New organotin(IV) bromides containing potential donor ligands. Synthesis, characterization and supramolecular architecture

Triorganotin(IV) bromides containing C,E-chelating ligands (E = O, Nimine), i.e. [2-{(CH2O)2CH}C6H4]SnMe2Br, [2-(OCH)C6H4]SnMe2Br and [2-(RNCH)C6H4]SnMe2Br [R=4′-{MeO(O)C}C6H4, 2′-PyCH2, 4′-PyCH2] were prepared and characterized. Supramolecular associations based on CH⋯Br, CH⋯π (Arcentroid) and/or CH⋯π (Pycentroid) intermolecular interactions are formed in solid state for all compounds, i.e. a double chain, ribbon-like polymer or complex 3D architectures. [Display omitted] •Triorganotin(IV) bromides as potential donor ligands.•[2-(RNCH)C6H4]SnMe2Br [R = 4′-{MeO(O)C}C6H4, 2′-PyCH2, 4′-PyCH2].•Multinuclear (1H, 13C and 119Sn) NMR spectroscopy and 2D NMR experiments.•Distorted trigonal bypiramidal (C,E)SnC2Br core (E = O, N).•CH⋯Br, CH⋯π (Arcentroid) and/or (Pycentroid) intermolecular interactions. The protective acetal group in [2-{(CH2O)2CH}C6H4]SnMe2Br (1) was removed by hydrolysis to give [2-(OCH)C6H4]SnMe2Br (2). Reaction of 2 with the appropriate amines, in the absence of a solvent or catalyst, afforded the isolation in high yields of [2-(RNCH)C6H4]SnMe2Br [R = 4′-{MeO(O)C}C6H4 (3), 2′-PyCH2 (4), 4′-PyCH2 (5)]. All compounds were characterised by multinuclear NMR and IR spectroscopies as well as mass spectrometry. The molecular structures of 1, 3, 4 and 5 were established by single crystal X-ray diffraction analysis. For all organotin(IV) bromides intramolecular O→Sn or Nimine→Sn coordination results in hypercoordinated species with a distorted trigonal bipyramidal metallic centre. Supramolecular associations based on CH⋯Br, CH⋯π (Arcentroid) and/or CH⋯π (Pycentroid) intermolecular interactions are formed in solid state for all compounds, i.e. a double chain, ribbon-like polymer or complex 3D architectures.