Li4V3O8 crystallizes in the trigonal R-3 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent O(2) atoms to form LiO6 octahedra that share edges with six equivalent Li(2)O6 octahedra and edges with six equivalent V(1)O6 octahedra. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2) and three equivalent V(1) atoms to form OLi3V3 octahedra that share corners with six equivalent O(1)Li3V3 octahedra and edges with twelve equivalent O(2)Li3V2 square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and two equivalent V(1) atoms to form OLi3V2 square pyramids that share corners with nine equivalent O(2)Li3V2 square pyramids, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li3V2 square pyramids.
Li4V3O8 crystallizes in the trigonal R-3 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent O(2) atoms to form LiO6 octahedra that share edges with six equivalent Li(2)O6 octahedra and edges with six equivalent V(1)O6 octahedra. All Li(1)-O(2) bond lengths are 2.04 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. Both Li(2)-O(1) bond lengths are 2.12 Å. There are two shorter (2.16 Å) and two longer (2.29 Å) Li(2)-O(2) bond lengths. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. Both V(1)-O(1) bond lengths are 2.04 Å. There are two shorter (1.87 Å) and two longer (2.02 Å) V(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2) and three equivalent V(1) atoms to form OLi3V3 octahedra that share corners with six equivalent O(1)Li3V3 octahedra and edges with twelve equivalent O(2)Li3V2 square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and two equivalent V(1) atoms to form OLi3V2 square pyramids that share corners with nine equivalent O(2)Li3V2 square pyramids, edges with four equivalent O(1)Li3V3 octahedra, and edges with four equivalent O(2)Li3V2 square pyramids.