Li5V3CrO8 crystallizes in the hexagonal P6_3mc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-58°. In the second Li site, Li(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form LiO6 octahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, edges with six equivalent V(1)O6 octahedra, and  a faceface with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms. 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 two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. Cr(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form CrO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with six equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-50°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), two equivalent V(1), and one Cr(1) atom. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), two equivalent V(1), and one Cr(1) atom to form OLi3V2Cr octahedra that share edges with four equivalent O(2)Li3V2Cr octahedra and edges with two equivalent O(4)Li3V3 pentagonal pyramids. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), three equivalent Li(3), and three equivalent V(1) atoms. In the fourth O site, O(4) is bonded to three equivalent Li(3) and three equivalent V(1) atoms to form distorted edge-sharing OLi3V3 pentagonal pyramids.
Li5V3CrO8 crystallizes in the hexagonal P6_3mc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-58°. The Li(1)-O(3) bond length is 1.89 Å. All Li(1)-O(1) bond lengths are 1.85 Å. In the second Li site, Li(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form LiO6 octahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, edges with six equivalent V(1)O6 octahedra, and  a faceface with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. All Li(2)-O(1) bond lengths are 2.18 Å. All Li(2)-O(2) bond lengths are 2.15 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms. The Li(3)-O(3) bond length is 2.34 Å. The Li(3)-O(4) bond length is 2.02 Å. Both Li(3)-O(1) bond lengths are 2.36 Å. Both Li(3)-O(2) bond lengths are 1.95 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 two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The V(1)-O(3) bond length is 2.07 Å. The V(1)-O(4) bond length is 2.06 Å. Both V(1)-O(1) bond lengths are 2.11 Å. Both V(1)-O(2) bond lengths are 2.07 Å. Cr(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form CrO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with six equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-50°. All Cr(1)-O(1) bond lengths are 2.07 Å. All Cr(1)-O(2) bond lengths are 2.08 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), two equivalent V(1), and one Cr(1) atom. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), two equivalent V(1), and one Cr(1) atom to form OLi3V2Cr octahedra that share edges with four equivalent O(2)Li3V2Cr octahedra and edges with two equivalent O(4)Li3V3 pentagonal pyramids. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), three equivalent Li(3), and three equivalent V(1) atoms. In the fourth O site, O(4) is bonded to three equivalent Li(3) and three equivalent V(1) atoms to form distorted edge-sharing OLi3V3 pentagonal pyramids.