Nine polymeric and discrete complexes including a couple of genuine supramolecular isomers have been successfully prepared from divalent transition metal ions (Mn(II), Co(II), Ni(II), Cu(II), and Zn(II)) and unsymmetrical quasi semirigid pyridinecarboxylate isomers, InMe-n-py (n = 2, 3, 4). Structural analyses reveal that the unsymmetrical quasi semirigid ligands manage the metal(II) ions to form discrete (0D) armed metallocycle and dinuclear paddlewheel molecule, 1D ribbon, simple 2D rhombus (4,4) grid, 2D chiral wavy square (4,4) grid, and 2D double-edged layer with decorated (4,4) topology. Noncovalent hydrogen bonds and aromatic stacking interactions are found to be accessorial secondary interactions that are helpful for the extension and stabilization of the final inorganic−organic hybrid supramolecular networks of metal(II) complexes. Positional isomerism and conformational diversity of the unsymmetrical quasi semirigid ligands and the coordination preference of divalent metal ions play key roles in dominating structure variation and network complexity. Thermogravimetric analysis of mass loss showed that the frameworks of these complexes are thermally stable up to ca. 220–400 °C. Variable-temperature, solid-state magnetic susceptibility studies suggest that Mn(II) complexes 1 and 2 exhibit antiferromagnetic exchange coupling.