This paper reports the syntheses of two new complexes, [Co(L 1 )(H 2 O) 2 ] (1) and [{Zn(L 2 ) (µ-OAc)Zn(n-PrOH)} 2 ] (2), from asymmetric halogen-substituted Salamo-type ligands H 2 L 1 and H 3 L 2 , respectively. Investigation of the crystal structure of complex 1 reveals that the complex includes one Co(II) ion, one (L 1 ) 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 (L 2 ) 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.