Li3V5O8 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m 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 six equivalent V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. There are three inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. 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 six equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the third V site, V(3) is bonded to six equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and three equivalent V(2) atoms to form OLi3V3 octahedra that share corners with six equivalent O(1)Li3V3 octahedra and edges with twelve equivalent O(2)Li2V4 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent Li(1), one V(1), one V(3), and two equivalent V(2) atoms to form OLi2V4 octahedra that share corners with six equivalent O(2)Li2V4 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with eight equivalent O(2)Li2V4 octahedra. The corner-sharing octahedra are not tilted.
Li3V5O8 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m 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 six equivalent V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Li(1)-O(1) bond lengths are 2.21 Å. All Li(1)-O(2) bond lengths are 2.23 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. All V(1)-O(2) bond lengths are 2.15 Å. 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 six equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both V(2)-O(1) bond lengths are 2.09 Å. All V(2)-O(2) bond lengths are 2.06 Å. In the third V site, V(3) is bonded to six equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. All V(3)-O(2) bond lengths are 2.15 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and three equivalent V(2) atoms to form OLi3V3 octahedra that share corners with six equivalent O(1)Li3V3 octahedra and edges with twelve equivalent O(2)Li2V4 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent Li(1), one V(1), one V(3), and two equivalent V(2) atoms to form OLi2V4 octahedra that share corners with six equivalent O(2)Li2V4 octahedra, edges with four equivalent O(1)Li3V3 octahedra, and edges with eight equivalent O(2)Li2V4 octahedra. The corner-sharing octahedra are not tilted.