Li2VCr3O8 is Spinel-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) 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 56-61°. V(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, 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. In the second Cr site, Cr(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Cr(2), and two equivalent Cr(1) atoms to form distorted OLiCr3 tetrahedra that share corners with three equivalent O(1)LiCr3 tetrahedra, corners with three equivalent O(2)LiVCr2 trigonal pyramids, and  an edgeedge with one O(2)LiVCr2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Cr(1) atoms to form distorted OLiVCr2 trigonal pyramids that share corners with three equivalent O(1)LiCr3 tetrahedra, corners with three equivalent O(2)LiVCr2 trigonal pyramids, and  an edgeedge with one O(1)LiCr3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one Cr(1), and one Cr(2) atom.
Li2VCr3O8 is Spinel-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) 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 56-61°. The Li(1)-O(1) bond length is 1.92 Å. The Li(1)-O(2) bond length is 2.03 Å. Both Li(1)-O(3) bond lengths are 2.04 Å. V(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. Both V(1)-O(2) bond lengths are 1.92 Å. All V(1)-O(3) bond lengths are 1.92 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, 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. Both Cr(1)-O(1) bond lengths are 1.99 Å. Both Cr(1)-O(2) bond lengths are 2.04 Å. Both Cr(1)-O(3) bond lengths are 2.04 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. Both Cr(2)-O(1) bond lengths are 2.00 Å. All Cr(2)-O(3) bond lengths are 2.04 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Cr(2), and two equivalent Cr(1) atoms to form distorted OLiCr3 tetrahedra that share corners with three equivalent O(1)LiCr3 tetrahedra, corners with three equivalent O(2)LiVCr2 trigonal pyramids, and  an edgeedge with one O(2)LiVCr2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Cr(1) atoms to form distorted OLiVCr2 trigonal pyramids that share corners with three equivalent O(1)LiCr3 tetrahedra, corners with three equivalent O(2)LiVCr2 trigonal pyramids, and  an edgeedge with one O(1)LiCr3 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one Cr(1), and one Cr(2) atom.