Ti3O4 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form edge-sharing TiO6 octahedra. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Ti(1) and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded to one Ti(1) and four equivalent Ti(2) atoms to form a mixture of corner and edge-sharing OTi5 square pyramids.
Ti3O4 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form edge-sharing TiO6 octahedra. Both Ti(1)-O(2) bond lengths are 2.09 Å. All Ti(1)-O(1) bond lengths are 2.04 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. Both Ti(2)-O(1) bond lengths are 2.04 Å. All Ti(2)-O(2) bond lengths are 2.10 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Ti(1) and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded to one Ti(1) and four equivalent Ti(2) atoms to form a mixture of corner and edge-sharing OTi5 square pyramids.