thiolato)di(γ-picoline)tetramercury(II), (Bu^tS)₄Cl₄Hg₄(C₆H₇N)₂(3), also resembles that of its pyridine analogue being based on an unusual tetranuclear grouping of mercury atoms linked by chloride and thiolate bridges. Crystals of (3) are monoclinic, P2₁/c, a 12.334(7), b 17.468(9), c 9.999(5) Å, β 91. 18(4)°, Z 2. Crystals of MeSHgBr (4) are monolinic, P2₁/c, a 7.770(9), b 7.500(5), c 7.945(10) Å, β 91.71(3)°, Z 4, and contain parallel chains (-Hg-SMe-), with neighbouring chains linked by bridging bromine atoms into parallel sheets. Each bromine is triply bridging, being coordinated to two mercury atoms in one chain, and one mercury atom in an adjacent chain. The structure of MeSHgCl appears to be isomorphous.