DOE OSTI2020
Ti(FeO2)3 is beta indium sulfide-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are four inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form distorted TiO6 octahedra that share corners with six FeO4 tetrahedra, an edgeedge with one TiO6 octahedra, and edges with four FeO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.80–2.29 Å. In the second Ti4+ site, Ti4+ is bonded to six O2- atoms to form distorted TiO6 octahedra that share corners with six FeO4 tetrahedra, an edgeedge with one TiO6 octahedra, and edges with three FeO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.79–2.21 Å. In the third Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six FeO4 tetrahedra, edges with two equivalent TiO6 octahedra, and edges with two FeO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.86–2.10 Å. In the fourth Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six FeO4 tetrahedra, edges with two equivalent TiO6 octahedra, and edges with two FeO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.88–2.08 Å. There are twelve inequivalent Fe+2.67+ sites. In the first Fe+2.67+ site, Fe+2.67+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with two TiO6 octahedra and corners with nine FeO6 octahedra. The corner-sharing octahedra tilt angles range from 53–60°. There are a spread of Fe–O bond distances ranging from 1.89–1.99 Å. In the second Fe+2.67+ site, Fe+2.67+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with five TiO6 octahedra and corners with five FeO6 octahedra. The corner-sharing octahedra tilt angles range from 48–66°. There are a spread of Fe–O bond distances ranging from 1.96–2.10 Å. In the third Fe+2.67+ site, Fe+2.67+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with four FeO6 octahedra and corners with five TiO6 octahedra. The corner-sharing octahedra tilt angles range from 48–63°. There are a spread of Fe–O bond distances ranging from 1.86–2.01 Å. In the fourth Fe+2.67+ site, Fe+2.67+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with four TiO6 octahedra and corners with seven FeO6 octahedra. The corner-sharing octahedra tilt angles range from 47–63°. There are a spread of Fe–O bond distances ranging from 1.86–1.99 Å. In the fifth Fe+2.67+ site, Fe+2.67+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with four TiO6 octahedra and corners with five FeO6 octahedra. The corner-sharing octahedra tilt angles range from 50–62°. There are a spread of Fe–O bond distances ranging from 1.93–2.13 Å. In the sixth Fe+2.67+ site, Fe+2.67+ is bonded to four O2- atoms to form FeO4 tetrahedra that share corners with four TiO6 octahedra and corners with six FeO6 octahedra. The corner-sharing octahedra tilt angles range from 53–60°. There are a spread of Fe–O bond distances ranging from 1.89–2.01 Å. In the seventh Fe+2.67+ site, Fe+2.67+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, an edgeedge with one FeO6 octahedra, and edges with three TiO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.99–2.24 Å. In the eighth Fe+2.67+ site, Fe+2.67+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, edges with two TiO6 octahedra, and edges with three FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.96–2.16 Å. In the ninth Fe+2.67+ site, Fe+2.67+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, an edgeedge with one TiO6 octahedra, and edges with five FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.01–2.12 Å. In the tenth Fe+2.67+ site, Fe+2.67+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, an edgeedge with one TiO6 octahedra, and edges with five FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 2.11–2.18 Å. In the eleventh Fe+2.67+ site, Fe+2.67+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, an edgeedge with one FeO6 octahedra, and edges with three TiO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.91–2.10 Å. In the twelfth Fe+2.67+ site, Fe+2.67+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six FeO4 tetrahedra, an edgeedge with one TiO6 octahedra, and edges with five FeO6 octahedra. There are a spread of Fe–O bond distances ranging from 1.99–2.11 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Fe+2.67+ atoms. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ti4+ and two Fe+2.67+ atoms. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to two Ti4+ and one Fe+2.67+ atom. In the fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Fe+2.67+ atoms. In the fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ti4+ and two Fe+2.67+ atoms. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ti4+ and two Fe+2.67+ atoms. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Fe+2.67+ atoms. In the eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ti4+ and two Fe+2.67+ atoms. In the ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ti4+ and two Fe+2.67+ atoms. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Fe+2.67+ atoms. In the eleventh O2- site, O2- is bonded in a distorted trigonal planar geometry to two Ti4+ and one Fe+2.67+ atom. In the twelfth O2- site, O2- is bonded in a 3-coordinate geometry to one Ti4+ and two Fe+2.67+ atoms. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to four Fe+2.67+ atoms. In the fourteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ti4+ and two Fe+2.67+ atoms. In the fifteenth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two Ti4+ and one Fe+2.67+ atom. In the sixteenth O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to one Ti4+ and three Fe+2.67+ atoms. In the seventeenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ti4+ and three Fe+2.67+ atoms. In the eighteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ti4+ and two Fe+2.67+ atoms. In the nineteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ti4+ and three Fe+2.67+ atoms. In the twentieth O2- site, O2- is bonded in a trigonal planar geometry to three Fe+2.67+ atoms. In the twenty-first O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ti4+ and two Fe+2.67+ atoms. In the twenty-second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ti4+ and three Fe+2.67+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ti4+ and two Fe+2.67+ atoms. In the twenty-fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ti4+ and two Fe+2.67+ atoms.