Recent progress in the solid-state coordination and structural chemistry of aromatic disulfonates as well as the amine interaction properties of crystalline Cd2+ sulfonate complexes will be outlined. Due to the weak coordination strength, most of the metal monosulfonates obtained from aqueous solution are water-coordinated metal sulfonate salts. However, by employing arenedisulfonates, which can provide multiple coordination sites, stable frameworks sustained by sulfonate-metal interactions can be obtained with various dimensionalities. The sulfonate groups show diverse coordination modes, which change starkly from eta(3) mu(3) bridging in sodium(I) 1,5-naphthalenedisulfonate dihydrate to eta(7) mu(5) bridging in sodium(I) 4,4'-phenyletherdisulfonate. The coordination strength of the alkali, alkaline earth metals and some divalent transition metals toward sulfonates will be evaluated. Moreover, layered sulfonate- and water-coordinated Cd2+ complexes can selectively uptake amine vapor via solid-state substitution reaction, in a reversible process under ambient conditions. The coordination modes and conformations of aromatic monosulfonates are analyzed based upon the crystal structures documented by CSD. The syn monodentate mode is most frequently adopted. (C) 2004 Elsevier B.V. All rights reserved.