Polynuclear Bismuth Oxido Sulfonato Clusters, Polymers, and Ion Pairs from Bi<sub>2</sub>O<sub>3</sub> under Mild Conditions

Eight novel bismuth­(III) sulfonato compounds have been synthesized and characterized using the sonochemical reaction of Bi<sub>2</sub>O<sub>3</sub> with a range of sulfonic acids, including 2,5-dimethylbenzenesulfonic acid (2,5-DMS<i>H</i>), 2,4-dinitrobenzenesulfonic acid (2,4-DNS<i>H</i>), 2,5-dichlorobenzenesulfonic acid (2,5-DCS<i>H</i>), 1,2-benzenedisulfonic acid (1,2-BDS<i>H</i><sub>2</sub>), 1,3-benzenedisulfonic acid (1,3-BDS<i>H</i><sub>2</sub>), 2-sulfobenzoic acid (2-SB<i>H</i><sub>2</sub>), 3-sulfobenzoic acid (3-SB<i>H</i><sub>2</sub>), and 2-naphthalenesulfonic acid (NPS<i>H</i>). Six of the complexes (<b>1</b>, <b>2</b>, <b>4</b>, and <b>6</b>–<b>8</b>) were structurally characterized through single-crystal X-ray crystallography. In the presence of the monosulfonic acids 2,5-DMS<i>H,</i> 2,4-DNS<i>H</i>, and 2,5-DCS<i>H</i>, polynuclear bismuth­(III) oxido clusters were isolated: namely, [Bi<sub>6</sub>O<sub>4</sub>(OH)<sub>4</sub>(2,5-DMS)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·10H<sub>2</sub>O (<b>1</b>·10H<sub>2</sub>O), [Bi<sub>6</sub>O<sub>4</sub>(OH)<sub>4</sub>(2,4-DNS)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·6H<sub>2</sub>O (<b>2</b>·6H<sub>2</sub>O), and [Bi<sub>6</sub>O<sub>4</sub>(OH)<sub>4</sub>(2,5-DCS)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>] (<b>3</b>). The disulfonic acid 1,3-BDS<i>H</i><sub>2</sub> also produced an oxido cluster: [Bi<sub>6</sub>O<sub>4</sub>(OH)<sub>4</sub>(1,3-BDS)<sub>3</sub>]·8H<sub>2</sub>O (<b>5</b>·8H<sub>2</sub>O). The remaining diacid ligands (1,2-BDS<i>H</i><sub>2</sub>, 2-SB<i>H</i><sub>2</sub>, and 3-SB<i>H</i><sub>2</sub>), upon reaction with Bi<sub>2</sub>O<sub>3</sub>, produced polymeric Bi­(III) sulfonato complexes: namely [Bi­(1,2-BDS)­(OH)­(H<sub>2</sub>O)<sub>2</sub>]<sub>∞</sub> (<b>4</b>), [Bi­(2-SB)­(2-SB<i>H</i>)­H<sub>2</sub>O]<sub>∞</sub>·2H<sub>2</sub>O (<b>6</b>·2H<sub>2</sub>O), and [NH<sub>2</sub>(Me)<sub>2</sub>]<sub>2</sub>[Bi<sub>2</sub>(3-SB)<sub>4</sub>]<sub>∞</sub> (<b>7</b>). The larger NPS<i>H</i> ligand produced the monomeric contact ion pair [Bi­(NPS)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub>]­[NPS]·3H<sub>2</sub>O (<b>8</b>·3H<sub>2</sub>O), upon sonication with Bi<sub>2</sub>O<sub>3</sub>.