DOE OSTI2020
TiOSO4 crystallizes in the orthorhombic Pmc2_1 space group. The structure is three-dimensional. there are eight inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with two equivalent TiO6 octahedra and corners with four SO4 tetrahedra. The corner-sharing octahedral tilt angles are 3°. There are a spread of Ti–O bond distances ranging from 1.81–2.15 Å. In the second Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with two equivalent TiO6 octahedra and corners with four SO4 tetrahedra. The corner-sharing octahedral tilt angles are 6°. There are a spread of Ti–O bond distances ranging from 1.80–2.14 Å. In the third Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with two equivalent TiO6 octahedra and corners with four SO4 tetrahedra. The corner-sharing octahedral tilt angles are 6°. There are a spread of Ti–O bond distances ranging from 1.80–2.13 Å. In the fourth Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with two equivalent TiO6 octahedra and corners with four SO4 tetrahedra. The corner-sharing octahedral tilt angles are 1°. There are a spread of Ti–O bond distances ranging from 1.81–2.13 Å. In the fifth Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with two equivalent TiO6 octahedra and corners with four SO4 tetrahedra. The corner-sharing octahedral tilt angles are 3°. There are a spread of Ti–O bond distances ranging from 1.81–2.16 Å. In the sixth Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with two equivalent TiO6 octahedra and corners with four SO4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. There are a spread of Ti–O bond distances ranging from 1.81–2.15 Å. In the seventh Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with two equivalent TiO6 octahedra and corners with four SO4 tetrahedra. The corner-sharing octahedral tilt angles are 1°. There are a spread of Ti–O bond distances ranging from 1.81–2.12 Å. In the eighth Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with two equivalent TiO6 octahedra and corners with four SO4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. There are a spread of Ti–O bond distances ranging from 1.80–2.15 Å. There are eight inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 2–19°. There are a spread of S–O bond distances ranging from 1.46–1.49 Å. In the second S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 8–29°. There is two shorter (1.47 Å) and two longer (1.49 Å) S–O bond length. In the third S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 14–33°. There are a spread of S–O bond distances ranging from 1.47–1.50 Å. In the fourth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 15–40°. There is two shorter (1.46 Å) and two longer (1.49 Å) S–O bond length. In the fifth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 10–19°. There is two shorter (1.47 Å) and two longer (1.49 Å) S–O bond length. In the sixth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 5–28°. There is two shorter (1.47 Å) and two longer (1.49 Å) S–O bond length. In the seventh S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 15–36°. There is two shorter (1.46 Å) and two longer (1.49 Å) S–O bond length. In the eighth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 15–39°. There are a spread of S–O bond distances ranging from 1.47–1.50 Å. There are twenty-eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a linear geometry to one Ti4+ and one S6+ atom. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the third O2- site, O2- is bonded in a linear geometry to two Ti4+ atoms. In the fourth O2- site, O2- is bonded in a distorted linear geometry to one Ti4+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a distorted linear geometry to one Ti4+ and one S6+ atom. In the sixth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the seventh O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the eighth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the ninth O2- site, O2- is bonded in a distorted linear geometry to one Ti4+ and one S6+ atom. In the tenth O2- site, O2- is bonded in a linear geometry to two Ti4+ atoms. In the eleventh O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the twelfth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the thirteenth O2- site, O2- is bonded in a linear geometry to one Ti4+ and one S6+ atom. In the fourteenth O2- site, O2- is bonded in a linear geometry to one Ti4+ and one S6+ atom. In the fifteenth O2- site, O2- is bonded in a linear geometry to one Ti4+ and one S6+ atom. In the sixteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the seventeenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the eighteenth O2- site, O2- is bonded in a distorted linear geometry to one Ti4+ and one S6+ atom. In the nineteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the twentieth O2- site, O2- is bonded in a linear geometry to one Ti4+ and one S6+ atom. In the twenty-first O2- site, O2- is bonded in a distorted linear geometry to one Ti4+ and one S6+ atom. In the twenty-second O2- site, O2- is bonded in a linear geometry to one Ti4+ and one S6+ atom. In the twenty-third O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the twenty-fourth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the twenty-fifth O2- site, O2- is bonded in a linear geometry to two Ti4+ atoms. In the twenty-sixth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one S6+ atom. In the twenty-seventh O2- site, O2- is bonded in a linear geometry to one Ti4+ and one S6+ atom. In the twenty-eighth O2- site, O2- is bonded in a linear geometry to two Ti4+ atoms.