Li2VCr2O6 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the second V site, V(2) is bonded to two equivalent O(5) and four equivalent O(6) atoms to form VO6 octahedra that share corners with four equivalent Li(2)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 9°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(3), one O(4), one O(5), one O(6), and two equivalent O(2) atoms to form CrO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. In the second Cr site, Cr(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-10°. There are six inequivalent O sites. In the first O site, O(3) is bonded to two equivalent Li(1), one V(1), one Cr(1), and one Cr(2) atom to form OLi2VCr2 square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid,  a cornercorner with one O(6)Li2V2Cr square pyramid,  a cornercorner with one O(5)Li2VCr2 square pyramid, corners with two equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids,  an edgeedge with one O(4)Li2Cr3 square pyramid,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid, edges with two equivalent O(2)Li2Cr3 square pyramids, and edges with two equivalent O(6)Li2V2Cr square pyramids. In the second O site, O(4) is bonded to two equivalent Li(1), one Cr(2), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid, corners with four equivalent O(6)Li2V2Cr square pyramids, corners with four equivalent O(3)Li2VCr2 square pyramids, edges with two equivalent O(3)Li2VCr2 square pyramids, edges with two equivalent O(5)Li2VCr2 square pyramids, and edges with four equivalent O(2)Li2Cr3 square pyramids. In the third O site, O(5) is bonded to two equivalent Li(1), one V(2), and two equivalent Cr(1) atoms to form OLi2VCr2 square pyramids that share  a cornercorner with one O(5)Li2VCr2 square pyramid, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with six equivalent O(2)Li2Cr3 square pyramids, edges with two equivalent O(4)Li2Cr3 square pyramids, edges with two equivalent O(3)Li2VCr2 square pyramids, and edges with four equivalent O(6)Li2V2Cr square pyramids. In the fourth O site, O(6) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(2)Li2Cr3 square pyramid,  a cornercorner with one O(3)Li2VCr2 square pyramid, corners with two equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with three equivalent O(6)Li2V2Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(6)Li2V2Cr square pyramid, edges with two equivalent O(2)Li2Cr3 square pyramids, edges with two equivalent O(3)Li2VCr2 square pyramids, and edges with two equivalent O(5)Li2VCr2 square pyramids. In the fifth O site, O(1) is bonded to two equivalent Li(2), two equivalent V(1), and one Cr(2) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(4)Li2Cr3 square pyramid, corners with two equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with four equivalent O(6)Li2V2Cr square pyramids, edges with two equivalent O(2)Li2Cr3 square pyramids, edges with two equivalent O(1)Li2V2Cr square pyramids, edges with two equivalent O(6)Li2V2Cr square pyramids, and edges with two equivalent O(3)Li2VCr2 square pyramids. In the sixth O site, O(2) is bonded to one Li(1), one Li(2), one Cr(2), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid,  a cornercorner with one O(6)Li2V2Cr square pyramid, corners with two equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with three equivalent O(5)Li2VCr2 square pyramids,  an edgeedge with one O(2)Li2Cr3 square pyramid,  an edgeedge with one O(1)Li2V2Cr square pyramid, edges with two equivalent O(4)Li2Cr3 square pyramids, edges with two equivalent O(6)Li2V2Cr square pyramids, and edges with two equivalent O(3)Li2VCr2 square pyramids.
