New pentacoordinate bicyclodiazastannsulfide formed between the functionalized cyclopentadienyl ring and tin

New pentacoordinate bicyclodiazastannsulfide fused cyclopentadienyl M–Sn (M = Mo or W) bonded organometallic heterocycle {μ-[C5H4(CH3)Cdouble bond; length as m-dashNsingle bondNdouble bond; length as m-dashC(S)Ar]M(CO)3SnCl2} has been obtained by the condensation reaction of CH3COC5H4M(CO)3SnCl3 with arylthiocarboxyhydrazide (ArCSNHNH2, Ar = 2-furanyl, 2-thienyl, 2- or 4-hydroxyphenyl) in mild conditions. While the similar reaction of CH3COC5H4M(CO)3SnCl3 with ArCONHNH2 (Ar = 2- or 4-hydroxyphenyl) only gives non-cyclic compound [C5H4(CH3)Cdouble bond; length as m-dashNsingle bondNHC(O)Ar]M(CO)3SnCl3, in which the tin atom remains tetracoordinate. In bicyclodiazastannsulfide the tin atom prefers to adopt pentacoordinate geometry, while in the corresponding bicyclodiazastannoxide the tin atom is hexacoordinate. In addition, phenylhydrazine, 2- or 4-hydroxyphenylcarboxyhydrazide is used to react with CH3COC5H4M(CO)3SnCl3, only tetracoordinate non-cyclic tin compound is obtained.