Distinct coordination geometries in bis-[N,N-bis-(2-meth-oxy-eth-yl)di-thio-carbamato-κ(2) S,S']di-phenyltin(IV) and bis-[N-(2-meth-oxy-eth-yl)-N-methyl-dithio-carbamato-κ(2) S,S']di-phenyl-tin(IV): crystal structures and Hirshfeld surface analysis.

Rapidah Mohamad,Edward R T Tiekink,Normah Awang,Mukesh M Jotani

doi:10.1107/s2056989016011385

Abstract

The crystal and mol-ecular structures of two di-phenyl-tin bis-(di-thio-carbamate)s, [Sn(C6H5)2(C5H10NOS2)2], (I), and [Sn(C6H5)2(C7H14NO2S2)2], (II), are described. In (I), in which the metal atom lies on a twofold rotation axis, the di-thio-carbamate ligand coordinates with approximately equal Sn-S bond lengths and the ipso-C atoms of the Sn-bound phenyl groups occupy cis-positions in the resulting octa-hedral C2S4 donor set. A quite distinct coordination geometry is noted in (II), arising as a result of quite disparate Sn-S bond lengths. Here, the four S-donors define a trapezoidal plane with the ipso-C atoms lying over the weaker of the Sn-S bonds so that the C2S4 donor set defines a skewed trapezoidal bipyramid. The packing of (I) features supra-molecular layers in the ab plane sustained by methyl-ene-C-H⋯π(Sn-ar-yl) inter-actions; these stack along the c-axis direction with no specific inter-actions between them. In (II), supra-molecular chains along the b-axis direction are formed by methyl-ene-C-O(ether) inter-actions; these pack with no directional inter-actions between them. A Hirshfeld surface analysis was conducted on both (I) and (II) and revealed the dominance of H⋯H inter-actions contributing to the respective surfaces, i.e. >60% in each case, and other features consistent with the description of the mol-ecular packing above.

Highlights

The crystal and molecular structures of two diphenyltin bis(dithiocarbamate)s, [Sn(C6H5)2(C5H10NOS2)2], (I), and [Sn(C6H5)2(C7H14NO2S2)2], (II), are described
In (I), in which the metal atom lies on a twofold rotation axis, the dithiocarbamate ligand coordinates with approximately equal Sn—S bond lengths and the ipso-C atoms of the Sn-bound phenyl groups occupy cispositions in the resulting octahedral C2S4 donor set
The four S-donors define a trapezoidal plane with the ipso-C atoms lying over the weaker of the Sn—S bonds so that the C2S4 donor set defines a skewed trapezoidal bipyramid

Summary

Chemical context

The C2S4 donor set is defined by two chelating dithiocarbamate ligands and the ipso-carbon atoms of the tin-bound phenyl substituents. The difference between the Sn—Sshort and Sn—Slong bond lengths, i.e. Á(Sn—S), is relatively small at 0.06 A , indicating an essentially symmetric coordination mode This symmetry is reflected in the near equivalence of the associated C1—S bond lengths with the difference between them being 0.024 A , Table 1. The tin-bound ipso-carbon atoms are disposed over the weaker Sn—S bonds so that the coordination geometry is skewed trapezoidal bipyramidal. As for (I), the methoxyethyl groups lie almost perpendicular to the plane through the S2CN atoms with the greatest deviation being for the O1-containing residue, i.e. the C1—N1—C5—C6 torsion angle is À81.5 (3). Extended conformation with the O4-residue showing the greatest deviation, albeit marginally, as seen in the C14—O4— C13—C12 torsion angle of 176.3 (2)

Supramolecular features

Hirshfeld surface analysis

Database survey

Synthesis and crystallization

Refinement