Structural Studies of RSHg(II) Complexes Containing (-Hg-SR-)n Rings and Chains

Crystals of acetato(methanethio1ato)-gamma-picolinemercury(II), MeSHg02CMe,C6H7N (1), are monoclinic, P21/a, a 16.617(9), b 7.271(3), c 20.476(2), beta = 113.31(5), Z 8. The structure resembles that of its pyridine analogue, being based on a polymeric (-Hg-SMe-)n chain with acetate and picoline groups coordinated at each mercury; a similar structure is found for EtSHg02CMe,C5H5N (2), monoclinic, P21/c, a 9.344(2), b 17.917(9), c 7.179(2) A, beta 106.24(3), Z 4. The structure of tetrachlorotetra(2-methylpropane-2-thiolato)di(gamma-picoline)tetramercury(11), (ButS)4CI4Hg4(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) A, beta 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) A, beta 91.71(3), Z 4, and contain parallel chains (-Hg-SMe-)n 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.