LiTi3VO8 is beta indium sulfide-derived structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to six equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. Ti(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. V(1) is bonded to six equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one V(1) atom.
LiTi3VO8 is beta indium sulfide-derived structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to six equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. All Li(1)-O(2) bond lengths are 2.24 Å. Ti(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Both Ti(1)-O(1) bond lengths are 1.99 Å. All Ti(1)-O(2) bond lengths are 1.98 Å. V(1) is bonded to six equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. All V(1)-O(2) bond lengths are 2.07 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one V(1) atom.