Organotin (IV) azepane dithiocarbamates: synthesis and characterization of the first organotin (IV) complexes with seven-membered cyclic dithiocarbamates

Abstract

We report the synthesis and spectroscopic characterization of the first organotin(IV) complexeswith cyclic seven-membered dithiocarbamate ligands: the azepane-1-carbodithioate andthe homopiperazine-1,4-bis-carbodithioate with two different organotin entities, di-n-butyltin andtri-cyclohexyltin: [(C4H9)2SnfS2CN(CH2)6g2](3), [(C6H11)3SnfS2CN(CH2)6g](4), and [(C6H11)3Sng2(l-S2CN(C5H10)NCS2)] (5). Compounds (3–5) are air-stable both in solid-state and in solution, andwere characterized by elemental analyses, IR, FABþ–MS, and multinuclear NMR (1H,13C, and119Sn)spectroscopy. Their molecular structures were unambiguously established by single-crystal X-raydiffraction studies. The geometrical arrangement around the tin atom can be described as dis-torted octahedral for (3) and distorted trigonal bipyramid for (4) and (5). The coordination modefor both ligands is considered as asymmetric bidentate, as happens in other organotin(IV) dithio-carbamates. Furthermore, (4) and (5) do not exhibit intermolecular secondary interactions, while(3) presents intermolecular interactions between the tin and a sulfur atom with the reciprocallyneighboring molecule, giving rise to a zig-zag polymeric structure.