Structures and spectral properties of some bis(.BETA.-diketonato)copper(II)-diazole complexes. II. The 1:1, 1:2, and 1:3 adducts of bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)copper(II) and 4-methyl-1H-pyrazole.

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The preparation of Cu(hfac)2(4-Hmpz) (1), Cu(hfac)2(4-Hmpz)2 (2), and Cu(hfac)2(4-Hmpz)3 (3) by stoichiometric reactions of Cu(hfac)2 (Hhfac=1,1,1,5,5,5-hexafluoro-2,4-pentanedione) with 4-methyl-1H-pyrazole (4-Hmpz) in petroleum ether is reported. The structure of 2 has been determined by X-ray analysis. Crystal data for 2: triclinic, P\bar1, a=9.301(3), b=10.815(2), c=6.457(1) Å, α=104.71(2), β=101.38(2), γ=75.41(2)°, V=601.8(3) Å3, Z=1, and R=0.057. The geometry about each copper atom is approximately a tetragonal bipyramid. The axial positions are occupied by two oxygen atoms one from each of the bidentate hfac ligands, the other oxygen atoms of which are in the basal plane with two nitrogen atoms from 4-Hmpz molecules. The two nitrogen atoms are situated trans to each other. The axial oxygen atoms have a considerably long Cu–O(2) distance (2.346(3) Å). In the IR spectrum of 2, unsplit ν C–O and ν N–H bands were observed at 1678 and 3441 cm−1, respectively. The structures of 1 and 3 are estimated on the basis of their IR spectra.
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