Abstract
We report the synthesis and spectroscopic characterization of the first organotin(IV) complexes with cyclic seven-membered dithiocarbamate ligands: the azepane-1-carbodithioate and the homopiperazine-1,4-bis-carbodithioate with two different organotin entities, di-n-butyltin and tri-cyclohexyltin: [(C4H9)2Sn{S2CN(CH2)6}2] (3), [(C6H11)3Sn{S2CN(CH2)6}] (4), and [(C6H11)3Sn}2 (μ-S2CN(C5H10)NCS2)] (5). Compounds (3–5) are air-stable both in solid-state and in solution, and were characterized by elemental analyses, IR, FAB+–MS, and multinuclear NMR (1H, 13C, and 119Sn) spectroscopy. Their molecular structures were unambiguously established by single-crystal X-ray diffraction studies. The geometrical arrangement around the tin atom can be described as distorted octahedral for (3) and distorted trigonal bipyramid for (4) and (5). The coordination mode for both ligands is considered as asymmetric bidentate, as happens in other organotin(IV) dithiocarbamates. Furthermore, (4) and (5) do not exhibit intermolecular secondary interactions, while (3) presents intermolecular interactions between the tin and a sulfur atom with the reciprocally neighboring molecule, giving rise to a zig-zag polymeric structure.
Graphical Abstract
Acknowledgments
The spectroscopic analyses (IR, EI-MS, and multinuclear NMR 1H, 13C, and 119Sn) were performed at the Centro de Investigaciones Químicas, UAEM and single-crystal X-ray diffraction at the Instituto de Química, UNAM. The authors are grateful to the staff for this service. We acknowledge to Prof. Bryan Sowerby and Prof. Mónica Moya-Cabrera for their helpful commentaries, and Dr. Perla -Bravo for her technical assistance.