Abstract

Abstract The introduction of hexafluorozirconium(IV), [ZrF6]2−, to a solution containing Fe(III) and citrate ions produced a rather unexpected condensation product, namely, [Fe6O2Zr2F6(cit)4(H2O)10] (1). X-ray crystal structure study has revealed that complex 1 is centrosymmetric, consisting of two FeZrO2 units interconnected to a central planar Fe4O2 core through fluoride and citrate bridges. The Fe⋯Fe separation within the Fe4O2 unit of 2.8952(6) A is similar to that found in other planar or bent Fe4O2 cores found in discrete complexes. Magnetic susceptibility as a function of temperature has revealed that the compound is paramagnetic with a Curie-Weiss behavior over the temperature range 5–150 K. The derived values are C = 24.7 emu K/mol Oe and a θ value of −6.6(1) K, consistent with six independent HS d5 centers. Mossbauer spectra of compound 1·24H2O at 92 and 295 K exhibits one apparent symmetric broad doublet suggesting that there are at least two very similar sites, which cannot otherwise be resolved.

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