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Synthesis and characterization of the face-sharing bioctahedral [Mo2O6F3]3- anion
Authors:Kirsch Janet E  Izumi Heather K  Stern Charlotte L  Poeppelmeier Kenneth R
Institution:Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, USA.
Abstract:The face-sharing bioctahedral molybdenum(VI) oxide fluoride anion Mo2O6F3]3- has been isolated in the new compound Cu(3-apy)4]3(Mo2O6F3)2 (3-apy = 3-aminopyridine) and has been characterized by experimental and computational techniques. Single-crystal X-ray diffraction studies show that the structure of the Mo2O6F3]3- anion resembles two distorted face-sharing octahedra, each with three short terminal metal-ligand bonds and three long metal-ligand-metal bridging interactions. Aspects of the electronic structure, as well as geometric comparisons of the bond lengths and angles in Mo2O6F3]3- with those in the similarly distorted MoO3F3]3- anion, suggest that the six terminal ligand positions of the confacial bioctahedra are occupied exclusively by oxide ligands and that the three bridging sites are occupied by fluorides. Crystal data for Cu(3-apy)4]3(Mo2O6F3)2: trigonal space group R3 (No. 148) with hexagonal axes of a = 13.881(1) A and c = 31.783(3) A (Z = 3).
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