LiVO3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 17°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-18°. V(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2) and three equivalent V(1) atoms. In the third O site, O(3) is bonded to two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form a mixture of edge and corner-sharing OLi4V square pyramids.
LiVO3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 17°. Both Li(1)-O(1) bond lengths are 2.16 Å. All Li(1)-O(3) bond lengths are 2.12 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-18°. Both Li(2)-O(2) bond lengths are 2.21 Å. All Li(2)-O(3) bond lengths are 2.12 Å. V(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 18°. The V(1)-O(3) bond length is 1.73 Å. Both V(1)-O(1) bond lengths are 1.85 Å. There are two shorter (2.01 Å) and one longer (2.04 Å) V(1)-O(2) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2) and three equivalent V(1) atoms. In the third O site, O(3) is bonded to two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form a mixture of edge and corner-sharing OLi4V square pyramids.