Polynuclear Bismuth Oxido Sulfonato Clusters, Polymers, and Ion Pairs from Bi2O3 under Mild Conditions

Eight novel bismuth­(III) sulfonato compounds have been synthesized and characterized using the sonochemical reaction of Bi2O3 with a range of sulfonic acids, including 2,5-dimethylbenzenesulfonic acid (2,5-DMSH), 2,4-dinitrobenzenesulfonic acid (2,4-DNSH), 2,5-dichlorobenzenesulfonic acid (2,5-DCSH), 1,2-benzenedisulfonic acid (1,2-BDSH2), 1,3-benzenedisulfonic acid (1,3-BDSH2), 2-sulfobenzoic acid (2-SBH2), 3-sulfobenzoic acid (3-SBH2), and 2-naphthalenesulfonic acid (NPSH). Six of the complexes (1, 2, 4, and 68) were structurally characterized through single-crystal X-ray crystallography. In the presence of the monosulfonic acids 2,5-DMSH, 2,4-DNSH, and 2,5-DCSH, polynuclear bismuth­(III) oxido clusters were isolated: namely, [Bi6O4(OH)4(2,5-DMS)6(H2O)6]·10H2O (1·10H2O), [Bi6O4(OH)4(2,4-DNS)6(H2O)6]·6H2O (2·6H2O), and [Bi6O4(OH)4(2,5-DCS)6(H2O)6] (3). The disulfonic acid 1,3-BDSH2 also produced an oxido cluster: [Bi6O4(OH)4(1,3-BDS)3]·8H2O (5·8H2O). The remaining diacid ligands (1,2-BDSH2, 2-SBH2, and 3-SBH2), upon reaction with Bi2O3, produced polymeric Bi­(III) sulfonato complexes: namely [Bi­(1,2-BDS)­(OH)­(H2O)2] (4), [Bi­(2-SB)­(2-SBH)­H2O]·2H2O (6·2H2O), and [NH2(Me)2]2[Bi2(3-SB)4] (7). The larger NPSH ligand produced the monomeric contact ion pair [Bi­(NPS)2(H2O)6]­[NPS]·3H2O (8·3H2O), upon sonication with Bi2O3.