Ti3VO8 is Rutile-derived structured and crystallizes in the hexagonal P6_3mc space group. Ti(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. V(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra and edges with three equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Ti(1) and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ti(1) atoms.
Ti3VO8 is Rutile-derived structured and crystallizes in the hexagonal P6_3mc space group. Ti(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Ti(1)-O(3) bond length is 1.99 Å. The Ti(1)-O(4) bond length is 1.95 Å. Both Ti(1)-O(1) bond lengths are 1.97 Å. Both Ti(1)-O(2) bond lengths are 1.99 Å. V(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra and edges with three equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. All V(1)-O(1) bond lengths are 2.00 Å. All V(1)-O(2) bond lengths are 1.97 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Ti(1) and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ti(1) atoms.