Li3VCr3O8 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with three equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(4)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(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the second Li site, Li(2) is bonded to one O(3), one O(7), two equivalent O(1), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one 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, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the third Li site, Li(3) is bonded to one O(4), one O(8), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(3)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, and edges with two equivalent Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. V(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(4)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 Cr(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(7) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the third Cr site, Cr(3) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form CrO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the fourth Cr site, Cr(4) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. There are eight inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one V(1), one Cr(2), and one Cr(3) atom to form OLi2VCr2 square pyramids that share  a cornercorner with one O(3)Li2VCr2 square pyramid, corners with two equivalent O(6)Li2VCr2 square pyramids, corners with three equivalent O(7)Li2VCr2 square pyramids, corners with three equivalent O(8)Li2VCr2 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid, and  an edgeedge with one O(7)Li2VCr2 square pyramid. In the second O site, O(4) is bonded to one Li(1), one Li(3), one V(1), one Cr(1), and one Cr(4) atom to form OLi2VCr2 square pyramids that share  a cornercorner with one O(4)Li2VCr2 square pyramid, corners with two equivalent O(5)Li2VCr2 square pyramids, corners with three equivalent O(7)Li2VCr2 square pyramids, corners with three equivalent O(8)Li2VCr2 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid, and  an edgeedge with one O(8)Li2VCr2 square pyramid. In the third O site, O(5) is bonded to two equivalent 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(4)Li2VCr2 square pyramids, corners with two equivalent O(5)Li2VCr2 square pyramids, corners with two equivalent O(8)Li2VCr2 square pyramids, corners with three equivalent O(6)Li2VCr2 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(7)Li2VCr2 square pyramid, and  an edgeedge with one O(8)Li2VCr2 square pyramid. In the fourth O site, O(6) is bonded to two equivalent Li(2), one V(1), one Cr(1), and one Cr(3) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(3)Li2VCr2 square pyramids, corners with two equivalent O(6)Li2VCr2 square pyramids, corners with two equivalent O(7)Li2VCr2 square pyramids, corners with three equivalent O(5)Li2VCr2 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(7)Li2VCr2 square pyramid, and  an edgeedge with one O(8)Li2VCr2 square pyramid. In the fifth O site, O(7) 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  a cornercorner with one O(7)Li2VCr2 square pyramid, corners with two equivalent O(6)Li2VCr2 square pyramids, corners with three equivalent O(3)Li2VCr2 square pyramids, corners with three equivalent O(4)Li2VCr2 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid, and  an edgeedge with one O(8)Li2VCr2 square pyramid. In the sixth O site, O(8) is bonded to one Li(1), one Li(3), one V(1), one Cr(3), and one Cr(4) atom to form OLi2VCr2 square pyramids that share  a cornercorner with one O(8)Li2VCr2 square pyramid, corners with two equivalent O(5)Li2VCr2 square pyramids, corners with three equivalent O(3)Li2VCr2 square pyramids, corners with three equivalent O(4)Li2VCr2 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid, and  an edgeedge with one O(7)Li2VCr2 square pyramid. In the seventh O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Cr(1), one Cr(2), and one Cr(3) atom to form OLi3Cr3 octahedra that share corners with three equivalent O(1)Li3Cr3 octahedra, corners with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(8)Li2VCr2 square pyramid, edges with three equivalent O(3)Li2VCr2 square pyramids, edges with three equivalent O(6)Li2VCr2 square pyramids, and edges with three equivalent O(7)Li2VCr2 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the eighth O site, O(2) is bonded to one Li(1), two equivalent Li(3), one Cr(1), one Cr(3), and one Cr(4) atom to form OLi3Cr3 octahedra that share corners with three equivalent O(1)Li3Cr3 octahedra, corners with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid,  an edgeedge with one O(7)Li2VCr2 square pyramid, edges with three equivalent O(4)Li2VCr2 square pyramids, edges with three equivalent O(5)Li2VCr2 square pyramids, and edges with three equivalent O(8)Li2VCr2 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°.
