Self-assemblies of N2O4 donor Schiff base ligands, that is, N,N′-Bis(3-ethoxysalicylidenimino) 1, 3-diaminopropane (H2LOEt) with cadmium acetate salts in presence of auxiliary co-ligands thiocyanato/azido/chloride allow the formation of three anion control complexes, specifically, [Cd2LOEt(μ1,3-SCN)(η1-SCN)]n (1), {Cd4(LOEt)2(μ1,1-N3)3(η1-N3)]2 (2) and [Cd2(LOEt)(Cl)2.CH3OH].CH3OH] (3). Crystal structures of complexes 1–3 were determined by single-crystal X-ray diffraction studies. The single-crystal X-ray diffraction analysis confirmed that complex 1 is an one-dimensional polymeric chain in which Cd(II) ions are bridged by one thiocyanate group bonding in an end-to-end fashion. Complex 2 is a centrosymmetric octanuclear complex with double end-on azide (μ1,1-N3 −) as linker. On the other hand, 3 is a dinuclear complex with terminally bound Cl− ions. Analysis of the structure revealed that all the complexes possess a 4-membered Cd2 (μ2-O)2 core fastened by the combined coordination action of a doubly deprotonated ligand. Complexes 1–3 have been successfully characterized by elemental analyses, IR and UV-Vis spectroscopy. The luminescent properties of complexes 1–3 have been studied in DMSO solution. The antibacterial and antibiofilm potential for complexes 1–3 were investigated against Gram-positive and Gram-negative bacterial strains. Intermolecular interactions with respect to percentages of hydrogen bonding of cadmium complexes were quantified by Hirshfeld surface. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim}, author_keywords={Antimicrobial; Cd(II) coordination compounds; Hirshfeld surface; Photoluminescence; Pseudohalides}, references={Jiang, P., Guo, Z., (2004) Coord. Chem. Rev., 248, pp. 205-229; Huang, W., Zhu, H.-B., Gou, S.-H., (2006) Coord. Chem. 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