Five novel arylsulfonates of Ni and Co have been hydrothermally obtained and their structures determined by X-ray single-crystal diffraction. [Ni(Phen)(H2O)(4)](1,5-NDS)center dot 2H(2)O (1) is a hydrogen-bonded supramolecular layered compound formed by self-assembly of tetraaqua-o-phenanthrolinenickel(II) cations and 1,5-naphthalenedisulfonate anions, [Ni(Phen)(2)(H2O)(1,5-NDS)] (2) and [Ni(Phen)(2)(H2O)(2,6-NDS)]center dot 2H(2)O (4) exhibit 2D structures via O-H center dot center dot center dot O and pi-pi (both perfect face-to-face and parallel-displaced) stacking interactions, [Co(Phen)(2)(H2O)(1,5-NDS)]center dot 2H(2)O (5) presents a 3D structure via O-H center dot center dot O hydrogen-bond layers and pi-pi parallel-displaced stacking interactions, and [Co(Phen)(2)(1,5-NDS)] (3) is the first example of a covalently bonded polymeric cobalt sulfonate. Its 1D structure comprises chains formed through bitopic 1,5-NDS linkers. Rates and selectivities for oxidation of organic sulfides with H2O2 were measured with 2-5.