Li2VCr3O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Cr(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 9-12°. V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CrO6 octahedra that share edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. In the second Cr site, Cr(2) 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)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 9-12°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(1), and two equivalent Cr(2) atoms to form OLi2VCr2 square pyramids that share corners with five equivalent O(1)Li2VCr2 square pyramids and edges with four equivalent O(2)Li2Cr3 square pyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Cr(1), and two equivalent Cr(2) atoms to form OLi2Cr3 square pyramids that share corners with five equivalent O(2)Li2Cr3 square pyramids and edges with four equivalent O(1)Li2VCr2 square pyramids. 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 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Cr(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 9-12°. Both Li(1)-O(1) bond lengths are 2.17 Å. Both Li(1)-O(2) bond lengths are 2.20 Å. Both Li(1)-O(3) bond lengths are 2.23 Å. V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. Both V(1)-O(1) bond lengths are 1.93 Å. All V(1)-O(3) bond lengths are 1.90 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CrO6 octahedra that share edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. Both Cr(1)-O(2) bond lengths are 1.99 Å. All Cr(1)-O(3) bond lengths are 2.02 Å. In the second Cr site, Cr(2) 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)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 9-12°. Both Cr(2)-O(1) bond lengths are 2.05 Å. Both Cr(2)-O(2) bond lengths are 2.02 Å. Both Cr(2)-O(3) bond lengths are 2.05 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(1), and two equivalent Cr(2) atoms to form OLi2VCr2 square pyramids that share corners with five equivalent O(1)Li2VCr2 square pyramids and edges with four equivalent O(2)Li2Cr3 square pyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Cr(1), and two equivalent Cr(2) atoms to form OLi2Cr3 square pyramids that share corners with five equivalent O(2)Li2Cr3 square pyramids and edges with four equivalent O(1)Li2VCr2 square pyramids. 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.