Li3Cr4O8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) 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 three equivalent Cr(4)O6 octahedra, corners with three equivalent Cr(6)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, edges with two equivalent Cr(5)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second Li site, Li(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 LiO6 octahedra that share corners with three equivalent Cr(3)O6 octahedra, corners with three equivalent Cr(5)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(3)O6 octahedra,  an edgeedge with one Cr(4)O6 octahedra,  an edgeedge with one Cr(5)O6 octahedra,  an edgeedge with one Cr(6)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are six inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(5) and four equivalent O(3) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(4)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(5)O6 octahedra. In the second Cr site, Cr(2) is bonded to two equivalent O(6) and four equivalent O(4) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(6)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. In the third Cr site, Cr(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) 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 Cr(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Cr(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the fourth Cr site, Cr(4) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 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(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the fifth Cr site, Cr(5) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) 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 Cr(1)O6 octahedra, edges with two equivalent Cr(4)O6 octahedra, and edges with two equivalent Cr(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the sixth Cr site, Cr(6) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. There are six inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(4), and one Cr(5) atom to form OLi2Cr3 square pyramids that share  a cornercorner with one O(5)Li2Cr3 square pyramid,  a cornercorner with one O(6)Li2Cr3 square pyramid, corners with three equivalent O(4)Li2Cr3 square pyramids, corners with four equivalent O(3)Li2Cr3 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(3)Li2Cr3 square pyramids, and edges with two equivalent O(5)Li2Cr3 square pyramids. In the second O site, O(4) is bonded to one Li(1), one Li(2), one Cr(2), one Cr(3), and one Cr(6) atom to form OLi2Cr3 square pyramids that share  a cornercorner with one O(5)Li2Cr3 square pyramid,  a cornercorner with one O(6)Li2Cr3 square pyramid, corners with three equivalent O(3)Li2Cr3 square pyramids, corners with four equivalent O(4)Li2Cr3 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(4)Li2Cr3 square pyramids, and edges with two equivalent O(6)Li2Cr3 square pyramids. In the third O site, O(5) is bonded to two equivalent Li(2), one Cr(1), and two equivalent Cr(5) atoms to form OLi2Cr3 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with two equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(6)Li2Cr3 square pyramids, corners with three equivalent O(5)Li2Cr3 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra, and edges with four equivalent O(3)Li2Cr3 square pyramids. In the fourth O site, O(6) is bonded to two equivalent Li(2), one Cr(2), and two equivalent Cr(3) atoms to form OLi2Cr3 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with two equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(5)Li2Cr3 square pyramids, corners with three equivalent O(6)Li2Cr3 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra, and edges with four equivalent O(4)Li2Cr3 square pyramids. In the fifth O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Cr(4), and two equivalent Cr(5) atoms 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(6)Li2Cr3 square pyramid, edges with two equivalent O(4)Li2Cr3 square pyramids, edges with three equivalent O(5)Li2Cr3 square pyramids, and edges with six equivalent O(3)Li2Cr3 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the sixth O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Cr(6), and two equivalent Cr(3) atoms 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(5)Li2Cr3 square pyramid, edges with two equivalent O(3)Li2Cr3 square pyramids, edges with three equivalent O(6)Li2Cr3 square pyramids, and edges with six equivalent O(4)Li2Cr3 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°.
