The First Ate Complex of Copper(II) 5-Chlorosalicylhydroximate Metallacrown with Outer-Sphere Nickel(II) Cation

Recently, there has been a significant interest towards heterometallic 3d-3d metallacrowns (MC) based on salicylhydroxamic acid. In this work, with use of the 5-clorosalicylhydroxamic acid in reaction with the copper(II) and nickel(II) salts the first 12-MC-4 ate complexes bearing the copper(II) ions in the MC ring and an outer-sphere nickel(II) cation were synthesized and characterized. The molecular and crystal structures of complexes were determined from single-crystal X-ray diffraction studies. Detailed DFT studies were carried out for the [Cu(II)[12-MCCu(II)N(Cl-shi)-4]](2)-metallamacrocyclic fragment. The nickel(II) cations appear to promote the formation of a fused metallacrown structure with practically flat copper(II) metallamacrocycles.