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Molecular structures and supramolecular association of chlorodiorganotin(IV) complexes with bis- and tris-dithiocarbamate ligand

2010; Elsevier BV; Volume: 696; Issue: 3 Linguagem: Inglês

10.1016/j.jorganchem.2010.09.061

1872-8561

Hugo Tlahuext, Reyna Reyes‐Martínez, Gabriela Vargas‐Pineda, Marcela López‐Cardoso, Herbert Höpfl,

Crystallography and molecular interactions

Two series of di and trinuclear chlorodiorganotin(IV) complexes derived from bis- and tris-dithiocarbamate ligands have been prepared and structurally characterized. The dinuclear complexes 1–2 of the composition {(R2SnCl)2(bis-dtc)} (1, R = Me; 2, R = nBu) have been obtained from R2SnCl2 (R = Me, nBu) and the triethylammonium salt of N,N′-dibenzyl-1,2-ethylene-bis(dithiocarbamate). The trinuclear complexes 3–9 with the general formula {(R2SnCl)3(tris-dtc)} 3, R = Me, tris-dtc = tris-dtc-Me; 4, R = Me, tris-dtc = tris-dtc-iPr; 5, R = Me, tris-dtc = tris-dtc-Bn; 6, R = nBu, tris-dtc = tris-dtc-Me; 7, R = nBu, tris-dtc = tris-dtc- iPr; 8, R = nBu, tris-dtc = tris-dtc-Bn; 9, R = tBu, tris-dtc = tris-dtc-Me) were prepared from R2SnCl2 (R = Me, nBu, tBu) and the potassium dithiocarbamate salts of (tris[2-(methylamino)ethyl]amine) (tris-dtc-Me), (tris[2-(isopropylamino)ethyl]amine) (=tris-dtc-iPr) and (tris[2-(benzylamino)ethyl]amine) (=tris-dtc-Bn). Compounds 1–9 have been analyzed as far as possible by elemental analysis, FAB+ mass spectrometry, IR and NMR (1H, 13C, 119Sn) spectroscopy, and single-crystal X-ray diffraction analysis. The solid state and solution studies showed that the dtc ligands are coordinated to the tin atoms in the anisobidentate manner. In all cases the metal centers are five-coordinate. The coordination geometry is intermediate between square-pyramidal and trigonal-bipyramidal coordination polyhedra with τ-values in the range of 0.32–0.53. For the members of each series characterized in the solid state by X-ray diffraction analysis, different molecular conformations were found. The crystal structures show the presence of C–H⋯Cl, C–H⋯S, C–H⋯π, S⋯Cl, S⋯S, Cl⋯Sn and S⋯Sn contacts.