Li3V2Cr2O8 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 LiO6 octahedra that share corners with six equivalent V(2)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(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)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 4-7°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) 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 V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 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(2)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 4-7°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form 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 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 5-7°. 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 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 V(2)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), two equivalent O(3), and two equivalent O(4) atoms to form 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 V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one V(2), one Cr(1), and one Cr(2) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(2)Li2V2Cr square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with five equivalent O(1)Li2VCr2 square pyramids, edges with four equivalent O(4)Li3V2Cr octahedra, edges with two equivalent O(2)Li2V2Cr square pyramids, and edges with two equivalent O(3)Li2VCr2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one Cr(1) atom to form OLi2V2Cr square pyramids that share corners with two equivalent O(1)Li2VCr2 square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with five equivalent O(2)Li2V2Cr square pyramids, edges with four equivalent O(4)Li3V2Cr octahedra, edges with two equivalent O(1)Li2VCr2 square pyramids, and edges with two equivalent O(3)Li2VCr2 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(1), one Cr(1), and one Cr(2) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(2)Li2V2Cr square pyramids, corners with two equivalent O(1)Li2VCr2 square pyramids, corners with five equivalent O(3)Li2VCr2 square pyramids, edges with four equivalent O(4)Li3V2Cr octahedra, edges with two equivalent O(2)Li2V2Cr square pyramids, and edges with two equivalent O(1)Li2VCr2 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one Cr(2) atom to form OLi3V2Cr octahedra that share corners with six equivalent O(4)Li3V2Cr octahedra, edges with four equivalent O(2)Li2V2Cr square pyramids, edges with four equivalent O(1)Li2VCr2 square pyramids, and edges with four equivalent O(3)Li2VCr2 square pyramids. The corner-sharing octahedra are not tilted.
Li3V2Cr2O8 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 LiO6 octahedra that share corners with six equivalent V(2)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(1)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Li(1)-O(1) bond lengths are 2.15 Å. Both Li(1)-O(2) bond lengths are 2.18 Å. Both Li(1)-O(4) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)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 4-7°. Both Li(2)-O(2) bond lengths are 2.16 Å. Both Li(2)-O(3) bond lengths are 2.16 Å. Both Li(2)-O(4) bond lengths are 2.16 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) 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 V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both Li(3)-O(1) bond lengths are 2.14 Å. Both Li(3)-O(3) bond lengths are 2.18 Å. Both Li(3)-O(4) bond lengths are 2.13 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 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(2)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 4-7°. Both V(1)-O(2) bond lengths are 2.00 Å. Both V(1)-O(3) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form 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 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 5-7°. Both V(2)-O(1) bond lengths are 2.00 Å. Both V(2)-O(2) bond lengths are 2.01 Å. Both V(2)-O(4) bond lengths are 2.02 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 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 V(2)O6 octahedra, and edges with two equivalent Cr(2)O6 octahedra. Both Cr(1)-O(1) bond lengths are 1.97 Å. Both Cr(1)-O(2) bond lengths are 1.99 Å. Both Cr(1)-O(3) bond lengths are 1.98 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form 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 V(2)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both Cr(2)-O(1) bond lengths are 2.02 Å. Both Cr(2)-O(3) bond lengths are 2.01 Å. Both Cr(2)-O(4) bond lengths are 2.02 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one V(2), one Cr(1), and one Cr(2) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(2)Li2V2Cr square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with five equivalent O(1)Li2VCr2 square pyramids, edges with four equivalent O(4)Li3V2Cr octahedra, edges with two equivalent O(2)Li2V2Cr square pyramids, and edges with two equivalent O(3)Li2VCr2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one Cr(1) atom to form OLi2V2Cr square pyramids that share corners with two equivalent O(1)Li2VCr2 square pyramids, corners with two equivalent O(3)Li2VCr2 square pyramids, corners with five equivalent O(2)Li2V2Cr square pyramids, edges with four equivalent O(4)Li3V2Cr octahedra, edges with two equivalent O(1)Li2VCr2 square pyramids, and edges with two equivalent O(3)Li2VCr2 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(1), one Cr(1), and one Cr(2) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(2)Li2V2Cr square pyramids, corners with two equivalent O(1)Li2VCr2 square pyramids, corners with five equivalent O(3)Li2VCr2 square pyramids, edges with four equivalent O(4)Li3V2Cr octahedra, edges with two equivalent O(2)Li2V2Cr square pyramids, and edges with two equivalent O(1)Li2VCr2 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one Cr(2) atom to form OLi3V2Cr octahedra that share corners with six equivalent O(4)Li3V2Cr octahedra, edges with four equivalent O(2)Li2V2Cr square pyramids, edges with four equivalent O(1)Li2VCr2 square pyramids, and edges with four equivalent O(3)Li2VCr2 square pyramids. The corner-sharing octahedra are not tilted.