Graphycal Abstract: Copper(II), syn-2-pyridinealdoxime (PaoH), and 4,4′-bipyridine (bpy) react to form a one-dimensional (1D) cationic coordination polymer. The structure consists of tetranuclear units interconnected by in situ generated PaoH ligands and further extended by bpy linkers. Nitrate anions, DMF, and water molecules are involved in hydrogen-bonding interactions with the metal complex. These intermolecular interactions were analyzed and quantified using Hirshfeld surface analysis.