Homo- and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates.

The synthesis and characterization of six homo- and heteroleptic coordination polymers and oxido clusters of bismuth(III) vinylsulfonates are reported. The solvent-mediated reaction of BiPh and vinylsulfonic acid in ethanol produces [{Ph Bi(O SCH=CH )} ] (1), which crystallizes as a one-dimensional coordination polymer as a result of bridging sulfonato ligands accompanied by intermolecular Bi⋅⋅⋅ π(arene) London dispersion interactions. In solution, compound 1 equilibrates to give [{PhBi(O SCH=CH ) } ] (2) and BiPh . Compound 2 is obtained as a single product by the reaction of BiPh with vinylsulfonic acid in acetonitrile and crystallizes as a one-dimensional coordination polymer. The homoleptic vinylsulfonate [{Bi(O SCH=CH ) } ] (3) was isolated as a two-dimensional coordination polymer, which is quite moisture sensitive, but did not provide a distinct polynuclear bismuth oxido cluster upon hydrolysis. However, by treatment of [Bi O (OH) (NO ) ]⋅H O or [Bi O (OMc) (dmso) (H O) ]⋅2 DMSO⋅5 H O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi O (OH)(O SCH=CH ) (dmso) ](O SCH=CH )⋅3 DMSO (4), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi O (NO ) (O SCH=CH ) (dmso) ](O SCH=CH ) ⋅2 DMSO (5), was observed as a co-crystallizing side product, which upon further hydrolysis afforded [Bi O (NO ) (OH) (O SCH=CH ) (dmso) (H O) ](O SCH=CH ) ⋅2 H O (6).