Li2VCr2O6 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. The Li(1)-O(2) bond length is 2.18 Å. The Li(1)-O(4) bond length is 2.18 Å. The Li(1)-O(5) bond length is 2.21 Å. The Li(1)-O(6) bond length is 2.15 Å. There is one shorter (2.22 Å) and one longer (2.25 Å) Li(1)-O(3) bond length. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Both Li(2)-O(1) bond lengths are 2.23 Å. Both Li(2)-O(2) bond lengths are 2.17 Å. Both Li(2)-O(6) bond lengths are 2.20 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both V(1)-O(1) bond lengths are 2.00 Å. Both V(1)-O(3) bond lengths are 1.93 Å. Both V(1)-O(6) bond lengths are 1.98 Å. In the second V site, V(2) is bonded to two equivalent O(5) and four equivalent O(6) atoms to form VO6 octahedra that share corners with four equivalent Li(2)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 9°. Both V(2)-O(5) bond lengths are 1.88 Å. All V(2)-O(6) bond lengths are 2.03 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(3), one O(4), one O(5), one O(6), and two equivalent O(2) atoms to form CrO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. The Cr(1)-O(3) bond length is 2.03 Å. The Cr(1)-O(4) bond length is 2.01 Å. The Cr(1)-O(5) bond length is 2.07 Å. The Cr(1)-O(6) bond length is 2.05 Å. There is one shorter (1.98 Å) and one longer (2.02 Å) Cr(1)-O(2) bond length. In the second Cr site, Cr(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-10°. The Cr(2)-O(1) bond length is 2.01 Å. The Cr(2)-O(4) bond length is 1.97 Å. Both Cr(2)-O(2) bond lengths are 2.03 Å. Both Cr(2)-O(3) bond lengths are 2.08 Å. There are six inequivalent O sites. In the first O site, O(3) is bonded to two equivalent Li(1), one V(1), one Cr(1), and one Cr(2) atom to form OLi2VCr2 square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid,  a cornercorner with one O(6)Li2V2Cr square pyramid,  a cornercorner with one O(5)Li2VCr2 square pyramid, corners with two equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids,  an edgeedge with one O(4)Li2Cr3 square pyramid,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid, edges with two equivalent O(2)Li2Cr3 square pyramids, and edges with two equivalent O(6)Li2V2Cr square pyramids. In the second O site, O(4) is bonded to two equivalent Li(1), one Cr(2), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid, corners with four equivalent O(6)Li2V2Cr square pyramids, corners with four equivalent O(3)Li2VCr2 square pyramids, edges with two equivalent O(3)Li2VCr2 square pyramids, edges with two equivalent O(5)Li2VCr2 square pyramids, and edges with four equivalent O(2)Li2Cr3 square pyramids. In the third O site, O(5) is bonded to two equivalent Li(1), one V(2), and two equivalent Cr(1) atoms to form OLi2VCr2 square pyramids that share  a cornercorner with one O(5)Li2VCr2 square pyramid, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with six equivalent O(2)Li2Cr3 square pyramids, edges with two equivalent O(4)Li2Cr3 square pyramids, edges with two equivalent O(3)Li2VCr2 square pyramids, and edges with four equivalent O(6)Li2V2Cr square pyramids. In the fourth O site, O(6) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(2)Li2Cr3 square pyramid,  a cornercorner with one O(3)Li2VCr2 square pyramid, corners with two equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with three equivalent O(6)Li2V2Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(6)Li2V2Cr square pyramid, edges with two equivalent O(2)Li2Cr3 square pyramids, edges with two equivalent O(3)Li2VCr2 square pyramids, and edges with two equivalent O(5)Li2VCr2 square pyramids. In the fifth O site, O(1) is bonded to two equivalent Li(2), two equivalent V(1), and one Cr(2) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(4)Li2Cr3 square pyramid, corners with two equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with four equivalent O(6)Li2V2Cr square pyramids, edges with two equivalent O(2)Li2Cr3 square pyramids, edges with two equivalent O(1)Li2V2Cr square pyramids, edges with two equivalent O(6)Li2V2Cr square pyramids, and edges with two equivalent O(3)Li2VCr2 square pyramids. In the sixth O site, O(2) is bonded to one Li(1), one Li(2), one Cr(2), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid,  a cornercorner with one O(6)Li2V2Cr square pyramid, corners with two equivalent O(2)Li2Cr3 square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with three equivalent O(5)Li2VCr2 square pyramids,  an edgeedge with one O(2)Li2Cr3 square pyramid,  an edgeedge with one O(1)Li2V2Cr square pyramid, edges with two equivalent O(4)Li2Cr3 square pyramids, edges with two equivalent O(6)Li2V2Cr square pyramids, and edges with two equivalent O(3)Li2VCr2 square pyramids.