Li3V3CrO8 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(5), one O(6), and two equivalent O(2) atoms to form LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 square pyramids,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(3)O5 square pyramid. The corner-sharing octahedral tilt angles range from 4-6°. In the second Li site, Li(2) is bonded to one O(3), one O(5), one O(8), and two equivalent O(1) atoms to form LiO5 square pyramids that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 square pyramids,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(6), and two equivalent O(7) atoms to form LiO5 square pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid, corners with two equivalent Li(3)O5 square pyramids,  an edgeedge with one Cr(1)O6 octahedra, 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  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 8-9°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(7), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, edges with two equivalent Li(2)O5 square pyramids, and edges with two equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 5-24°. In the second V site, V(2) is bonded to one O(3), one O(5), one O(7), one O(8), and two equivalent O(4) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid,  an edgeedge with one Li(2)O5 square pyramid, and edges with two equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-24°. In the third V site, V(3) is bonded to one O(2), one O(5), one O(7), one O(8), and two equivalent O(6) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-24°. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(5) atoms to form CrO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O5 square pyramid, 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 5-24°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one Cr(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one V(1), one V(3), and one Cr(1) atom to form OLi2V2Cr trigonal bipyramids that share  a cornercorner with one O(5)Li2V2Cr2 octahedra,  a cornercorner with one O(6)Li2V2Cr square pyramid, corners with two equivalent O(2)Li2V2Cr trigonal bipyramids, edges with two equivalent O(5)Li2V2Cr2 octahedra, edges with two equivalent O(3)Li3V3 octahedra,  an edgeedge with one O(4)LiV3Cr square pyramid, edges with two equivalent O(6)Li2V2Cr square pyramids, and  an edgeedge with one O(7)Li2V3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 23°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(5)Li2V2Cr2 octahedra, corners with two equivalent O(3)Li3V3 octahedra,  a cornercorner with one O(4)LiV3Cr square pyramid,  a cornercorner with one O(7)Li2V3 trigonal bipyramid,  an edgeedge with one O(5)Li2V2Cr2 octahedra,  an edgeedge with one O(6)Li2V2Cr square pyramid, edges with two equivalent O(4)LiV3Cr square pyramids, edges with two equivalent O(2)Li2V2Cr trigonal bipyramids, and edges with two equivalent O(7)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-10°. In the fourth O site, O(4) is bonded to one Li(3), one V(1), two equivalent V(2), and one Cr(1) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(3)Li3V3 octahedra, corners with two equivalent O(4)LiV3Cr square pyramids,  a cornercorner with one O(7)Li2V3 trigonal bipyramid, edges with two equivalent O(5)Li2V2Cr2 octahedra, edges with two equivalent O(3)Li3V3 octahedra,  an edgeedge with one O(6)Li2V2Cr square pyramid,  an edgeedge with one O(2)Li2V2Cr trigonal bipyramid, and edges with two equivalent O(7)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 10°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(2), one V(3), and two equivalent Cr(1) atoms to form OLi2V2Cr2 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra, corners with two equivalent O(5)Li2V2Cr2 octahedra,  a cornercorner with one O(6)Li2V2Cr square pyramid,  a cornercorner with one O(2)Li2V2Cr trigonal bipyramid,  an edgeedge with one O(3)Li3V3 octahedra, edges with two equivalent O(6)Li2V2Cr square pyramids, edges with two equivalent O(4)LiV3Cr square pyramids,  an edgeedge with one O(7)Li2V3 trigonal bipyramid, and edges with two equivalent O(2)Li2V2Cr trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-10°. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), two equivalent V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(5)Li2V2Cr2 octahedra, corners with two equivalent O(6)Li2V2Cr square pyramids,  a cornercorner with one O(2)Li2V2Cr trigonal bipyramid,  an edgeedge with one O(3)Li3V3 octahedra, edges with two equivalent O(5)Li2V2Cr2 octahedra,  an edgeedge with one O(4)LiV3Cr square pyramid, edges with two equivalent O(2)Li2V2Cr trigonal bipyramids, and edges with two equivalent O(7)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°. In the seventh O site, O(7) is bonded to two equivalent Li(3), one V(1), one V(2), and one V(3) atom to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(4)LiV3Cr square pyramid, corners with two equivalent O(7)Li2V3 trigonal bipyramids,  an edgeedge with one O(5)Li2V2Cr2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(6)Li2V2Cr square pyramids, edges with two equivalent O(4)LiV3Cr square pyramids, and  an edgeedge with one O(2)Li2V2Cr trigonal bipyramid. The corner-sharing octahedral tilt angles are 12°. In the eighth O site, O(8) is bonded in a T-shaped geometry to one Li(2), one V(2), and one V(3) atom.
