(N,N-Di­allyl­di­thio­carbamato-κ2S,S′)tri­phenyltin(IV) and bis­­(N,N-di­allyl­di­thio­carbamato-κ2S,S′)di­phenyl­tin(IV): crystal structure, Hirshfeld surface analysis and computational study

The crystal and mol­ecular structures of the title organotin di­thio­carbamate compounds, [Sn(C6H5)3(C7H10NS2)] (I) and [Sn(C6H5)2(C7H10NS2)2] (II), present very distinct tin atom coordination geometries. In (I), the di­thio­carbamate ligand is asymmetrically coordinating with the resulting C3S2 donor set defining a coordination geometry inter­mediate between square-pyramidal and trigonal–bipyramidal. In (II), two independent mol­ecules comprise the asymmetric unit, which differ in the conformations of the allyl substituents and in the relative orientations of the tin-bound phenyl rings. The di­thio­carbamate ligands in (II) coordinate in an asymmetric mode but the Sn—S bonds are more symmetric than observed in (I). The resulting C2S4 donor set approximates an octa­hedral coordination geometry with a cis-disposition of the ipso-carbon atoms and with the more tightly bound sulfur atoms approximately trans. The only directional inter­molecular contacts in the crystals of (I) and (II) are of the type phenyl-C—H⋯π(phen­yl) and vinyl­idene-C—H⋯π(phen­yl), respectively, with each leading to a supra­molecular chain propagating along the a-axis direction. The calculated Hirshfeld surfaces emphasize the importance of H⋯H contacts in the crystal of (I), i.e. contributing 62.2% to the overall surface. The only other two significant contacts also involve hydrogen, i.e. C⋯H/H⋯C (28.4%) and S⋯H/H⋯S (8.6%). Similar observations pertain to the individual mol­ecules of (II), which are clearly distinguishable in their surface contacts, with H⋯H being clearly dominant (59.9 and 64.9%, respectively) along with C⋯H/H⋯C (24.3 and 20.1%) and S⋯H/H⋯S (14.4 and 13.6%) contacts. The calculations of energies of inter­action suggest dispersive forces make a significant contribution to the stabilization of the crystals. The exception is for the C—H⋯π contacts in (II) where, in addition to the dispersive contribution, significant contributions are made by the electrostatic forces.