Synthesis, crystal structure and magnetic properties of a polymeric copper(II) Schiff-base complex having binuclear units covalently linked by isonicotinate ligands †

Abstract

The polynuclear copper(II) complex [{Cu₂L(O₂CC₅H₄N)}·C₂H₅OH]_x (1), where H₃L is a 1∶2 Schiff base derived from 1,3-diaminopropan-2-ol and salicylaldehyde, has been prepared and structurally characterized. The structure consists of a one-dimensional zigzag chain in which the binuclear [Cu₂L]⁺ units are covalently linked by isonicotinate ligands to give a syndiotactic arrangement of the copper ions protruding outside the chain. In the basic unit, the copper(II) centres are bridged by an alkoxo and a carboxylato ligand, giving a Cu  · · ·  Cu distance of 3.492(3) Å and a Cu–O–Cu angle of 130.9(2)°. While one copper centre has a square-planar geometry, the other copper is square-pyramidal with the pyridine nitrogen being the axial ligand. The visible electronic spectrum of 1 shows a broad d–d band at 615 nm. The complex shows a rhombic X-band EPR spectral pattern in the polycrystalline phase at 77 K. Magnetic susceptibility measurements in the temperature range 22 to 295 K demonstrate the antiferromagnetic behaviour of 1. A theoretical fit to the magnetic data is based on a model assuming 1 as an equimolar mixture of copper atoms belonging to an antiferromagnetically coupled one-dimensional Heisenberg chain with the other copper atoms outside the chain behaving like paramagnetic centres.

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