Li3Cr4FeO8 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two 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(3) atoms to form LiO6 octahedra that share corners with six equivalent Cr(3)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(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Fe(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with six equivalent Cr(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the second Cr site, Cr(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the third Cr site, Cr(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)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(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. Fe(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Cr(3), and one Fe(1) atom to form OLi3Cr2Fe octahedra that share corners with six equivalent O(1)Li3Cr2Fe octahedra, edges with four equivalent O(3)Li2Cr4 octahedra, and edges with eight equivalent O(2)Li2Cr3Fe octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), one Cr(3), and one Fe(1) atom to form OLi2Cr3Fe octahedra that share corners with six equivalent O(2)Li2Cr3Fe octahedra, edges with four equivalent O(2)Li2Cr3Fe octahedra, edges with four equivalent O(3)Li2Cr4 octahedra, and edges with four equivalent O(1)Li3Cr2Fe octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to two equivalent Li(1), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms to form OLi2Cr4 octahedra that share corners with six equivalent O(3)Li2Cr4 octahedra, edges with four equivalent O(1)Li3Cr2Fe octahedra, and edges with eight equivalent O(2)Li2Cr3Fe octahedra. The corner-sharing octahedra are not tilted.
Li3Cr4FeO8 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two 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(3) atoms to form LiO6 octahedra that share corners with six equivalent Cr(3)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(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. Both Li(1)-O(1) bond lengths are 2.15 Å. Both Li(1)-O(2) bond lengths are 2.40 Å. Both Li(1)-O(3) bond lengths are 2.14 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Fe(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. Both Li(2)-O(1) bond lengths are 2.28 Å. All Li(2)-O(2) bond lengths are 2.07 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with six equivalent Cr(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. Both Cr(1)-O(3) bond lengths are 2.41 Å. All Cr(1)-O(2) bond lengths are 2.13 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CrO6 octahedra that share corners with six equivalent Cr(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. Both Cr(2)-O(3) bond lengths are 2.07 Å. All Cr(2)-O(2) bond lengths are 2.05 Å. In the third Cr site, Cr(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with six equivalent Li(1)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(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. Both Cr(3)-O(1) bond lengths are 2.02 Å. Both Cr(3)-O(2) bond lengths are 2.08 Å. Both Cr(3)-O(3) bond lengths are 2.04 Å. Fe(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. Both Fe(1)-O(1) bond lengths are 2.20 Å. All Fe(1)-O(2) bond lengths are 2.11 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Cr(3), and one Fe(1) atom to form OLi3Cr2Fe octahedra that share corners with six equivalent O(1)Li3Cr2Fe octahedra, edges with four equivalent O(3)Li2Cr4 octahedra, and edges with eight equivalent O(2)Li2Cr3Fe octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), one Cr(3), and one Fe(1) atom to form OLi2Cr3Fe octahedra that share corners with six equivalent O(2)Li2Cr3Fe octahedra, edges with four equivalent O(2)Li2Cr3Fe octahedra, edges with four equivalent O(3)Li2Cr4 octahedra, and edges with four equivalent O(1)Li3Cr2Fe octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to two equivalent Li(1), one Cr(1), one Cr(2), and two equivalent Cr(3) atoms to form OLi2Cr4 octahedra that share corners with six equivalent O(3)Li2Cr4 octahedra, edges with four equivalent O(1)Li3Cr2Fe octahedra, and edges with eight equivalent O(2)Li2Cr3Fe octahedra. The corner-sharing octahedra are not tilted.