Li3V3CrO8 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(5), one O(6), and two equivalent O(2) atoms to form LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 square pyramids,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(3)O5 square pyramid. The corner-sharing octahedral tilt angles range from 4-6°. The Li(1)-O(3) bond length is 2.05 Å. The Li(1)-O(5) bond length is 2.20 Å. The Li(1)-O(6) bond length is 2.12 Å. Both Li(1)-O(2) bond lengths are 2.05 Å. In the second Li site, Li(2) is bonded to one O(3), one O(5), one O(8), and two equivalent O(1) atoms to form LiO5 square pyramids that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 square pyramids,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. The Li(2)-O(3) bond length is 1.98 Å. The Li(2)-O(5) bond length is 2.05 Å. The Li(2)-O(8) bond length is 2.02 Å. Both Li(2)-O(1) bond lengths are 2.08 Å. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(6), and two equivalent O(7) atoms to form LiO5 square pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid, corners with two equivalent Li(3)O5 square pyramids,  an edgeedge with one Cr(1)O6 octahedra, 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  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 8-9°. The Li(3)-O(3) bond length is 2.13 Å. The Li(3)-O(4) bond length is 2.14 Å. The Li(3)-O(6) bond length is 1.97 Å. Both Li(3)-O(7) bond lengths are 2.05 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(4), one O(7), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, edges with two equivalent Li(2)O5 square pyramids, and edges with two equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 5-24°. The V(1)-O(1) bond length is 1.79 Å. The V(1)-O(2) bond length is 2.09 Å. The V(1)-O(4) bond length is 2.11 Å. The V(1)-O(7) bond length is 1.90 Å. Both V(1)-O(3) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to one O(3), one O(5), one O(7), one O(8), and two equivalent O(4) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid,  an edgeedge with one Li(2)O5 square pyramid, and edges with two equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-24°. The V(2)-O(3) bond length is 2.14 Å. The V(2)-O(5) bond length is 2.25 Å. The V(2)-O(7) bond length is 2.06 Å. The V(2)-O(8) bond length is 1.85 Å. Both V(2)-O(4) bond lengths are 2.09 Å. In the third V site, V(3) is bonded to one O(2), one O(5), one O(7), one O(8), and two equivalent O(6) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-24°. The V(3)-O(2) bond length is 2.02 Å. The V(3)-O(5) bond length is 2.13 Å. The V(3)-O(7) bond length is 2.16 Å. The V(3)-O(8) bond length is 1.85 Å. Both V(3)-O(6) bond lengths are 2.07 Å. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(5) atoms to form CrO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O5 square pyramid, 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 5-24°. The Cr(1)-O(1) bond length is 2.04 Å. The Cr(1)-O(2) bond length is 2.02 Å. The Cr(1)-O(4) bond length is 2.04 Å. The Cr(1)-O(6) bond length is 2.00 Å. Both Cr(1)-O(5) bond lengths are 2.06 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one Cr(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one V(1), one V(3), and one Cr(1) atom to form OLi2V2Cr trigonal bipyramids that share  a cornercorner with one O(5)Li2V2Cr2 octahedra,  a cornercorner with one O(6)Li2V2Cr square pyramid, corners with two equivalent O(2)Li2V2Cr trigonal bipyramids, edges with two equivalent O(5)Li2V2Cr2 octahedra, edges with two equivalent O(3)Li3V3 octahedra,  an edgeedge with one O(4)LiV3Cr square pyramid, edges with two equivalent O(6)Li2V2Cr square pyramids, and  an edgeedge with one O(7)Li2V3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 23°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(5)Li2V2Cr2 octahedra, corners with two equivalent O(3)Li3V3 octahedra,  a cornercorner with one O(4)LiV3Cr square pyramid,  a cornercorner with one O(7)Li2V3 trigonal bipyramid,  an edgeedge with one O(5)Li2V2Cr2 octahedra,  an edgeedge with one O(6)Li2V2Cr square pyramid, edges with two equivalent O(4)LiV3Cr square pyramids, edges with two equivalent O(2)Li2V2Cr trigonal bipyramids, and edges with two equivalent O(7)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-10°. In the fourth O site, O(4) is bonded to one Li(3), one V(1), two equivalent V(2), and one Cr(1) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(3)Li3V3 octahedra, corners with two equivalent O(4)LiV3Cr square pyramids,  a cornercorner with one O(7)Li2V3 trigonal bipyramid, edges with two equivalent O(5)Li2V2Cr2 octahedra, edges with two equivalent O(3)Li3V3 octahedra,  an edgeedge with one O(6)Li2V2Cr square pyramid,  an edgeedge with one O(2)Li2V2Cr trigonal bipyramid, and edges with two equivalent O(7)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 10°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(2), one V(3), and two equivalent Cr(1) atoms to form OLi2V2Cr2 octahedra that share  a cornercorner with one O(3)Li3V3 octahedra, corners with two equivalent O(5)Li2V2Cr2 octahedra,  a cornercorner with one O(6)Li2V2Cr square pyramid,  a cornercorner with one O(2)Li2V2Cr trigonal bipyramid,  an edgeedge with one O(3)Li3V3 octahedra, edges with two equivalent O(6)Li2V2Cr square pyramids, edges with two equivalent O(4)LiV3Cr square pyramids,  an edgeedge with one O(7)Li2V3 trigonal bipyramid, and edges with two equivalent O(2)Li2V2Cr trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-10°. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), two equivalent V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(5)Li2V2Cr2 octahedra, corners with two equivalent O(6)Li2V2Cr square pyramids,  a cornercorner with one O(2)Li2V2Cr trigonal bipyramid,  an edgeedge with one O(3)Li3V3 octahedra, edges with two equivalent O(5)Li2V2Cr2 octahedra,  an edgeedge with one O(4)LiV3Cr square pyramid, edges with two equivalent O(2)Li2V2Cr trigonal bipyramids, and edges with two equivalent O(7)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°. In the seventh O site, O(7) is bonded to two equivalent Li(3), one V(1), one V(2), and one V(3) atom to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(3)Li3V3 octahedra,  a cornercorner with one O(4)LiV3Cr square pyramid, corners with two equivalent O(7)Li2V3 trigonal bipyramids,  an edgeedge with one O(5)Li2V2Cr2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(6)Li2V2Cr square pyramids, edges with two equivalent O(4)LiV3Cr square pyramids, and  an edgeedge with one O(2)Li2V2Cr trigonal bipyramid. The corner-sharing octahedral tilt angles are 12°. In the eighth O site, O(8) is bonded in a T-shaped geometry to one Li(2), one V(2), and one V(3) atom.