Mono-organotin(IV) and tin(IV) derivatives of 2-mercaptopyridine and 2-mercaptopyrimidine: X-ray structures of methyl-tris(2-pyridinethiolato)tin(IV) and phenyl-tris(2-pyridinethiolato)tin(IV)center dot 1.5CHCl(3)

Mono-organotin(IV) and tin(IV) derivatives of 2-mercaptopyridine (HSPy) and 2-mercaptopyrimidine (HSPym), RSnL3 (R=Me, n-Bu, Ph; L=SPy, SPym; R=Bz=benzyl, o-CIBz, o-CIC6H4, p-CIC6H4, o-tolyl, p-tolyl; L=SPy), RSnCIL2 (R=Me, n-Bu, Ph; L=SPyS, SPym), RSnCl2L (R=Me, n-Bu; L=SPy, SPym) and SnCl4-nLn (L=SPy, SPym; n=2,4) were obtained from RSnCl3 or SnCl4 and NaL or by neutralization (R=Ph, p-tolyl; L=SPy; SPym). RSnCIL2 and RSnCI2L were better prepared by comproportionation of RSnCl3 and RSnL3. MeSn(SPy)(3) and PhSn(SPy)(3) . 1.5CHCl(3) crystals, as determined by single-crystal X-ray diffraction, are monoclinic. In the discrete monomeric RSn(SPy)(3) units, three bidentate SPy ligands together with R form a distorted pentagonal bipyramid around tin. One S and the C(R) atom are in the axial positions. Two S atoms and three N atoms form the pentagonal plane. From Sn-119 Mossbauer and IR data, analogous structures are inferred for the other solid RSnL, compounds, except for R=Bz, o-CIBz, o-CIC6H4 and o-tolyl, in which tin would be hexacoordinated. In the compounds RSnCIL2 and RSnCI,L, tin is at the center of an octahedron or a trigonal bipyramid, respectively. For Sn(SPym)(4) and SnCl2(SPym)(2), the same type of octahedral structure as previously found for Sn(SPy)(4) . HSPy was and SnCl2(SPy)(2) is proposed. According to IR and H-1, C-13 and Sn-119 NMR data, the solid-state molecular structures are retained in chloroform and dimethyl sulfoxide solution. (C) 1997 John Wiley & Sons, Ltd.