Li2VCrO4 is alpha Po-derived structured and 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(1) and four 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 Cr(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second Li site, Li(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form LiO6 octahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with three equivalent Cr(1)O6 octahedra, and edges with six equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. V(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. Cr(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), two equivalent V(1), and one Cr(1) atom to form OLi3V2Cr octahedra that share corners with three equivalent O(1)Li3V2Cr octahedra, corners with three equivalent O(2)Li3V2Cr octahedra,  an edgeedge with one O(2)Li3V2Cr octahedra, edges with two equivalent O(4)Li3VCr2 octahedra, edges with three equivalent O(1)Li3V2Cr octahedra, and edges with six equivalent O(3)Li3VCr2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to three equivalent Li(2), two equivalent V(1), and one Cr(1) atom to form OLi3V2Cr octahedra that share corners with three equivalent O(1)Li3V2Cr octahedra, corners with three equivalent O(4)Li3VCr2 octahedra,  an edgeedge with one O(1)Li3V2Cr octahedra, edges with two equivalent O(3)Li3VCr2 octahedra, edges with four equivalent O(2)Li3V2Cr octahedra, and edges with five equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), one V(1), and two equivalent Cr(1) atoms to form OLi3VCr2 octahedra that share corners with three equivalent O(3)Li3VCr2 octahedra, corners with three equivalent O(4)Li3VCr2 octahedra,  an edgeedge with one O(4)Li3VCr2 octahedra, edges with two equivalent O(2)Li3V2Cr octahedra, edges with three equivalent O(3)Li3VCr2 octahedra, and edges with six equivalent O(1)Li3V2Cr octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to three equivalent Li(2), one V(1), and two equivalent Cr(1) atoms to form OLi3VCr2 octahedra that share corners with three equivalent O(2)Li3V2Cr octahedra, corners with three equivalent O(3)Li3VCr2 octahedra,  an edgeedge with one O(3)Li3VCr2 octahedra, edges with two equivalent O(1)Li3V2Cr octahedra, edges with four equivalent O(4)Li3VCr2 octahedra, and edges with five equivalent O(2)Li3V2Cr octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li2VCrO4 is alpha Po-derived structured and 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(1) and four 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 Cr(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)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(3) bond lengths are 2.18 Å. In the second Li site, Li(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form LiO6 octahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with three equivalent Cr(1)O6 octahedra, and edges with six equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. There are two shorter (2.17 Å) and one longer (2.23 Å) Li(2)-O(2) bond length. There is one shorter (2.16 Å) and two longer (2.18 Å) Li(2)-O(4) bond lengths. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Li(3)-O(3) bond lengths are 2.18 Å. All Li(3)-O(1) bond lengths are 2.17 Å. V(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The V(1)-O(3) bond length is 2.09 Å. The V(1)-O(4) bond length is 2.09 Å. Both V(1)-O(1) bond lengths are 2.05 Å. Both V(1)-O(2) bond lengths are 2.05 Å. Cr(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form CrO6 octahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. The Cr(1)-O(1) bond length is 2.06 Å. The Cr(1)-O(2) bond length is 2.06 Å. Both Cr(1)-O(3) bond lengths are 2.03 Å. Both Cr(1)-O(4) bond lengths are 2.03 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), two equivalent V(1), and one Cr(1) atom to form OLi3V2Cr octahedra that share corners with three equivalent O(1)Li3V2Cr octahedra, corners with three equivalent O(2)Li3V2Cr octahedra,  an edgeedge with one O(2)Li3V2Cr octahedra, edges with two equivalent O(4)Li3VCr2 octahedra, edges with three equivalent O(1)Li3V2Cr octahedra, and edges with six equivalent O(3)Li3VCr2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to three equivalent Li(2), two equivalent V(1), and one Cr(1) atom to form OLi3V2Cr octahedra that share corners with three equivalent O(1)Li3V2Cr octahedra, corners with three equivalent O(4)Li3VCr2 octahedra,  an edgeedge with one O(1)Li3V2Cr octahedra, edges with two equivalent O(3)Li3VCr2 octahedra, edges with four equivalent O(2)Li3V2Cr octahedra, and edges with five equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), one V(1), and two equivalent Cr(1) atoms to form OLi3VCr2 octahedra that share corners with three equivalent O(3)Li3VCr2 octahedra, corners with three equivalent O(4)Li3VCr2 octahedra,  an edgeedge with one O(4)Li3VCr2 octahedra, edges with two equivalent O(2)Li3V2Cr octahedra, edges with three equivalent O(3)Li3VCr2 octahedra, and edges with six equivalent O(1)Li3V2Cr octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to three equivalent Li(2), one V(1), and two equivalent Cr(1) atoms to form OLi3VCr2 octahedra that share corners with three equivalent O(2)Li3V2Cr octahedra, corners with three equivalent O(3)Li3VCr2 octahedra,  an edgeedge with one O(3)Li3VCr2 octahedra, edges with two equivalent O(1)Li3V2Cr octahedra, edges with four equivalent O(4)Li3VCr2 octahedra, and edges with five equivalent O(2)Li3V2Cr octahedra. The corner-sharing octahedral tilt angles range from 0-1°.