Li3Cr3FeO8 crystallizes in the monoclinic P2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with four equivalent Cr(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)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) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with four equivalent Cr(2)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. 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(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. There are three inequivalent Cr sites. In the first Cr site, Cr(1) 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,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the second Cr site, Cr(2) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the third Cr site, Cr(3) is bonded to two equivalent O(2) and four equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(4) and four equivalent O(6) atoms to form FeO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. In the second Fe site, Fe(2) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form FeO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Cr(2), and two equivalent Cr(1) atoms to form OLi3Cr3 octahedra that share corners with two equivalent O(1)Li3Cr3 octahedra, corners with four equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(3)Li2Cr2Fe square pyramids, edges with two equivalent O(4)Li2Cr2Fe square pyramids, edges with four equivalent O(5)Li2Cr2Fe square pyramids, and edges with four equivalent O(6)Li2Cr2Fe square pyramids. 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(3), and two equivalent Cr(1) atoms to form OLi3Cr3 octahedra that share corners with two equivalent O(2)Li3Cr3 octahedra, corners with four equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(3)Li2Cr2Fe square pyramids, edges with two equivalent O(4)Li2Cr2Fe square pyramids, edges with four equivalent O(5)Li2Cr2Fe square pyramids, and edges with four equivalent O(6)Li2Cr2Fe square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to two equivalent Li(3), two equivalent Cr(1), and one Fe(2) atom to form OLi2Cr2Fe square pyramids that share  a cornercorner with one O(3)Li2Cr2Fe square pyramid, corners with four equivalent O(4)Li2Cr2Fe square pyramids, corners with four equivalent O(6)Li2Cr2Fe square pyramids, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, and edges with four equivalent O(5)Li2Cr2Fe square pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(3), two equivalent Cr(1), and one Fe(1) atom to form OLi2Cr2Fe square pyramids that share  a cornercorner with one O(4)Li2Cr2Fe square pyramid, corners with four equivalent O(3)Li2Cr2Fe square pyramids, corners with four equivalent O(5)Li2Cr2Fe square pyramids, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, and edges with four equivalent O(6)Li2Cr2Fe square pyramids. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Cr(1), one Cr(2), and one Fe(2) atom to form OLi2Cr2Fe square pyramids that share corners with two equivalent O(4)Li2Cr2Fe square pyramids, corners with two equivalent O(6)Li2Cr2Fe square pyramids, corners with five equivalent O(5)Li2Cr2Fe square pyramids, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(3)Li2Cr2Fe square pyramids, and edges with two equivalent O(5)Li2Cr2Fe square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Cr(1), one Cr(3), and one Fe(1) atom to form OLi2Cr2Fe square pyramids that share corners with two equivalent O(3)Li2Cr2Fe square pyramids, corners with two equivalent O(5)Li2Cr2Fe square pyramids, corners with five equivalent O(6)Li2Cr2Fe square pyramids, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(4)Li2Cr2Fe square pyramids, and edges with two equivalent O(6)Li2Cr2Fe square pyramids.
Li3Cr3FeO8 crystallizes in the monoclinic P2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Cr(2)O6 octahedra, corners with four equivalent Cr(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Li(1)-O(1) bond lengths are 2.18 Å. All Li(1)-O(6) bond lengths are 2.17 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Cr(3)O6 octahedra, corners with four equivalent Cr(2)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. Both Li(2)-O(2) bond lengths are 2.17 Å. All Li(2)-O(5) bond lengths are 2.18 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(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The Li(3)-O(1) bond length is 2.17 Å. The Li(3)-O(2) bond length is 2.17 Å. The Li(3)-O(3) bond length is 2.19 Å. The Li(3)-O(4) bond length is 2.16 Å. The Li(3)-O(5) bond length is 2.18 Å. The Li(3)-O(6) bond length is 2.17 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) 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,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra,  an edgeedge with one Cr(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. 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(3) bond length is 2.06 Å. The Cr(1)-O(4) bond length is 2.00 Å. The Cr(1)-O(5) bond length is 2.05 Å. The Cr(1)-O(6) bond length is 2.03 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Both Cr(2)-O(1) bond lengths are 2.03 Å. All Cr(2)-O(5) bond lengths are 2.03 Å. In the third Cr site, Cr(3) is bonded to two equivalent O(2) and four equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Cr(3)-O(2) bond lengths are 2.04 Å. All Cr(3)-O(6) bond lengths are 2.03 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(4) and four equivalent O(6) atoms to form FeO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. Both Fe(1)-O(4) bond lengths are 2.04 Å. All Fe(1)-O(6) bond lengths are 1.99 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form FeO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. Both Fe(2)-O(3) bond lengths are 1.92 Å. All Fe(2)-O(5) bond lengths are 1.96 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Cr(2), and two equivalent Cr(1) atoms to form OLi3Cr3 octahedra that share corners with two equivalent O(1)Li3Cr3 octahedra, corners with four equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(3)Li2Cr2Fe square pyramids, edges with two equivalent O(4)Li2Cr2Fe square pyramids, edges with four equivalent O(5)Li2Cr2Fe square pyramids, and edges with four equivalent O(6)Li2Cr2Fe square pyramids. 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(3), and two equivalent Cr(1) atoms to form OLi3Cr3 octahedra that share corners with two equivalent O(2)Li3Cr3 octahedra, corners with four equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(3)Li2Cr2Fe square pyramids, edges with two equivalent O(4)Li2Cr2Fe square pyramids, edges with four equivalent O(5)Li2Cr2Fe square pyramids, and edges with four equivalent O(6)Li2Cr2Fe square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to two equivalent Li(3), two equivalent Cr(1), and one Fe(2) atom to form OLi2Cr2Fe square pyramids that share  a cornercorner with one O(3)Li2Cr2Fe square pyramid, corners with four equivalent O(4)Li2Cr2Fe square pyramids, corners with four equivalent O(6)Li2Cr2Fe square pyramids, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, and edges with four equivalent O(5)Li2Cr2Fe square pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(3), two equivalent Cr(1), and one Fe(1) atom to form OLi2Cr2Fe square pyramids that share  a cornercorner with one O(4)Li2Cr2Fe square pyramid, corners with four equivalent O(3)Li2Cr2Fe square pyramids, corners with four equivalent O(5)Li2Cr2Fe square pyramids, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, and edges with four equivalent O(6)Li2Cr2Fe square pyramids. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Cr(1), one Cr(2), and one Fe(2) atom to form OLi2Cr2Fe square pyramids that share corners with two equivalent O(4)Li2Cr2Fe square pyramids, corners with two equivalent O(6)Li2Cr2Fe square pyramids, corners with five equivalent O(5)Li2Cr2Fe square pyramids, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(3)Li2Cr2Fe square pyramids, and edges with two equivalent O(5)Li2Cr2Fe square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Cr(1), one Cr(3), and one Fe(1) atom to form OLi2Cr2Fe square pyramids that share corners with two equivalent O(3)Li2Cr2Fe square pyramids, corners with two equivalent O(5)Li2Cr2Fe square pyramids, corners with five equivalent O(6)Li2Cr2Fe square pyramids, edges with two equivalent O(1)Li3Cr3 octahedra, edges with two equivalent O(2)Li3Cr3 octahedra, edges with two equivalent O(4)Li2Cr2Fe square pyramids, and edges with two equivalent O(6)Li2Cr2Fe square pyramids.