Li4CrFe3O8 is alpha Po-derived structured and 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), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Fe(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 Cr(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with four 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 Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Cr(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(3)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 Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form FeO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 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 Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Cr(1), one Fe(1), and one Fe(2) atom to form OLi3CrFe2 octahedra that share corners with six equivalent O(1)Li3CrFe2 octahedra, edges with four equivalent O(1)Li3CrFe2 octahedra, edges with four equivalent O(2)Li3CrFe2 octahedra, and edges with four equivalent O(3)Li3Fe3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Cr(1), and two equivalent Fe(2) atoms to form OLi3CrFe2 octahedra that share corners with two equivalent O(2)Li3CrFe2 octahedra, corners with four equivalent O(3)Li3Fe3 octahedra, edges with two equivalent O(2)Li3CrFe2 octahedra, edges with two equivalent O(3)Li3Fe3 octahedra, and edges with eight equivalent O(1)Li3CrFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), one Fe(1), and two equivalent Fe(2) atoms to form OLi3Fe3 octahedra that share corners with two equivalent O(3)Li3Fe3 octahedra, corners with four equivalent O(2)Li3CrFe2 octahedra, edges with two equivalent O(2)Li3CrFe2 octahedra, edges with two equivalent O(3)Li3Fe3 octahedra, and edges with eight equivalent O(1)Li3CrFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li4CrFe3O8 is alpha Po-derived structured and 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), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Fe(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 Cr(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. Both Li(1)-O(1) bond lengths are 2.17 Å. Both Li(1)-O(2) bond lengths are 2.17 Å. Both Li(1)-O(3) bond lengths are 2.17 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Li(2)-O(2) bond lengths are 2.19 Å. All Li(2)-O(1) bond lengths are 2.17 Å. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with four 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 Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Li(3)-O(3) bond lengths are 2.17 Å. All Li(3)-O(1) bond lengths are 2.18 Å. Cr(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(3)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 Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Cr(1)-O(2) bond lengths are 2.04 Å. All Cr(1)-O(1) bond lengths are 2.04 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form FeO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Fe(1)-O(3) bond lengths are 2.06 Å. All Fe(1)-O(1) bond lengths are 2.05 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 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 Li(3)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. Both Fe(2)-O(1) bond lengths are 2.05 Å. Both Fe(2)-O(2) bond lengths are 2.05 Å. Both Fe(2)-O(3) bond lengths are 2.05 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Cr(1), one Fe(1), and one Fe(2) atom to form OLi3CrFe2 octahedra that share corners with six equivalent O(1)Li3CrFe2 octahedra, edges with four equivalent O(1)Li3CrFe2 octahedra, edges with four equivalent O(2)Li3CrFe2 octahedra, and edges with four equivalent O(3)Li3Fe3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Cr(1), and two equivalent Fe(2) atoms to form OLi3CrFe2 octahedra that share corners with two equivalent O(2)Li3CrFe2 octahedra, corners with four equivalent O(3)Li3Fe3 octahedra, edges with two equivalent O(2)Li3CrFe2 octahedra, edges with two equivalent O(3)Li3Fe3 octahedra, and edges with eight equivalent O(1)Li3CrFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), one Fe(1), and two equivalent Fe(2) atoms to form OLi3Fe3 octahedra that share corners with two equivalent O(3)Li3Fe3 octahedra, corners with four equivalent O(2)Li3CrFe2 octahedra, edges with two equivalent O(2)Li3CrFe2 octahedra, edges with two equivalent O(3)Li3Fe3 octahedra, and edges with eight equivalent O(1)Li3CrFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.