Li4VCr3O8 is alpha Po-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(6), 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(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom 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 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 5-6°. V(1) is bonded to one O(5), one O(6), two equivalent O(3), 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 Cr(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) 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 V(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom 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 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 5-6°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(3), one Cr(1), and two equivalent Cr(2) atoms to form OLi3Cr3 octahedra that share corners with six equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(5)Li3VCr2 octahedra, edges with two equivalent O(6)Li3VCr2 octahedra, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), one Cr(1), and two equivalent Cr(2) atoms to form OLi3Cr3 octahedra that share corners with six equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(5)Li3VCr2 octahedra, edges with two equivalent O(6)Li3VCr2 octahedra, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Cr(1), and one Cr(2) atom to form OLi3VCr2 octahedra that share corners with six equivalent O(4)Li3VCr2 octahedra, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(3)Li3VCr2 octahedra, edges with two equivalent O(4)Li3VCr2 octahedra, edges with two equivalent O(5)Li3VCr2 octahedra, and edges with two equivalent O(6)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Cr(1), and one Cr(2) atom to form OLi3VCr2 octahedra that share corners with six equivalent O(3)Li3VCr2 octahedra, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(3)Li3VCr2 octahedra, edges with two equivalent O(4)Li3VCr2 octahedra, edges with two equivalent O(5)Li3VCr2 octahedra, and edges with two equivalent O(6)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(3), one V(1), and two equivalent Cr(2) atoms to form OLi3VCr2 octahedra that share corners with six equivalent O(6)Li3VCr2 octahedra, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Li(3), one V(1), and two equivalent Cr(2) atoms to form OLi3VCr2 octahedra that share corners with six equivalent O(5)Li3VCr2 octahedra, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li4VCr3O8 is alpha Po-derived structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(6), 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(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The Li(1)-O(5) bond length is 2.18 Å. The Li(1)-O(6) bond length is 2.15 Å. Both Li(1)-O(3) bond lengths are 2.15 Å. Both Li(1)-O(4) bond lengths are 2.17 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The Li(2)-O(1) bond length is 2.19 Å. The Li(2)-O(2) bond length is 2.18 Å. Both Li(2)-O(3) bond lengths are 2.18 Å. Both Li(2)-O(4) bond lengths are 2.17 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom 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 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 5-6°. The Li(3)-O(1) bond length is 2.18 Å. The Li(3)-O(2) bond length is 2.18 Å. The Li(3)-O(3) bond length is 2.19 Å. The Li(3)-O(4) bond length is 2.17 Å. The Li(3)-O(5) bond length is 2.17 Å. The Li(3)-O(6) bond length is 2.18 Å. V(1) is bonded to one O(5), one O(6), two equivalent O(3), 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 Cr(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The V(1)-O(5) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.05 Å. Both V(1)-O(3) bond lengths are 2.05 Å. Both V(1)-O(4) bond lengths are 2.05 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) 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 V(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The Cr(1)-O(1) bond length is 2.03 Å. The Cr(1)-O(2) bond length is 2.03 Å. Both Cr(1)-O(3) bond lengths are 2.04 Å. Both Cr(1)-O(4) bond lengths are 2.04 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom 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 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 5-6°. The Cr(2)-O(1) bond length is 2.03 Å. The Cr(2)-O(2) bond length is 2.03 Å. The Cr(2)-O(3) bond length is 2.04 Å. The Cr(2)-O(4) bond length is 2.04 Å. The Cr(2)-O(5) bond length is 2.04 Å. The Cr(2)-O(6) bond length is 2.04 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(3), one Cr(1), and two equivalent Cr(2) atoms to form OLi3Cr3 octahedra that share corners with six equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(5)Li3VCr2 octahedra, edges with two equivalent O(6)Li3VCr2 octahedra, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), one Cr(1), and two equivalent Cr(2) atoms to form OLi3Cr3 octahedra that share corners with six equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(5)Li3VCr2 octahedra, edges with two equivalent O(6)Li3VCr2 octahedra, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Cr(1), and one Cr(2) atom to form OLi3VCr2 octahedra that share corners with six equivalent O(4)Li3VCr2 octahedra, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(3)Li3VCr2 octahedra, edges with two equivalent O(4)Li3VCr2 octahedra, edges with two equivalent O(5)Li3VCr2 octahedra, and edges with two equivalent O(6)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Cr(1), and one Cr(2) atom to form OLi3VCr2 octahedra that share corners with six equivalent O(3)Li3VCr2 octahedra, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(3)Li3VCr2 octahedra, edges with two equivalent O(4)Li3VCr2 octahedra, edges with two equivalent O(5)Li3VCr2 octahedra, and edges with two equivalent O(6)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(3), one V(1), and two equivalent Cr(2) atoms to form OLi3VCr2 octahedra that share corners with six equivalent O(6)Li3VCr2 octahedra, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the sixth O site, O(6) is bonded to one Li(1), two equivalent Li(3), one V(1), and two equivalent Cr(2) atoms to form OLi3VCr2 octahedra that share corners with six equivalent O(5)Li3VCr2 octahedra, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with four equivalent O(3)Li3VCr2 octahedra, and edges with four equivalent O(4)Li3VCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.