Abstract

The preparation and characterization of [CrnFe4-nO2(O2CMe)7(bipy)2]Cl (1, n=0; 2, n=2; 3, n=4, bipy=2,2'-bipyridine) are described. The three complexes (1, 2 and 3) are obtained by bipyridine-mediated conversion of trinuclear [CrnFe3-nO(O2CMe)6(H2O)3]+(1, n=0; 2, n=1; 3, n=3), and crystallized as three of approximate isomorphs. Crystal 2 is monoclinic with space group C2/c, a=27.454(5)A, b=11.789(1)A, c=16.570(3)A, β=118.78(1)°, V=4700.8A3, z=4, μ(MoK)=11.64cm−1, F(000)=2056, final R=0.058 and Rw=0.066 for 3479 reflections with I ⩽ 3σ(I). The Fe and Cr atoms in the cation are all +3 oxide state and disordered in the lattice, which is also supported by its Mossbauer studies. The [Cr2Fe2O2]8+ core can be thought of as being derived from two edge-sharing M3O units (M=Fe or Cr), and as a butterfly-like structure. The cations' structure of all three crystals are similar to each other and have C2 symmetry. The species are characterized by IR spectra and magnetic techniques, with particular emphasis on differentiation of coordination bond strengths and electronic environment of metal atoms in these complexes.

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