Stabilization of [(nBu2SnCl)(μ-Cl)2(ClSnnBu2)] within the solid-state structure of a Chlorodi-n-butyltin(IV) dithiocarbamate

• Chlorodiorganotin dithiocarbamates have been prepared.
• S⋯S, S⋯Cl, Cl⋯Cl, Cl⋯N and Cl⋯Sn contacts were found in the solid state.
• Unusual dimers of the composition [(nBu2SnCl)(μ-Cl)2(ClSnnBu2)] are described.
• The latter are stored in form of a co-crystalline assembly.

The combination of bis-dithiocarbamate ligands derived from N,N′-dibenzylcyclohexane-trans-1,4-diamine with dimethyl- and di-n-butyltin(IV) dichloride provided two discrete dinuclear complexes of the composition [(Me2SnCl)2(bis-dtc)]·2CHCl3 (1) and [(nBu2SnCl)2(bis-dtc)] (2) with bis-dtc = N,N′-dibenzylcyclohexane-trans-1,4-diamine-bisdithiocarbamate. Additionally, single crystals of the composition [(nBu2SnCl)(mono-dtc)]·[nBu2SnCl2]2 (3) with mono-dtc = N,N′-dibenzylcyclohexane-trans-1,4-diamine-monodithiocarbamate were isolated. Within the crystal structures of the three complexes, a varied number of common (C–H⋯S, C–H⋯Cl and N–H⋯Cl) and less common (S⋯S, S⋯Cl, Cl⋯Cl, Cl⋯N and Cl⋯Sn) secondary interactions were observed and analyzed. The supramolecular solid-state organization of [(Me2SnCl)2(bis-dtc)]·2CHCl3 revealed the presence of channels, which were filled with chloroform molecules. In the crystal structure of [(nBu2SnCl)(mono-dtc)]·[nBu2SnCl2]2, the di-n-butyltin dichloride units are arranged in form of a so far unknown dimeric aggregate of the composition [(nBu2SnCl)(μ-Cl)2(ClSnnBu2)]. The latter assembly represents thus a rare example for a two-component co-crystalline assembly, in which a relatively large non-solvent molecule with unusual molecular structure is stored and stabilized.

The single-crystal X-ray diffraction analysis of three chlorodiorganotin dithiocarbamates revealed the presence of a variety of intermolecular interactions including C–H∙∙∙S, C–H∙∙∙Cl, N–H∙∙∙Cl, S∙∙∙S, S∙∙∙Cl, Cl∙∙∙Cl, Cl∙∙∙N and Cl∙∙∙Sn contacts, which can stabilize supramolecular co-crystalline assemblies containing unusual molecular aggregates such as the [nBu2SnCl2] dimer.Figure optionsDownload as PowerPoint slide