Li5VCr3O8 crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to three equivalent O(2) atoms. 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 Cr(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. V(1) is bonded to six equivalent O(2) atoms to form VO6 octahedra that share edges with six equivalent Li(2)O6 octahedra and edges with six equivalent Cr(1)O6 octahedra. Cr(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2) and three equivalent Cr(1) atoms to form OLi3Cr3 octahedra that share corners with six equivalent O(1)Li3Cr3 octahedra and edges with twelve equivalent O(2)Li3VCr2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one V(1), and two equivalent Cr(1) atoms to form distorted OLi3VCr2 octahedra that share corners with seven equivalent O(2)Li3VCr2 octahedra, edges with four equivalent O(1)Li3Cr3 octahedra, and edges with six equivalent O(2)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-88°.
Li5VCr3O8 crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to three equivalent O(2) atoms. All Li(1)-O(2) bond lengths are 1.84 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 Cr(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. Both Li(2)-O(1) bond lengths are 2.23 Å. All Li(2)-O(2) bond lengths are 2.25 Å. V(1) is bonded to six equivalent O(2) atoms to form VO6 octahedra that share edges with six equivalent Li(2)O6 octahedra and edges with six equivalent Cr(1)O6 octahedra. All V(1)-O(2) bond lengths are 2.14 Å. Cr(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. Both Cr(1)-O(1) bond lengths are 2.08 Å. All Cr(1)-O(2) bond lengths are 2.06 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2) and three equivalent Cr(1) atoms to form OLi3Cr3 octahedra that share corners with six equivalent O(1)Li3Cr3 octahedra and edges with twelve equivalent O(2)Li3VCr2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one V(1), and two equivalent Cr(1) atoms to form distorted OLi3VCr2 octahedra that share corners with seven equivalent O(2)Li3VCr2 octahedra, edges with four equivalent O(1)Li3Cr3 octahedra, and edges with six equivalent O(2)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-88°.