Octa‐, Hexa‐, and Tetracoordination in Tin(IV) Derivatives of cis ‐β‐(Methylthio)stilbene‐α‐thiol

The S ‐methyl‐cis‐stilbene‐α,β‐dithiolate of Sn(IV), Sn[Ph(S)C=C(SCH 3 )Ph] 4 , has an octacoordinate structure with two sets of four covalent and coordinate Sn–S and Sn–S(CH 3 ) bonds of 2.425(3) and 3.599(3) Å, respectively. Both types of Sn–S bonds are close to being tetrahedral, the coordination geometry is a distorted cube. This unprecedented structure appears to involve conventional covalent and outer‐sphere coordinative Sn–S bonds. In the diphenyl derivative Ph 2 Sn[Ph(S)C=C(SCH 3 )Ph] 2 the SnC 2 S 2 core formed by the covalent Sn–C and Sn–S(thiolato) bonds is tetrahedral, but two coordinate outer‐sphere Sn‐S(CH 3 ) bonds of 3.500(3) Å are also present. In the related SnCl 2 [Ph(S)C=C(SCH 3 )Ph] 2 the presence of the polar Sn–Cl bonds prevents outer‐sphere bonding; the coordination geometry is distorted octahedral. In the triphenyltin derivative Ph 3 Sn[Ph(S)C=C(SCH 3 )Ph] the coordination geometry is tetrahedral, the thiol‐thioether ligand being monodentate with the SCH 3 group in a non‐interactive position.