Li2V3CrO8 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(8), and two equivalent O(5) atoms to form LiO5 square pyramids that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles are 3°. In the second Li site, Li(2) is bonded to one O(1), one O(7), one O(8), and two equivalent O(4) atoms to form LiO5 square pyramids that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(2)O5 square pyramids,  an edgeedge with one Cr(1)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)O5 square pyramid. The corner-sharing octahedral tilt angles range from 3-11°. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and two equivalent O(8) atoms. In the second V site, V(2) is bonded to one O(4), one O(5), one O(6), one O(7), and two equivalent O(1) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 6-23°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 17-23°. Cr(1) is bonded to one O(5), one O(6), one O(7), one O(8), and two equivalent O(2) atoms to form CrO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 6-16°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(3), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share  a cornercorner with one O(7)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V3 square pyramids,  a cornercorner with one O(4)Li2V3 trigonal bipyramid,  an edgeedge with one O(8)Li2V2Cr square pyramid,  an edgeedge with one O(2)LiV2Cr2 square pyramid, edges with two equivalent O(7)LiV3Cr square pyramids, edges with two equivalent O(5)Li2V2Cr trigonal bipyramids, and edges with two equivalent O(4)Li2V3 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(3), and two equivalent Cr(1) atoms to form OLiV2Cr2 square pyramids that share  a cornercorner with one O(8)Li2V2Cr square pyramid, corners with two equivalent O(2)LiV2Cr2 square pyramids,  a cornercorner with one O(5)Li2V2Cr trigonal bipyramid,  an edgeedge with one O(1)Li2V3 square pyramid, edges with two equivalent O(8)Li2V2Cr square pyramids, edges with two equivalent O(7)LiV3Cr square pyramids,  an edgeedge with one O(4)Li2V3 trigonal bipyramid, and edges with two equivalent O(5)Li2V2Cr trigonal bipyramids. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(1), one V(2), and one V(3) atom to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(7)LiV3Cr square pyramid, corners with two equivalent O(4)Li2V3 trigonal bipyramids,  an edgeedge with one O(2)LiV2Cr2 square pyramid, edges with two equivalent O(8)Li2V2Cr square pyramids, edges with two equivalent O(1)Li2V3 square pyramids, edges with two equivalent O(7)LiV3Cr square pyramids, and  an edgeedge with one O(5)Li2V2Cr trigonal bipyramid. In the fifth O site, O(5) is bonded to two equivalent Li(1), one V(1), one V(2), and one Cr(1) atom to form OLi2V2Cr trigonal bipyramids that share  a cornercorner with one O(8)Li2V2Cr square pyramid,  a cornercorner with one O(2)LiV2Cr2 square pyramid, corners with two equivalent O(5)Li2V2Cr trigonal bipyramids,  an edgeedge with one O(7)LiV3Cr square pyramid, edges with two equivalent O(8)Li2V2Cr square pyramids, edges with two equivalent O(1)Li2V3 square pyramids, edges with two equivalent O(2)LiV2Cr2 square pyramids, and  an edgeedge with one O(4)Li2V3 trigonal bipyramid. In the sixth O site, O(6) is bonded in a linear geometry to one V(2) and one Cr(1) atom. In the seventh O site, O(7) is bonded to one Li(2), one V(2), two equivalent V(3), and one Cr(1) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid, corners with two equivalent O(7)LiV3Cr square pyramids,  a cornercorner with one O(4)Li2V3 trigonal bipyramid,  an edgeedge with one O(8)Li2V2Cr square pyramid, edges with two equivalent O(1)Li2V3 square pyramids, edges with two equivalent O(2)LiV2Cr2 square pyramids,  an edgeedge with one O(5)Li2V2Cr trigonal bipyramid, and edges with two equivalent O(4)Li2V3 trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(1), one Li(2), two equivalent V(1), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(2)LiV2Cr2 square pyramid, corners with two equivalent O(8)Li2V2Cr square pyramids,  a cornercorner with one O(5)Li2V2Cr trigonal bipyramid,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(7)LiV3Cr square pyramid, edges with two equivalent O(2)LiV2Cr2 square pyramids, edges with two equivalent O(5)Li2V2Cr trigonal bipyramids, and edges with two equivalent O(4)Li2V3 trigonal bipyramids.