Li3Cr4O8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) 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 three equivalent Cr(4)O6 octahedra, corners with three equivalent Cr(6)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, edges with two equivalent Cr(5)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. The Li(1)-O(1) bond length is 2.17 Å. The Li(1)-O(2) bond length is 2.17 Å. Both Li(1)-O(3) bond lengths are 2.18 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), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with three equivalent Cr(3)O6 octahedra, corners with three equivalent Cr(5)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(3)O6 octahedra,  an edgeedge with one Cr(4)O6 octahedra,  an edgeedge with one Cr(5)O6 octahedra,  an edgeedge with one Cr(6)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. The Li(2)-O(1) bond length is 2.17 Å. The Li(2)-O(2) bond length is 2.18 Å. The Li(2)-O(3) bond length is 2.17 Å. The Li(2)-O(4) bond length is 2.16 Å. The Li(2)-O(5) bond length is 2.18 Å. The Li(2)-O(6) bond length is 2.19 Å. There are six inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(5) and four equivalent O(3) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(4)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(5)O6 octahedra. Both Cr(1)-O(5) bond lengths are 1.95 Å. All Cr(1)-O(3) bond lengths are 1.94 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(6) and four equivalent O(4) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(6)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. Both Cr(2)-O(6) bond lengths are 1.93 Å. All Cr(2)-O(4) bond lengths are 1.95 Å. In the third Cr site, Cr(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) 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 Cr(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Cr(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Cr(3)-O(2) bond lengths are 2.03 Å. Both Cr(3)-O(4) bond lengths are 2.04 Å. Both Cr(3)-O(6) bond lengths are 2.04 Å. In the fourth Cr site, Cr(4) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 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(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Cr(4)-O(1) bond lengths are 2.02 Å. All Cr(4)-O(3) bond lengths are 2.04 Å. In the fifth Cr site, Cr(5) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) 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 Cr(1)O6 octahedra, edges with two equivalent Cr(4)O6 octahedra, and edges with two equivalent Cr(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. Both Cr(5)-O(1) bond lengths are 2.03 Å. Both Cr(5)-O(3) bond lengths are 2.03 Å. Both Cr(5)-O(5) bond lengths are 2.03 Å. In the sixth Cr site, Cr(6) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. Both Cr(6)-O(2) bond lengths are 2.03 Å. All Cr(6)-O(4) bond lengths are 2.04 Å. There are six inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(4), and one Cr(5) atom to form OLi2Cr3 square pyramids that share  a cornercorner with one O(5)Li2Cr3 square pyramid,  a cornercorner with one O(6)Li2Cr3 square pyramid, corners with three equivalent O(4)Li2Cr3 square pyramids, corners with four equivalent O(3)Li2Cr3 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(3)Li2Cr3 square pyramids, and edges with two equivalent O(5)Li2Cr3 square pyramids. In the second O site, O(4) is bonded to one Li(1), one Li(2), one Cr(2), one Cr(3), and one Cr(6) atom to form OLi2Cr3 square pyramids that share  a cornercorner with one O(5)Li2Cr3 square pyramid,  a cornercorner with one O(6)Li2Cr3 square pyramid, corners with three equivalent O(3)Li2Cr3 square pyramids, corners with four equivalent O(4)Li2Cr3 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(4)Li2Cr3 square pyramids, and edges with two equivalent O(6)Li2Cr3 square pyramids. In the third O site, O(5) is bonded to two equivalent Li(2), one Cr(1), and two equivalent Cr(5) atoms to form OLi2Cr3 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with two equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(6)Li2Cr3 square pyramids, corners with three equivalent O(5)Li2Cr3 square pyramids,  an edgeedge with one O(2)Li3Cr3 octahedra, edges with three equivalent O(1)Li3Cr3 octahedra, and edges with four equivalent O(3)Li2Cr3 square pyramids. In the fourth O site, O(6) is bonded to two equivalent Li(2), one Cr(2), and two equivalent Cr(3) atoms to form OLi2Cr3 square pyramids that share corners with two equivalent O(3)Li2Cr3 square pyramids, corners with two equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(5)Li2Cr3 square pyramids, corners with three equivalent O(6)Li2Cr3 square pyramids,  an edgeedge with one O(1)Li3Cr3 octahedra, edges with three equivalent O(2)Li3Cr3 octahedra, and edges with four equivalent O(4)Li2Cr3 square pyramids. In the fifth O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Cr(4), and two equivalent Cr(5) atoms 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(6)Li2Cr3 square pyramid, edges with two equivalent O(4)Li2Cr3 square pyramids, edges with three equivalent O(5)Li2Cr3 square pyramids, and edges with six equivalent O(3)Li2Cr3 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the sixth O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Cr(6), and two equivalent Cr(3) atoms 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(5)Li2Cr3 square pyramid, edges with two equivalent O(3)Li2Cr3 square pyramids, edges with three equivalent O(6)Li2Cr3 square pyramids, and edges with six equivalent O(4)Li2Cr3 square pyramids. The corner-sharing octahedral tilt angles range from 0-1°.