DOE OSTI2020
Zn2TiO4 is Spinel-like structured and crystallizes in the monoclinic C2 space group. The structure is three-dimensional. there are five inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two TiO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.91–2.10 Å. In the second Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two TiO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.97–2.04 Å. In the third Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two equivalent TiO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.92–2.08 Å. In the fourth Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two TiO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.92–2.07 Å. In the fifth Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two equivalent TiO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Ti–O bond distances ranging from 1.92–2.08 Å. There are nine inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four TiO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.08–2.22 Å. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four TiO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.20 Å. In the third Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four TiO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.23 Å. In the fourth Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with six TiO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–63°. There are a spread of Zn–O bond distances ranging from 1.98–2.02 Å. In the fifth Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with six TiO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 52–64°. There are three shorter (2.00 Å) and one longer (2.01 Å) Zn–O bond lengths. In the sixth Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with six TiO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 52–63°. There are two shorter (2.00 Å) and two longer (2.01 Å) Zn–O bond lengths. In the seventh Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with six TiO6 octahedra and corners with six ZnO6 octahedra. The corner-sharing octahedra tilt angles range from 52–63°. There are a spread of Zn–O bond distances ranging from 1.98–2.02 Å. In the eighth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four TiO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.07–2.19 Å. In the ninth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two equivalent ZnO6 octahedra, and edges with four TiO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.10–2.19 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ti4+ and three Zn2+ atoms. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ti4+ and three Zn2+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ti4+ and three Zn2+ atoms. In the fourth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Ti4+ and two Zn2+ atoms. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ti4+ and two Zn2+ atoms. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ti4+ and two Zn2+ atoms. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ti4+ and two Zn2+ atoms. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ti4+ and two Zn2+ atoms. In the ninth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ti4+ and three Zn2+ atoms. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ti4+ and three Zn2+ atoms. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ti4+ and three Zn2+ atoms. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Ti4+ and three Zn2+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ti4+ and two Zn2+ atoms. In the fourteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ti4+ and two Zn2+ atoms. In the fifteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Ti4+ and two Zn2+ atoms. In the sixteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Ti4+ and three Zn2+ atoms.