Li2V3CrO8 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(8), and two equivalent O(5) atoms to form LiO5 square pyramids that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles are 3°. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 2.15 Å. The Li(1)-O(8) bond length is 2.13 Å. Both Li(1)-O(5) bond lengths are 2.02 Å. In the second Li site, Li(2) is bonded to one O(1), one O(7), one O(8), and two equivalent O(4) atoms to form LiO5 square pyramids that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(2)O5 square pyramids,  an edgeedge with one Cr(1)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)O5 square pyramid. The corner-sharing octahedral tilt angles range from 3-11°. The Li(2)-O(1) bond length is 2.08 Å. The Li(2)-O(7) bond length is 2.16 Å. The Li(2)-O(8) bond length is 2.02 Å. Both Li(2)-O(4) bond lengths are 2.02 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and two equivalent O(8) atoms. The V(1)-O(2) bond length is 2.08 Å. The V(1)-O(3) bond length is 1.69 Å. The V(1)-O(4) bond length is 2.23 Å. The V(1)-O(5) bond length is 1.98 Å. Both V(1)-O(8) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to one O(4), one O(5), one O(6), one O(7), and two equivalent O(1) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 6-23°. The V(2)-O(4) bond length is 1.97 Å. The V(2)-O(5) bond length is 2.19 Å. The V(2)-O(6) bond length is 1.71 Å. The V(2)-O(7) bond length is 2.12 Å. Both V(2)-O(1) bond lengths are 2.04 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 17-23°. The V(3)-O(1) bond length is 2.06 Å. The V(3)-O(2) bond length is 2.14 Å. The V(3)-O(3) bond length is 1.97 Å. The V(3)-O(4) bond length is 1.98 Å. Both V(3)-O(7) bond lengths are 2.04 Å. Cr(1) is bonded to one O(5), one O(6), one O(7), one O(8), and two equivalent O(2) atoms to form CrO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 6-16°. The Cr(1)-O(5) bond length is 2.00 Å. The Cr(1)-O(6) bond length is 1.97 Å. The Cr(1)-O(7) bond length is 2.11 Å. The Cr(1)-O(8) bond length is 2.02 Å. Both Cr(1)-O(2) bond lengths are 2.04 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(3), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share  a cornercorner with one O(7)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V3 square pyramids,  a cornercorner with one O(4)Li2V3 trigonal bipyramid,  an edgeedge with one O(8)Li2V2Cr square pyramid,  an edgeedge with one O(2)LiV2Cr2 square pyramid, edges with two equivalent O(7)LiV3Cr square pyramids, edges with two equivalent O(5)Li2V2Cr trigonal bipyramids, and edges with two equivalent O(4)Li2V3 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(3), and two equivalent Cr(1) atoms to form OLiV2Cr2 square pyramids that share  a cornercorner with one O(8)Li2V2Cr square pyramid, corners with two equivalent O(2)LiV2Cr2 square pyramids,  a cornercorner with one O(5)Li2V2Cr trigonal bipyramid,  an edgeedge with one O(1)Li2V3 square pyramid, edges with two equivalent O(8)Li2V2Cr square pyramids, edges with two equivalent O(7)LiV3Cr square pyramids,  an edgeedge with one O(4)Li2V3 trigonal bipyramid, and edges with two equivalent O(5)Li2V2Cr trigonal bipyramids. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(1), one V(2), and one V(3) atom to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(7)LiV3Cr square pyramid, corners with two equivalent O(4)Li2V3 trigonal bipyramids,  an edgeedge with one O(2)LiV2Cr2 square pyramid, edges with two equivalent O(8)Li2V2Cr square pyramids, edges with two equivalent O(1)Li2V3 square pyramids, edges with two equivalent O(7)LiV3Cr square pyramids, and  an edgeedge with one O(5)Li2V2Cr trigonal bipyramid. In the fifth O site, O(5) is bonded to two equivalent Li(1), one V(1), one V(2), and one Cr(1) atom to form OLi2V2Cr trigonal bipyramids that share  a cornercorner with one O(8)Li2V2Cr square pyramid,  a cornercorner with one O(2)LiV2Cr2 square pyramid, corners with two equivalent O(5)Li2V2Cr trigonal bipyramids,  an edgeedge with one O(7)LiV3Cr square pyramid, edges with two equivalent O(8)Li2V2Cr square pyramids, edges with two equivalent O(1)Li2V3 square pyramids, edges with two equivalent O(2)LiV2Cr2 square pyramids, and  an edgeedge with one O(4)Li2V3 trigonal bipyramid. In the sixth O site, O(6) is bonded in a linear geometry to one V(2) and one Cr(1) atom. In the seventh O site, O(7) is bonded to one Li(2), one V(2), two equivalent V(3), and one Cr(1) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid, corners with two equivalent O(7)LiV3Cr square pyramids,  a cornercorner with one O(4)Li2V3 trigonal bipyramid,  an edgeedge with one O(8)Li2V2Cr square pyramid, edges with two equivalent O(1)Li2V3 square pyramids, edges with two equivalent O(2)LiV2Cr2 square pyramids,  an edgeedge with one O(5)Li2V2Cr trigonal bipyramid, and edges with two equivalent O(4)Li2V3 trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(1), one Li(2), two equivalent V(1), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(2)LiV2Cr2 square pyramid, corners with two equivalent O(8)Li2V2Cr square pyramids,  a cornercorner with one O(5)Li2V2Cr trigonal bipyramid,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(7)LiV3Cr square pyramid, edges with two equivalent O(2)LiV2Cr2 square pyramids, edges with two equivalent O(5)Li2V2Cr trigonal bipyramids, and edges with two equivalent O(4)Li2V3 trigonal bipyramids.