Issue 22, 1996

Crystal structure, magnetic properties and spectroscopic studies of bis[1,3-bis(pyrazol-3-yl)triazenido]dicopper(II) trihydrate: a dinuclear complex with an asymmetric double pyrazolate bridge

Abstract

The crystal and molecular structure of [{Cu(bpzt)}2]·3H2O [H2bpzt = 1,3-bis(pyrazol-3-yl)triazene] was determined by X-ray diffraction methods. The complex has a quasi-planar dinuclear structure with an asymmetric double pyrazolate bridge. The asymmetry results from the presence, on the C3 of each bridging pyrazolate, of a pyrazolyltriazenide chelating arm which completes the equatorial CuN4 co-ordination. The centrosymmetric dinuclear units have intramolecular Cu ⋯ Cu distances of 3.852(5) and 3.839(4)Å respectively. The units are stacked in columns along the b axis. The cell also contains crossing channels filled with water molecules. The complex was characterized by spectroscopic and magnetic measurements. Magnetic susceptibility data show antiferromagnetic behaviour with an exchange parameter |J|= 151 cm–1 significantly decreased with respect to symmetric doubly bridged complexes (|J|=≈200 cm–1). The X-band powder EPR spectrum recorded at 77 K is typical of a triplet spin state lying above the singlet ground state. The results obtained for this complex are compared to recent literature data on other planar doubly bridged pyrazolate dicopper(II) complexes. A correlation, valid for symmetric as well as asymmetric systems, is described between the exchange parameter J and the deviation of the Cu–N–N bridge angle from the optimum value corresponding to the highest |J|.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1996, 4275-4281

Crystal structure, magnetic properties and spectroscopic studies of bis[1,3-bis(pyrazol-3-yl)triazenido]dicopper(II) trihydrate: a dinuclear complex with an asymmetric double pyrazolate bridge

V. P. Hanot, T. D. Robert, J. Kolnaar, J. G. Haasnoot, J. Reedijk, H. Kooijman and A. L. Spek, J. Chem. Soc., Dalton Trans., 1996, 4275 DOI: 10.1039/DT9960004275

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