To examine the influence of the metal ions and their counter ions on crystalline networks, we have designed and synthesized six MX2/8-aminoquinoline (8-aq) (M = MnII, CuII, CdII and X = Cl-, Br-, I-, NO3-, SCN-) complexes, having the formula [Mn(8-aq)2 I2]•(1), [Mn(8-aq)2 (H2O)2](8-aq)3•Br2 (2), [Mn(8-aq)2(SCN)2] (3), [Cu(8-aq)2Cl(H2O)]•Cl•H2O (4), [Cu(8-aq)2(NO3)(H2O)].NO3 (5), and Cd(8-aq)2I2 (6). Single crystal X-ray diffraction analyses showed that all of complexes have a distorted octahedral geometry, in which each 8-aq molecule acts as a bidentate ligand and coordinates to the central metal ion with its common coordination mode, to form a N,N' chelating motive. Remarkably, the influence of the counter ion on the geometry of the complex is very significant since both I(-) and SCN(-) anions are coordinated to the metal ion in compounds1, 3 and 6 adopting a cis-configuration, whilst a single anion occupies an axial position in compounds 4 and 5 (Cl- and NO3-, respectively) and the other counterion is not coordinated. Finally, both Br‾ anions are not coordinated in the cationic complex 2 (Mn metal centre). In all cases, there are extended supramolecular networks due to cooperativity hydrogen-bonding and pi-pi stacking interactions that play an essential role in the formation and stability of the crystalline materials. The binding energies attributed to the different interactions have been evaluated using DFT calculations.