Synthesis and structural studies of three‐dimensional supramolecular motifs derived from neutral and cationic zinc‐alkanesulfonates

The one-pot reactions between anhydrous zinc acetate, diethyl or di-n-propyl sulfite, and tetraalkylammonium iodide (120 degrees C, 12 h) proceed through sulfur-centered Arbuzov-type rearrangement to afford [(R4N)-N-1](2)[Zn(OSO2R)(4)] [R-1, R = Et (1); R-1 = nBu, R = nPr (2)] bearing alkanesulfonate groups bound to the metal center. The zincate salts 1 and 2 are used as precursors for the synthesis of neutral and cationic coordination complexes, namely, [Zn(OSO2Et)(2)(bipy)(dmso)(2)] (3; bipy = 4,4-bipyridine, dmso = dimethyl sulfoxide), [Zn(OSO(2)nPr)(2)(bipy)(2)]dmsoH(2)O (4), [Zn(bipy)(H2O)(4)](OSO2Et)(2) (5), [Zn(H2O)(6)](OSO2Et)(2) (6), and [Zn(H2O)(6)](OSO(2)nPr)(2) (7). X-ray crystallographic studies of 3-7 reveal that the alkanesulfonate groups act as prolific H-bond acceptors and assist the transformation of zero-, one-, or two-dimensional coordination frameworks into three-dimensional structural motifs.