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Abstract
The crystal and mol-ecular structures of the title organotin di-thio-carbamate compounds, [Sn(C6H5)3(C7H10NS2)] (I) and [Sn(C6H5)2(C7H10NS2)2] (II), present very distinct tin atom coordination geometries. In (I), the di-thio-carbamate ligand is asymmetrically coordinating with the resulting C3S2 donor set defining a coordination geometry inter-mediate between square-pyramidal and trigonal-bipyramidal. In (II), two independent mol-ecules 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 di-thio-carbamate 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 octa-hedral coordination geometry with a cis-disposition of the ipso-carbon atoms and with the more tightly bound sulfur atoms approximately trans. The only directional inter-molecular contacts in the crystals of (I) and (II) are of the type phenyl-C-H⋯π(phen-yl) and vinyl-idene-C-H⋯π(phen-yl), respectively, with each leading to a supra-molecular 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 mol-ecules 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 inter-action 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.
Highlights
Farah Natasha Haezam,a Normah Awang,a‡ Nurul Farahana Kamaludin,a Mukesh M
The only directional intermolecular contacts in the crystals of (I) and (II) are of the type phenyl-C—HÁ Á Á(phenyl) and vinylidene-C—HÁ Á Á(phenyl), respectively, with each leading to a supramolecular chain propagating along the a-axis direction
Similar observations pertain to the individual molecules of (II), which are clearly distinguishable in their surface contacts, with HÁ Á ÁH being clearly dominant (59.9 and 64.9%, respectively) along with CÁ Á ÁH/ HÁ Á ÁC (24.3 and 20.1%) and SÁ Á ÁH/HÁ Á ÁS (14.4 and 13.6%) contacts
Summary
The tin atom in (I), Fig. 1, is coordinated by three ipso-carbon atoms of the phenyl groups as well as by an asymmetrically bound dithiocarbamate anion, Table 1. Should the coordination geometry be considered C3S tetrahedral, i.e. the weak Sn—S2 bond was ignored, the range of tetrahedral angles would be 91.01 (5), for S1—Sn—C31, to 128.76 (5), for S1—Sn—C11 It is noted the C1—N1 bond length of 1.330 (3) Ais consistent with significant double-bond character in this bond, which arises from a major contribution of the 2ÀS2C N+(CH2C(H) CH2) canonical form to the electronic structure of the dithiocarbamate ligand. A distinct coordination geometry for the tin atoms is noted for (II), Fig. 2, for which two independent molecules comprise the crystallographic asymmetric unit. The only connections evident are vinylidene-C—HÁ Á Á(phenyl) interactions, Table 4, which serve to link the independent molecules comprising the asymmetric unit into a supramolecular chain aligned along the a-axis direction. The chains pack without directional interactions between them, Fig. 5(b)
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