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A new phase of Cd(py)4NbOF5 (py = pyridine) (A) is a rare example of a mixed metal oxide fluoride in an ordered linear chain structure. This phase is of particular interest because it is a polymorph of a previously reported Cd(py)4NbOF5 phase (B) that crystallizes in disordered linear chains. The ordered polymorph A contains two distinct Cd2+ sites:  one which is coordinated to the oxide ligands from two [NbOF5]2- units, and another that is coordinated to two trans fluoride ligands. As a result, the structure of polymorph A features nonpolar linear chains with locally ordered [NbOF5]2- anions. This ordering is explained in terms of the inherent electronic differences between oxide and fluoride ligands. The stabilization provided by π-stacking interactions between pyridine ligands on neighboring chains, as well as the effects of reactant stoichiometry on the general structure of the products in the CdO·1/2Nb2O5/(HF)x·py/H2O system, is also discussed. Crystal data for the ordered Cd(py)4NbOF5 polymorph:  mo...

Evidence for Nonpolar Alignment of [NbOF5]2- Anions in Cd(pyridine)4NbOF5 Chains

Evidence for Nonpolar Alignment of [NbOF₅]^2- Anions in Cd(pyridine)₄NbOF₅ Chains