Li2VCr3O8 is Spinel-derived structured and crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(6), and two equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, and corners with six equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-64°. V(1) is bonded to one O(3), one O(6), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with four equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one Cr(1), and one Cr(2) atom. In the second O site, O(6) is bonded to one Li(1), one V(1), and two equivalent Cr(1) atoms to form a mixture of distorted corner and edge-sharing OLiVCr2 tetrahedra. In the third O site, O(1) is bonded to one Li(1), one Cr(2), and two equivalent Cr(1) atoms to form distorted OLiCr3 trigonal pyramids that share  a cornercorner with one O(6)LiVCr2 tetrahedra, corners with three equivalent O(2)LiCr3 tetrahedra, and  an edgeedge with one O(6)LiVCr2 tetrahedra. In the fourth O site, O(2) is bonded to one Li(2), one Cr(2), and two equivalent Cr(1) atoms to form OLiCr3 tetrahedra that share corners with two equivalent O(6)LiVCr2 tetrahedra and corners with three equivalent O(1)LiCr3 trigonal pyramids. In the fifth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), and two equivalent Cr(1) atoms. In the sixth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one Cr(1), and one Cr(2) atom.
Li2VCr3O8 is Spinel-derived structured and crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(6), and two equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, and corners with six equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. The Li(1)-O(1) bond length is 1.93 Å. The Li(1)-O(6) bond length is 2.00 Å. Both Li(1)-O(5) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Cr(2)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-64°. The Li(2)-O(2) bond length is 1.76 Å. The Li(2)-O(3) bond length is 2.01 Å. Both Li(2)-O(4) bond lengths are 2.01 Å. V(1) is bonded to one O(3), one O(6), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. The V(1)-O(3) bond length is 1.86 Å. The V(1)-O(6) bond length is 2.03 Å. Both V(1)-O(4) bond lengths are 1.86 Å. Both V(1)-O(5) bond lengths are 2.03 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The Cr(1)-O(1) bond length is 1.96 Å. The Cr(1)-O(2) bond length is 1.96 Å. The Cr(1)-O(3) bond length is 2.12 Å. The Cr(1)-O(4) bond length is 2.12 Å. The Cr(1)-O(5) bond length is 2.00 Å. The Cr(1)-O(6) bond length is 1.99 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with four equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The Cr(2)-O(1) bond length is 1.95 Å. The Cr(2)-O(2) bond length is 1.96 Å. Both Cr(2)-O(4) bond lengths are 2.13 Å. Both Cr(2)-O(5) bond lengths are 2.00 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one Cr(1), and one Cr(2) atom. In the second O site, O(6) is bonded to one Li(1), one V(1), and two equivalent Cr(1) atoms to form a mixture of distorted corner and edge-sharing OLiVCr2 tetrahedra. In the third O site, O(1) is bonded to one Li(1), one Cr(2), and two equivalent Cr(1) atoms to form distorted OLiCr3 trigonal pyramids that share  a cornercorner with one O(6)LiVCr2 tetrahedra, corners with three equivalent O(2)LiCr3 tetrahedra, and  an edgeedge with one O(6)LiVCr2 tetrahedra. In the fourth O site, O(2) is bonded to one Li(2), one Cr(2), and two equivalent Cr(1) atoms to form OLiCr3 tetrahedra that share corners with two equivalent O(6)LiVCr2 tetrahedra and corners with three equivalent O(1)LiCr3 trigonal pyramids. In the fifth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), and two equivalent Cr(1) atoms. In the sixth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one Cr(1), and one Cr(2) atom.