Li5V2Cr2O8 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) 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 four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. In the third Li site, Li(3) is bonded in a trigonal planar geometry to one O(1) and two equivalent O(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(3) 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 four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(2), one V(1), and two equivalent Cr(1) atoms to form distorted OLi3VCr2 octahedra that share corners with two equivalent O(3)Li3V2Cr octahedra, corners with five equivalent O(1)Li3VCr2 octahedra, edges with four equivalent O(2)Li3VCr2 octahedra, and edges with six equivalent O(3)Li3V2Cr octahedra. The corner-sharing octahedral tilt angles range from 0-87°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one V(2), and two equivalent Cr(1) atoms to form OLi3VCr2 octahedra that share corners with six equivalent O(2)Li3VCr2 octahedra, edges with four equivalent O(1)Li3VCr2 octahedra, and edges with eight equivalent O(3)Li3V2Cr octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one Cr(1) atom to form distorted OLi3V2Cr octahedra that share  a cornercorner with one O(1)Li3VCr2 octahedra, corners with six equivalent O(3)Li3V2Cr octahedra, edges with three equivalent O(3)Li3V2Cr octahedra, edges with three equivalent O(1)Li3VCr2 octahedra, and edges with four equivalent O(2)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-87°.
Li5V2Cr2O8 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) 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 four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Li(1)-O(2) bond lengths are 2.13 Å. All Li(1)-O(3) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. Both Li(2)-O(1) bond lengths are 2.20 Å. Both Li(2)-O(2) bond lengths are 2.21 Å. Both Li(2)-O(3) bond lengths are 2.23 Å. In the third Li site, Li(3) is bonded in a trigonal planar geometry to one O(1) and two equivalent O(3) atoms. The Li(3)-O(1) bond length is 1.86 Å. Both Li(3)-O(3) bond lengths are 1.83 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(3) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. Both V(1)-O(1) bond lengths are 2.13 Å. All V(1)-O(3) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(3) 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 four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both V(2)-O(2) bond lengths are 2.16 Å. All V(2)-O(3) bond lengths are 2.15 Å. Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. Both Cr(1)-O(1) bond lengths are 2.07 Å. Both Cr(1)-O(2) bond lengths are 2.06 Å. Both Cr(1)-O(3) bond lengths are 2.06 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(2), one V(1), and two equivalent Cr(1) atoms to form distorted OLi3VCr2 octahedra that share corners with two equivalent O(3)Li3V2Cr octahedra, corners with five equivalent O(1)Li3VCr2 octahedra, edges with four equivalent O(2)Li3VCr2 octahedra, and edges with six equivalent O(3)Li3V2Cr octahedra. The corner-sharing octahedral tilt angles range from 0-87°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one V(2), and two equivalent Cr(1) atoms to form OLi3VCr2 octahedra that share corners with six equivalent O(2)Li3VCr2 octahedra, edges with four equivalent O(1)Li3VCr2 octahedra, and edges with eight equivalent O(3)Li3V2Cr octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one Cr(1) atom to form distorted OLi3V2Cr octahedra that share  a cornercorner with one O(1)Li3VCr2 octahedra, corners with six equivalent O(3)Li3V2Cr octahedra, edges with three equivalent O(3)Li3V2Cr octahedra, edges with three equivalent O(1)Li3VCr2 octahedra, and edges with four equivalent O(2)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-87°.