The enamine (HEAID) obtained from aniline and 2-acetyl-1,3-indandione (2AID) behaves as a bidentate ligand in coordination with copper (II) ion. Two types of crystals, apparently different in shape, were isolated and studied by single-crystal X-ray diffraction. The X-ray data for the brown rhombic crystals of compound 1 shows a mononuclear complex of Cu(II) coordinated with two EAID-anions, Cu(EAID)2. The X-ray data for the green crystals of compound 2 shows a dinuclear Cu(II) complex with two OH− groups acting as bridging ligands, [Cu2(μ-OH)2(EAID)2]. In both cases the ligand coordinates after deprotonation of the amine group.