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 BiPh3 and vinylsulfonic acid in ethanol produces [{Ph2Bi(O3SCH=CH2)}(n)] (1), which crystallizes as a one-dimensional coordination polymer as a result of bridging sulfonato ligands accompanied by intermolecular Bi center dot center dot center dot pi(arene) London dispersion interactions. In solution, compound 1 equilibrates to give [{PhBi(O3SCH=CH2)(2)}(n)] (2) and BiPh3. Compound 2 is obtained as a single product by the reaction of BiPh3 with vinylsulfonic acid in acetonitrile and crystallizes as a one-dimensional coordination polymer. The homoleptic vinylsulfonate [{Bi(O3SCH=CH2)(3)}(n)] (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 [Bi6O4(OH)(4)(NO3)(6)]center dot H2O or [Bi38O45(OMc)(24)(dmso)(9)(H2O)(2)]center dot 2 DMSO center dot 5 H2O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi9O7(OH)(O3SCH=CH2)(11)(dmso)(11)](O3SCH=CH2)center dot 3 DMSO (4), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi38O45(NO3)(8)(O3SCH=CH2)(14)(dmso)(18)](O3SCH=CH2)(2)center dot 2 DMSO (5), was observed as a co-crystallizing side product, which upon further hydrolysis afforded [Bi38O45(NO3)(6)(OH)(4)(O3SCH=CH2)(12)(dmso)(23)(H2O)(2)](O3SCH=CH2)(2)center dot 2 H2O (6).