Li5V3CrO8 crystallizes in the monoclinic Cc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-60°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  a faceface with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom 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 two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom 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 two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. In the third V site, V(3) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom 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 two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-50°. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-52°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), one V(1), one V(3), and one Cr(1) atom. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Li(4), one V(1), one V(2), and one Cr(1) atom to form OLi3V2Cr octahedra that share edges with two equivalent O(5)Li3V2Cr octahedra, edges with two equivalent O(7)Li3V2Cr octahedra, and edges with two equivalent O(6)Li3V3 pentagonal pyramids. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(4), one Li(5), one V(2), one V(3), and one Cr(1) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one Li(5), one V(1), one V(3), and one Cr(1) atom to form OLi3V2Cr octahedra that share edges with two equivalent O(2)Li3V2Cr octahedra, edges with two equivalent O(7)Li3V2Cr octahedra, and edges with two equivalent O(6)Li3V3 pentagonal pyramids. In the sixth O site, O(6) is bonded to one Li(3), one Li(4), one Li(5), one V(1), one V(2), and one V(3) atom to form distorted edge-sharing OLi3V3 pentagonal pyramids. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(5), one V(2), one V(3), and one Cr(1) atom to form OLi3V2Cr octahedra that share edges with two equivalent O(2)Li3V2Cr octahedra, edges with two equivalent O(5)Li3V2Cr octahedra, and edges with two equivalent O(6)Li3V3 pentagonal pyramids. In the eighth O site, O(8) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), one V(2), and one Cr(1) atom.
Li5V3CrO8 crystallizes in the monoclinic Cc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-60°. The Li(1)-O(1) bond length is 1.89 Å. The Li(1)-O(3) bond length is 1.89 Å. The Li(1)-O(4) bond length is 1.89 Å. The Li(1)-O(8) bond length is 1.88 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  a faceface with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. The Li(2)-O(1) bond length is 2.19 Å. The Li(2)-O(2) bond length is 2.21 Å. The Li(2)-O(4) bond length is 2.21 Å. The Li(2)-O(5) bond length is 2.15 Å. The Li(2)-O(7) bond length is 2.17 Å. The Li(2)-O(8) bond length is 2.21 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom. The Li(3)-O(1) bond length is 2.40 Å. The Li(3)-O(2) bond length is 1.95 Å. The Li(3)-O(3) bond length is 2.32 Å. The Li(3)-O(6) bond length is 2.03 Å. The Li(3)-O(7) bond length is 1.95 Å. The Li(3)-O(8) bond length is 2.34 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. The Li(4)-O(2) bond length is 1.97 Å. The Li(4)-O(3) bond length is 2.36 Å. The Li(4)-O(4) bond length is 2.44 Å. The Li(4)-O(5) bond length is 1.96 Å. The Li(4)-O(6) bond length is 2.14 Å. The Li(4)-O(8) bond length is 2.41 Å. In the fifth Li site, Li(5) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. The Li(5)-O(1) bond length is 2.39 Å. The Li(5)-O(3) bond length is 2.38 Å. The Li(5)-O(4) bond length is 2.36 Å. The Li(5)-O(5) bond length is 1.95 Å. The Li(5)-O(6) bond length is 2.06 Å. The Li(5)-O(7) bond length is 1.97 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom 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 two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The V(1)-O(1) bond length is 2.14 Å. The V(1)-O(2) bond length is 2.05 Å. The V(1)-O(3) bond length is 2.06 Å. The V(1)-O(5) bond length is 2.11 Å. The V(1)-O(6) bond length is 2.05 Å. The V(1)-O(8) bond length is 2.11 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom 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 two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. The V(2)-O(2) bond length is 2.13 Å. The V(2)-O(3) bond length is 2.13 Å. The V(2)-O(4) bond length is 2.17 Å. The V(2)-O(6) bond length is 2.11 Å. The V(2)-O(7) bond length is 2.13 Å. The V(2)-O(8) bond length is 2.16 Å. In the third V site, V(3) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom 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 two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-50°. The V(3)-O(1) bond length is 2.13 Å. The V(3)-O(3) bond length is 2.06 Å. The V(3)-O(4) bond length is 2.11 Å. The V(3)-O(5) bond length is 2.10 Å. The V(3)-O(6) bond length is 2.04 Å. The V(3)-O(7) bond length is 2.04 Å. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-52°. The Cr(1)-O(1) bond length is 2.08 Å. The Cr(1)-O(2) bond length is 2.09 Å. The Cr(1)-O(4) bond length is 2.08 Å. The Cr(1)-O(5) bond length is 2.07 Å. The Cr(1)-O(7) bond length is 2.08 Å. The Cr(1)-O(8) bond length is 2.10 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), one V(1), one V(3), and one Cr(1) atom. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Li(4), one V(1), one V(2), and one Cr(1) atom to form OLi3V2Cr octahedra that share edges with two equivalent O(5)Li3V2Cr octahedra, edges with two equivalent O(7)Li3V2Cr octahedra, and edges with two equivalent O(6)Li3V3 pentagonal pyramids. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(4), one Li(5), one V(2), one V(3), and one Cr(1) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one Li(5), one V(1), one V(3), and one Cr(1) atom to form OLi3V2Cr octahedra that share edges with two equivalent O(2)Li3V2Cr octahedra, edges with two equivalent O(7)Li3V2Cr octahedra, and edges with two equivalent O(6)Li3V3 pentagonal pyramids. In the sixth O site, O(6) is bonded to one Li(3), one Li(4), one Li(5), one V(1), one V(2), and one V(3) atom to form distorted edge-sharing OLi3V3 pentagonal pyramids. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(5), one V(2), one V(3), and one Cr(1) atom to form OLi3V2Cr octahedra that share edges with two equivalent O(2)Li3V2Cr octahedra, edges with two equivalent O(5)Li3V2Cr octahedra, and edges with two equivalent O(6)Li3V3 pentagonal pyramids. In the eighth O site, O(8) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), one V(2), and one Cr(1) atom.