Li3VCr3O8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the second Li site, Li(2) 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 Li(2)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 6-9°. V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)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(2)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, 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 6-9°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Cr(1), and two equivalent Cr(2) atoms to form OLi2Cr3 square pyramids that share corners with four equivalent O(2)Li2VCr2 square pyramids, corners with five equivalent O(1)Li2Cr3 square pyramids, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(2)Li2VCr2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), one Cr(1), and one Cr(2) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(1)Li2Cr3 square pyramids, corners with seven equivalent O(2)Li2VCr2 square pyramids, edges with four equivalent O(3)Li3VCr2 octahedra, edges with two equivalent O(1)Li2Cr3 square pyramids, and edges with two equivalent O(2)Li2VCr2 square pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), one V(1), and two equivalent Cr(2) atoms to form OLi3VCr2 octahedra that share corners with six equivalent O(3)Li3VCr2 octahedra, edges with four equivalent O(1)Li2Cr3 square pyramids, and edges with eight equivalent O(2)Li2VCr2 square pyramids. The corner-sharing octahedra are not tilted.
Li3VCr3O8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Li(1)-O(3) bond lengths are 2.23 Å. All Li(1)-O(2) bond lengths are 2.22 Å. In the second Li site, Li(2) 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 Li(2)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 6-9°. Both Li(2)-O(1) bond lengths are 2.18 Å. Both Li(2)-O(2) bond lengths are 2.22 Å. Both Li(2)-O(3) bond lengths are 2.15 Å. V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both V(1)-O(3) bond lengths are 2.02 Å. All V(1)-O(2) bond lengths are 1.97 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. Both Cr(1)-O(1) bond lengths are 1.99 Å. All Cr(1)-O(2) bond lengths are 2.01 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(2)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, 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 6-9°. Both Cr(2)-O(1) bond lengths are 2.01 Å. Both Cr(2)-O(2) bond lengths are 2.04 Å. Both Cr(2)-O(3) bond lengths are 2.03 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Cr(1), and two equivalent Cr(2) atoms to form OLi2Cr3 square pyramids that share corners with four equivalent O(2)Li2VCr2 square pyramids, corners with five equivalent O(1)Li2Cr3 square pyramids, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(2)Li2VCr2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), one Cr(1), and one Cr(2) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(1)Li2Cr3 square pyramids, corners with seven equivalent O(2)Li2VCr2 square pyramids, edges with four equivalent O(3)Li3VCr2 octahedra, edges with two equivalent O(1)Li2Cr3 square pyramids, and edges with two equivalent O(2)Li2VCr2 square pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), one V(1), and two equivalent Cr(2) atoms to form OLi3VCr2 octahedra that share corners with six equivalent O(3)Li3VCr2 octahedra, edges with four equivalent O(1)Li2Cr3 square pyramids, and edges with eight equivalent O(2)Li2VCr2 square pyramids. The corner-sharing octahedra are not tilted.