LiV3O6 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-13°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. In the second V site, V(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), 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(1), one V(2), and two equivalent V(1) atoms.
LiV3O6 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-13°. Both Li(1)-O(1) bond lengths are 2.24 Å. All Li(1)-O(2) bond lengths are 2.20 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. Both V(1)-O(1) bond lengths are 1.97 Å. There are two shorter (2.00 Å) and two longer (2.06 Å) V(1)-O(2) bond lengths. In the second V site, V(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. Both V(2)-O(1) bond lengths are 2.06 Å. All V(2)-O(2) bond lengths are 1.93 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), 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(1), one V(2), and two equivalent V(1) atoms.