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This paper reports the syntheses of two new complexes, [Co(L1)(H2O)2] (1) and [{Zn(L2)(μ-OAc)Zn(n-PrOH)}2] (2), from asymmetric halogen-substituted Salamo-type ligands H2L1 and H3L2, respectively. Investigation of the crystal structure of complex 1 reveals that the complex includes one Co(II) ion, one (L1)2− unit and two coordinated water molecules. Complex 1 shows slightly distorted octahedral coordination geometry, forming an infinite 2D supramolecular structure by intermolecular hydrogen bond and π–π stacking interactions. Complex 2 contains four Zn(II)ions, two completely deprotonated (L2)3− moieties, two coordinated μ-OAc− ions and n-propanol molecules. The Zn(II) ions in complex 2 display slightly distorted trigonal bipyramidal or square pyramidal geometries.