Reaction of copper(II) chloride with an unsymmetrical tetradentate (NNNO) Schiff base ligand, N-(2-pyridyl-methyl)-N'-(salicyaldimino)-1,3-propanediamine (Hpaip), was investigated as a possible route to a square-planar monocationic copper radiopharmaceutical. In the solid state the [Cu(paip)Cl] complex was found to instead adopt a square-pyramidal geometry with the deprotonated tetradentate ligand in the basal plane and a weakly bound chloride ligand in the apical position.