Hydrogen bonded supramolecular structures of cationic and anionic module assemblies containing square-planar oximate complex anions

The formation of the molecular assemblies consisting of anionic and cationic molecules may lead to their interesting structural properties. In this work, we present three new structures based on the tetradentate oxime and amide open-chain ligand CH3–C(NOH)–C(O)–NH–(CH2)3–NH–C(O)–C(NOH)–CH3 (PAP). All the structures contain the complex cations, complex anions [M(PAP-3H)]− and solvating water molecules. These are H-bonded complex anions: [Ni(1,3-pn)2(H2O)2][Ni(PAP-3H)]2 · 4 H2O (1), [Ni(Im)4(H2O)2][Ni(PAP-3H)]2 (2) and [Cu(Im)4(H2O)2][Cu(PAP-3H)]2 · 2H2O (3) (Im=imidazole; 1-3-pn=1,3-diaminopropane). All compounds were synthesised by co-crystallisation of octahedral amine-containing cationic complex with oxime-containing anionic complexes in methanol solution. They were compared with some earlier reported assemblies based on the same ligand (PAP). The comparison of the structures reveals one distinct difference in the separation between the cis-situated oximate oxygen atoms O(1)⋯O(4) in the copper complexes. The consequence of this effect is the lengthening of the Cu–N distances. In the nickel complexes containing [Ni(PAP-3H)]− anion this effect is much less pronounced.