One-dimensional oxalato-bridged copper(II) complexes with 3-hydroxypyridine and 2-amino-4-methylpyridine

Abstract

Two new one-dimensional oxalato-bridged copper(II) compounds of formula [Cu(ox)L 2] n ( 1) and {[Cu 2(ox) 2L′ 3]·L′} n ( 2) [ox=oxalate dianion, L=3-hydroxypyridine (pyOH) and L′=2-amino-4-methylpyridine (ampy)] have been synthesized and characterized by FT-IR spectroscopy, variable-temperature magnetic measurements and single-crystal X-ray diffraction. The crystal structure of 1 comprises chains of copper atoms in which cis-[Cu(pyOH) 2] 2+ units are sequentially bridged by asymmetric bis-bidentate oxalato ligands with an intrachain copper–copper separation of 5.548(1) Å. Each copper atom is six-coordinated: four oxygen atoms belonging to two bridging oxalato ligands and two nitrogen atoms from two 3-hydroxypyridine ligands build a distorted octahedral environment around the metal atom. As in 1, the structure of compound 2 is made up of chains of copper atoms bridged sequentially by bis-bidentate oxalato ligands. Two types of copper(II) ion, one being six-coordinated (Cu(1)) and the other five-coordinated (Cu(2)), alternate regularly within the chain. The environment around Cu(1) is elongated octahedral with two cis-coordinated pyridine–nitrogen and two oxygen atoms from two oxalate ligands building the equatorial plane, the apical positions being filled by two oxalate-oxygen atoms. The environment around Cu(2) is distorted square pyramidal with four oxalato-oxygen atoms in the basal plane, and the pyridine nitrogen atom from one aromatic base in the apical position. Magnetic susceptibility data in the temperature range 2.0–300 K reveal regular ferromagnetic ( J=+1.3 cm −1) and alternating antiferromagnetic ( J=−66.6 cm −1, αJ=−58.6 cm −1) chain behaviours for 1 and 2. The nature and magnitude of the magnetic coupling through the oxalato bridge in 1 and 2 are analysed and discussed in the light of the available structural data.