Composition Space Diagrams for Mixed Transition Metal Oxide Fluorides

Composition space diagrams have been used to study phase stability of mixed transition metal oxide fluorides
synthesized by hydrothermal reaction of the metal oxides in (HF)x·pyridine/H2O/pyridine solution (150 °C,
autogenous pressure). The combination of early (Ti, Zr, Hf, Nb, Ta, Mo, W) and late (Cu, Cd, Zn) transition
metals and the effects of varying the mole ratios of the metals, (HF)x·pyridine, and water are examined in this
study. Single-crystal products containing [Cu(py)4]2+, [Cd(py)4]2+, or [Zn(py)4]2+ cations and [TiF6]2-, [ZrF6]2-,
[HfF6]2-, [NbOF5]2-, [TaOF5]2-, [MoO2F4]2-, or [WO2F4]2- anions are recovered. Relative stability of the
crystalline products is governed by the negative charge distribution on the anions, as well as the concentrations
of each reactant in solution. Two new structures are reported:  Cu(NC5H5)4TaOF5 and Cu(NC5H5)4TiF6·3H2O.
Crystal data:  for Cu(NC5H5)4TaOF5, monoclinic, space group C2/c (No. 15), with a = 10.541(3) Å, b = 13.547(6)
Å, c = 16.04(1) Å, β = 97.73(5)°, and Z = 4; for Cu(NC5H5)4TiF6·3H2O, monoclinic, space group C2/c (No.
15), with a = 12.767(4) Å, b = 12.048(2) Å, c = 17.787(6) Å, β = 109.9(1)°, and Z = 4.