Li3VCr3O8 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with three equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(4)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(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Li(1)-O(1) bond length is 2.19 Å. The Li(1)-O(2) bond length is 2.19 Å. The Li(1)-O(3) bond length is 2.16 Å. The Li(1)-O(4) bond length is 2.16 Å. The Li(1)-O(7) bond length is 2.18 Å. The Li(1)-O(8) bond length is 2.18 Å. In the second Li site, Li(2) is bonded to one O(3), one O(7), two equivalent O(1), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one 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, and edges with two equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(7) bond length is 2.18 Å. There is one shorter (2.16 Å) and one longer (2.17 Å) Li(2)-O(1) bond length. Both Li(2)-O(6) bond lengths are 2.17 Å. In the third Li site, Li(3) is bonded to one O(4), one O(8), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(3)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, and edges with two equivalent Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Li(3)-O(4) bond length is 2.18 Å. The Li(3)-O(8) bond length is 2.20 Å. There is one shorter (2.16 Å) and one longer (2.17 Å) Li(3)-O(2) bond length. Both Li(3)-O(5) bond lengths are 2.17 Å. V(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(4)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 Cr(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The V(1)-O(3) bond length is 1.95 Å. The V(1)-O(4) bond length is 1.96 Å. The V(1)-O(5) bond length is 1.98 Å. The V(1)-O(6) bond length is 1.98 Å. The V(1)-O(7) bond length is 1.95 Å. The V(1)-O(8) bond length is 1.95 Å. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Cr(1)-O(1) bond length is 2.03 Å. The Cr(1)-O(2) bond length is 2.03 Å. The Cr(1)-O(4) bond length is 2.05 Å. The Cr(1)-O(5) bond length is 2.04 Å. The Cr(1)-O(6) bond length is 2.04 Å. The Cr(1)-O(7) bond length is 2.05 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(7) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Both Cr(2)-O(1) bond lengths are 2.04 Å. Both Cr(2)-O(3) bond lengths are 2.04 Å. Both Cr(2)-O(7) bond lengths are 2.04 Å. In the third Cr site, Cr(3) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form CrO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Cr(3)-O(1) bond length is 2.04 Å. The Cr(3)-O(2) bond length is 2.04 Å. The Cr(3)-O(3) bond length is 2.05 Å. The Cr(3)-O(5) bond length is 2.04 Å. The Cr(3)-O(6) bond length is 2.03 Å. The Cr(3)-O(8) bond length is 2.04 Å. In the fourth Cr site, Cr(4) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Both Cr(4)-O(2) bond lengths are 2.04 Å. Both Cr(4)-O(4) bond lengths are 2.04 Å. Both Cr(4)-O(8) bond lengths are 2.04 Å. There are eight inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one V(1), one Cr(2), and one Cr(3) atom to form OLi2VCr2 square pyramids that share  a cornercorner with one O(3)Li2VCr2 square pyramid, corners with two equivalent O(6)Li2VCr2 square pyramids, corners with three equivalent O(7)Li2VCr2 square pyramids, corners with three equivalent O(8)Li2VCr2 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid, and  an edgeedge with one O(7)Li2VCr2 square pyramid. In the second O site, O(4) is bonded to one Li(1), one Li(3), one V(1), one Cr(1), and one Cr(4) atom to form OLi2VCr2 square pyramids that share  a cornercorner with one O(4)Li2VCr2 square pyramid, corners with two equivalent O(5)Li2VCr2 square pyramids, corners with three equivalent O(7)Li2VCr2 square pyramids, corners with three equivalent O(8)Li2VCr2 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid, and  an edgeedge with one O(8)Li2VCr2 square pyramid. In the third O site, O(5) is bonded to two equivalent 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(4)Li2VCr2 square pyramids, corners with two equivalent O(5)Li2VCr2 square pyramids, corners with two equivalent O(8)Li2VCr2 square pyramids, corners with three equivalent O(6)Li2VCr2 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(7)Li2VCr2 square pyramid, and  an edgeedge with one O(8)Li2VCr2 square pyramid. In the fourth O site, O(6) is bonded to two equivalent Li(2), one V(1), one Cr(1), and one Cr(3) atom to form OLi2VCr2 square pyramids that share corners with two equivalent O(3)Li2VCr2 square pyramids, corners with two equivalent O(6)Li2VCr2 square pyramids, corners with two equivalent O(7)Li2VCr2 square pyramids, corners with three equivalent O(5)Li2VCr2 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(7)Li2VCr2 square pyramid, and  an edgeedge with one O(8)Li2VCr2 square pyramid. In the fifth O site, O(7) 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  a cornercorner with one O(7)Li2VCr2 square pyramid, corners with two equivalent O(6)Li2VCr2 square pyramids, corners with three equivalent O(3)Li2VCr2 square pyramids, corners with three equivalent O(4)Li2VCr2 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid, and  an edgeedge with one O(8)Li2VCr2 square pyramid. In the sixth O site, O(8) is bonded to one Li(1), one Li(3), one V(1), one Cr(3), and one Cr(4) atom to form OLi2VCr2 square pyramids that share  a cornercorner with one O(8)Li2VCr2 square pyramid, corners with two equivalent O(5)Li2VCr2 square pyramids, corners with three equivalent O(3)Li2VCr2 square pyramids, corners with three equivalent O(4)Li2VCr2 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid, and  an edgeedge with one O(7)Li2VCr2 square pyramid. In the seventh O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Cr(1), one Cr(2), and one Cr(3) atom to form OLi3Cr3 octahedra that share corners with three equivalent O(1)Li3Cr3 octahedra, corners with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(4)Li2VCr2 square pyramid,  an edgeedge with one O(5)Li2VCr2 square pyramid,  an edgeedge with one O(8)Li2VCr2 square pyramid, edges with three equivalent O(3)Li2VCr2 square pyramids, edges with three equivalent O(6)Li2VCr2 square pyramids, and edges with three equivalent O(7)Li2VCr2 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the eighth O site, O(2) is bonded to one Li(1), two equivalent Li(3), one Cr(1), one Cr(3), and one Cr(4) atom to form OLi3Cr3 octahedra that share corners with three equivalent O(1)Li3Cr3 octahedra, corners with three equivalent O(2)Li3Cr3 octahedra,  an edgeedge with one O(3)Li2VCr2 square pyramid,  an edgeedge with one O(6)Li2VCr2 square pyramid,  an edgeedge with one O(7)Li2VCr2 square pyramid, edges with three equivalent O(4)Li2VCr2 square pyramids, edges with three equivalent O(5)Li2VCr2 square pyramids, and edges with three equivalent O(8)Li2VCr2 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°.