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Crystal and Molecular Structure and Magnetic Properties of a Tetrameric Copper(II) Complex with 3-Hydroxy-4--5-hydroxymethyl-2-methylpyridine (H2L2), 2)4>.9CH3OH

DOI: 10.1039/DT9830000657

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 657 - 664 (1983)

Update date:2022-07-30

Topics:

Authors:

Walz, LeonhardWalz, Leonhard

Paulus, HelmutPaulus, Helmut

Haase, WolfgangHaase, Wolfgang

Langhof, HaraldLanghof, Harald

Nepveu, FrancoiseNepveu, Francoise

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Article abstract of DOI:10.1039/DT9830000657

The crystal and molecular structure of the title compound has been determined using three-dimensional X-ray diffractometer data involving 7045 independent reflections.The compound crystallizes in the monoclinic space group /2/c with eight formula units <(CuL2)4>.9CH3OH in a unit cell with dimensions a=27.062(5), b=25.062(5), c=26.390(5) Angstroem, and β=92.39(1) deg.The structure has been calculated by direct methods and refined by least-squares methods to a final R value of 0.054.In the cubane structure (C1 symmetry) each copper atom is bonded to one deprotonated phenolic oxygen, one imine nitrogen, and three deprotonated alkoxo-oxygen atoms giving a distorted square-pyramidal co-ordination.The six copper-copper distances are in the range 3.021(1)-3.492(2) Angstroem (mean 3.254 +/- 0.184 Angstroem).Within the Cu4O4 core there are eight shorter copper-oxygen distances <1.917(5)-2.057(5) Angstroem, mean 1.983 Angstroem> and four longer ones <2.327(5)-2.690(6) Angstroem, mean 2.496 +/- 0.166 Angstroem>.There are 72 methanol molecules per unit cell which are easily lost in air, giving an amorphous powder.The magnetic properties of the complex can be explained using the isotropic Heisenberg-Dirac-van Vleck model.The exchange parameters for the complex with approximate S4 symmetry obtained (J12=-9.9 +/- 3.0 cm-1, J13=20.5 +/- 3.0 cm-1, and g=2.08 +/- 0.02) are in good agreement with those of similar substances and show the presence of both ferromagnetic and antiferromagnetic interactions.The amorphous modification shows a predominant ferromagnetic interaction.

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