Li3VCr3O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-23°. 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 distorted 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(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-25°. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with six equivalent Cr(3)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 12-23°. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-23°. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(3)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 distorted 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(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-25°. In the third Cr site, Cr(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted CrO6 octahedra that share corners with six equivalent Li(3)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 12-23°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), one Cr(1), and one Cr(2) atom to form distorted OLi2VCr2 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with two equivalent O(4)Li2VCr2 square pyramids, corners with five equivalent O(1)Li2VCr2 square pyramids, edges with two equivalent O(3)Li2Cr3 square pyramids, and edges with two equivalent O(4)Li2VCr2 square pyramids. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one V(1), one Cr(2), and one Cr(3) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Cr(1), one Cr(2), and one Cr(3) atom to form distorted OLi2Cr3 square pyramids that share corners with two equivalent O(1)Li2VCr2 square pyramids, corners with two equivalent O(4)Li2VCr2 square pyramids, corners with five equivalent O(3)Li2Cr3 square pyramids, edges with two equivalent O(1)Li2VCr2 square pyramids, and edges with two equivalent O(4)Li2VCr2 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(1), one Cr(1), and one Cr(3) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with two equivalent O(1)Li2VCr2 square pyramids, corners with five equivalent O(4)Li2VCr2 square pyramids, edges with two equivalent O(3)Li2Cr3 square pyramids, and edges with two equivalent O(1)Li2VCr2 square pyramids.
Li3VCr3O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-23°. Both Li(1)-O(1) bond lengths are 2.21 Å. Both Li(1)-O(2) bond lengths are 1.97 Å. Both Li(1)-O(4) bond lengths are 2.36 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 distorted 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(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-25°. Both Li(2)-O(1) bond lengths are 2.00 Å. Both Li(2)-O(2) bond lengths are 2.21 Å. Both Li(2)-O(3) bond lengths are 2.48 Å. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with six equivalent Cr(3)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 12-23°. Both Li(3)-O(2) bond lengths are 2.51 Å. Both Li(3)-O(3) bond lengths are 2.26 Å. Both Li(3)-O(4) bond lengths are 2.03 Å. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-23°. Both V(1)-O(1) bond lengths are 2.05 Å. Both V(1)-O(2) bond lengths are 2.36 Å. Both V(1)-O(4) bond lengths are 1.83 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. Both Cr(1)-O(1) bond lengths are 1.72 Å. Both Cr(1)-O(3) bond lengths are 2.37 Å. Both Cr(1)-O(4) bond lengths are 2.05 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 distorted 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(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-25°. Both Cr(2)-O(1) bond lengths are 2.32 Å. Both Cr(2)-O(2) bond lengths are 2.05 Å. Both Cr(2)-O(3) bond lengths are 1.74 Å. In the third Cr site, Cr(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted CrO6 octahedra that share corners with six equivalent Li(3)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 12-23°. Both Cr(3)-O(2) bond lengths are 1.70 Å. Both Cr(3)-O(3) bond lengths are 2.00 Å. Both Cr(3)-O(4) bond lengths are 2.25 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), one Cr(1), and one Cr(2) atom to form distorted OLi2VCr2 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with two equivalent O(4)Li2VCr2 square pyramids, corners with five equivalent O(1)Li2VCr2 square pyramids, edges with two equivalent O(3)Li2Cr3 square pyramids, and edges with two equivalent O(4)Li2VCr2 square pyramids. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one V(1), one Cr(2), and one Cr(3) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Cr(1), one Cr(2), and one Cr(3) atom to form distorted OLi2Cr3 square pyramids that share corners with two equivalent O(1)Li2VCr2 square pyramids, corners with two equivalent O(4)Li2VCr2 square pyramids, corners with five equivalent O(3)Li2Cr3 square pyramids, edges with two equivalent O(1)Li2VCr2 square pyramids, and edges with two equivalent O(4)Li2VCr2 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(1), one Cr(1), and one Cr(3) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with two equivalent O(1)Li2VCr2 square pyramids, corners with five equivalent O(4)Li2VCr2 square pyramids, edges with two equivalent O(3)Li2Cr3 square pyramids, and edges with two equivalent O(1)Li2VCr2 square pyramids.