Ti4VO8 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the second Ti site, Ti(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the third Ti site, Ti(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(3) and one V(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(3), and one V(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), and two equivalent Ti(3) atoms.
Ti4VO8 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles are 3°. Both Ti(1)-O(3) bond lengths are 2.08 Å. All Ti(1)-O(2) bond lengths are 2.08 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles are 3°. Both Ti(2)-O(3) bond lengths are 2.09 Å. All Ti(2)-O(2) bond lengths are 2.08 Å. In the third Ti site, Ti(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. Both Ti(3)-O(1) bond lengths are 1.95 Å. Both Ti(3)-O(2) bond lengths are 2.04 Å. Both Ti(3)-O(3) bond lengths are 2.04 Å. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. Both V(1)-O(1) bond lengths are 2.00 Å. All V(1)-O(2) bond lengths are 2.05 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(3) and one V(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(3), and one V(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), and two equivalent Ti(3) atoms.