Synthesis, characterization and bioactivity of four novel trinuclear copper(II) and nickel(II) complexes with pentadentate ligands derived from N-acylsalicylhydrazide

Four novel trinuclear copper(II)/nickel(II) complexes with four trianionic pentadentate ligands, N-(3-t-butylbenzoyl)-5-nitrosalicylhydrazide (H33-t-bbznshz), N-(3,5-dimethylbenzoyl)salicylhydrazide (H33,5-dmbzshz), N-(phenylacetyl)-5-bromosalicylhydrazide (H3pabshz) and N-(3-t-butylbenzoyl)salicylhydrazide (H33-t-bbzshz) have been synthesized and characterized by X-ray crystallography. These trinuclear compounds all have an M–N–N–M–N–N–M core formed by three metal ions and two ligands. The geometries of three Cu(II) ions in compound Cu3(3-t-bbznshz)2(H2O)(DMF)(py)2 · DMF (1) alternate between distorted square pyramidal and square planar, while in compound Cu3(3,5-dmbzshz)2(py)2 (2), they are all square planar. Three Ni(II) ions in compound Ni3(pabshz)2(DMF)2(py)2 (3) and Ni3(3-t-bbzshz)2(py)4 · 2H2O (4) follow square-planar/octahedral/square-planar coordination geometry. Compounds 1, 2 and 4 are bent trinuclear, with the bend angles of 156.4°, 141.49° and 127.1°, respectively, while the three nickel ions in compound 3 are strictly linear, with an angle of 180°. Studies on the trinuclear Ni(II) complexes show that the β-branched N-acylsalicylhydrazide ligands with sterically flexible Cα methylene groups are easier to yield linear trinuclear Ni(II) complexes, while α-branched N-acylsalicylhydrazides ligands tend to form bent trinuclear Ni(II) complexes. Antibacterial screening data indicate that the trinuclear Cu(II) compound 2 is more active than 1 and mononuclear Cu(II) compound, bent trinuclear Ni(II) compound 4 is more active than linear compound 3 and less active than tetranuclear nickel compound in the previous study.

Four novel trinuclear compounds Cu3(3-t-bbznshz)2(H2O)(DMF)(py)2 · DMF (1), Cu3(3,5-dmbzshz)2(py)2 (2), Ni3(pabshz)2(DMF)2(py)2 (3) and Ni3(3-t-bbzshz)2(py)4 · 2H2O (4) have been obtained by the reaction of metal salts with four novel trianionic pentadentate ligands, N-(3-t-butylbenzoyl)-5-nitrosalicylhydrazide, N-(3,5-dimethylbenzoyl)salicylhydrazide, N-(phenylacetyl)-5-bromosalicylhydrazide and N-(3-t-butylbenzoyl)salicylhydrazide. The coordination modes of the ligands are the same, but the metal ions show different coordination environments. Compounds 1, 2 and 4 are bent trinuclear, with the bent angles larger than 120°, while the three nickel ions in compound 3 are strictly linear, with an angle of 180°. They all get a M–N–N–M–N–N–M core formed by three metal ions and two ligands.Figure optionsDownload as PowerPoint slide