Li4VCr3O8 is alpha Po-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. 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(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two 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(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second Cr site, Cr(2) 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(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one V(1), and two equivalent Cr(2) atoms to form OLi3VCr2 octahedra that share corners with three equivalent O(2)Li3Cr3 octahedra, corners with three equivalent O(1)Li3VCr2 octahedra,  an edgeedge with one O(1)Li3VCr2 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra, and edges with eight equivalent O(3)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Cr(1), and two equivalent Cr(2) atoms to form OLi3Cr3 octahedra that share corners with three equivalent O(2)Li3Cr3 octahedra, corners with three equivalent O(1)Li3VCr2 octahedra,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3VCr2 octahedra, and edges with eight equivalent O(3)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one V(1), one Cr(1), and one Cr(2) atom to form OLi3VCr2 octahedra that share corners with six equivalent O(3)Li3VCr2 octahedra, edges with four equivalent O(2)Li3Cr3 octahedra, edges with four equivalent O(1)Li3VCr2 octahedra, and edges with four equivalent O(3)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li4VCr3O8 is alpha Po-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The Li(1)-O(1) bond length is 2.13 Å. The Li(1)-O(2) bond length is 2.21 Å. There are two shorter (2.14 Å) and two longer (2.19 Å) Li(1)-O(3) bond lengths. 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(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Li(2)-O(1) bond lengths are 2.17 Å. Both Li(2)-O(2) bond lengths are 2.18 Å. Both Li(2)-O(3) bond lengths are 2.18 Å. V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. Both V(1)-O(1) bond lengths are 2.08 Å. All V(1)-O(3) bond lengths are 2.05 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two 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(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Cr(1)-O(2) bond lengths are 2.03 Å. All Cr(1)-O(3) bond lengths are 2.03 Å. In the second Cr site, Cr(2) 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(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Cr(2)-O(1) bond lengths are 2.03 Å. Both Cr(2)-O(2) bond lengths are 2.04 Å. Both Cr(2)-O(3) bond lengths are 2.04 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one V(1), and two equivalent Cr(2) atoms to form OLi3VCr2 octahedra that share corners with three equivalent O(2)Li3Cr3 octahedra, corners with three equivalent O(1)Li3VCr2 octahedra,  an edgeedge with one O(1)Li3VCr2 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra, and edges with eight equivalent O(3)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Cr(1), and two equivalent Cr(2) atoms to form OLi3Cr3 octahedra that share corners with three equivalent O(2)Li3Cr3 octahedra, corners with three equivalent O(1)Li3VCr2 octahedra,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3VCr2 octahedra, and edges with eight equivalent O(3)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one V(1), one Cr(1), and one Cr(2) atom to form OLi3VCr2 octahedra that share corners with six equivalent O(3)Li3VCr2 octahedra, edges with four equivalent O(2)Li3Cr3 octahedra, edges with four equivalent O(1)Li3VCr2 octahedra, and edges with four equivalent O(3)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.