Synthesis and crystal structure of Mg-bearing Fe9O11: New insight in the complexity of Fe-Mg oxides at conditions of the deep upper mantle

Abstract

A novel Mg-bearing iron oxide Mg0.87(1)Fe4.13(1)2+Fe43+O11 was synthesized at 12 GPa and 1300 °C using a large volume press. Rietveld structural analysis was conducted with a laboratory X‑ray diffraction pattern obtained at ambient conditions. The crystal structure, which has one oxygen trigonal prism site and four octahedral sites for the cations, was found to be isostructural with Ca2Fe7O11. The unit-cell lattice parameters are a = 9.8441(5) Å, b = 2.8920(1) Å, c = 14.1760(6) Å, β = 99.956(4)°, V = 397.50(3) Å3, and Z = 2 (monoclinic, C2/m). Mg and Fe cations are disordered on the trigonal prism site and on two of the four octahedral sites, and the remaining Fe is accommodated at the other two octahedral sites. The present structure is closely related to the other recently discovered Fe oxide structures, e.g., Fe4O5 and Fe5O6, by distortion derived either from incorporation (Fe4O5) or removal (Fe5O6) of an edge-shared FeO6 single octahedral chain in their structures. The present synthesis at deep upper mantle conditions and the structural relationships observed between various novel Mg-Fe oxides indicate that a series of different phases become stable above 10 GPa and that their relative stabilities (Fe2+/Fe3+) must be controlled by oxygen fugacity.