The reaction of 2-hydroxy-5-chlorobenzenesulfonic acid (H(2)L1), 2-hydroxy-5-chloro-1,3-benzenedisulfonic acid (H(3)L2), N-heterocyclic auxiliaries and CdX2 (X = NO3- and Ac-) salts leads to the formation of five new Cd(II) complexes, namely [Cd-2(L1)(2)(phen)(2)] (1), [Cd-2(L1)(2)(2,2'-bipy)(2)] (2), [Cd(HL1)(2)(2,2'-bipy)(2)] (3), [Cd-1.5(L2)(2)(phen)(2)(H2O)(n)center dot 2nH(2)O (4) and [Cd(HL2)(2,2'-bipy)(2)](n)center dot 3nH(2)O (5), which have been characterized by elemental analysis, IR, TG, PL (photoluminescence), powder and single-crystal X-ray diffraction. Adjacent dinuclear units in complexes 1 and 2 are extended by extensive it pi center dot center dot center dot pi and anion center dot center dot center dot pi interactions to generate layer and chain motifs. Mononuclear units in complex 3 are interconnected by anion center dot center dot center dot pi and hydrogen bonding interactions to form a 3-D supramolecular network which contains 1-D guest-free hydrophobic channels. In contrast, the Cd(II) cations in complexes 4 and 5 are joined by tri- and dianions to form chain structures, which are further extended by pi center dot center dot center dot pi interactions to give rise to 3-D supramolecular frameworks and chain structures. The different mono-, di- and trianions in the five complexes present diverse monodentate, mu(2) (kappa O-1: kappa O-1': kappa O-2 ''), mu(3) (kappa(1)O1: kappa(2)O6: kappa(2)O7) and mu(2) (kappa(1)O2: kappa(1)O3) modes, respectively. Moreover, solid-state luminescent properties of the five complexes were also investigated at room temperature. (C) 2015 Elsevier Ltd. All rights reserved.