The new ligand dapmp (1) has been synthesized and the reactions of CuCl 2 ·2H 2 O and Cu(CH 3 COO) 2 ·H 2 O with the new ligand in methanol afforded two crystalline polymorphic forms: [Cu(dapmp)Cl 2 ] (2) and [Cu(dapmp)(CH 3 COO) 2 ]·H 2 O (3), where dapmp=2,4-di(2-aminopyridine)-6-methylpyrimidine. Single crystal X-ray diffraction showed that (1) and (2) are each connected by hydrogen bonding to form a one-dimensional supermolecular compound and (3) is connected by hydrogen bonding to form a three-dimensional supermolecular compound.