Li3MnFe3O8 crystallizes in the triclinic P-1 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 Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Fe(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-15°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) 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 Mn(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with six 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 Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-15°. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form FeO6 octahedra that share 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 Mn(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Mn(1), one Fe(2), and one Fe(3) atom to form OLi2MnFe2 square pyramids that share corners with two equivalent O(4)Li2Fe3 square pyramids, corners with two equivalent O(2)Li2MnFe2 square pyramids, corners with five equivalent O(1)Li2MnFe2 square pyramids, edges with four equivalent O(3)Li3MnFe2 octahedra, edges with two equivalent O(4)Li2Fe3 square pyramids, and edges with two equivalent O(2)Li2MnFe2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Fe(1), and one Fe(3) atom to form OLi2MnFe2 square pyramids that share corners with two equivalent O(4)Li2Fe3 square pyramids, corners with two equivalent O(1)Li2MnFe2 square pyramids, corners with five equivalent O(2)Li2MnFe2 square pyramids, edges with four equivalent O(3)Li3MnFe2 octahedra, edges with two equivalent O(4)Li2Fe3 square pyramids, and edges with two equivalent O(1)Li2MnFe2 square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Fe(1), and one Fe(2) atom to form distorted OLi3MnFe2 octahedra that share corners with six equivalent O(3)Li3MnFe2 octahedra, edges with four equivalent O(4)Li2Fe3 square pyramids, edges with four equivalent O(1)Li2MnFe2 square pyramids, and edges with four equivalent O(2)Li2MnFe2 square pyramids. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Fe(1), one Fe(2), and one Fe(3) atom to form OLi2Fe3 square pyramids that share corners with two equivalent O(1)Li2MnFe2 square pyramids, corners with two equivalent O(2)Li2MnFe2 square pyramids, corners with five equivalent O(4)Li2Fe3 square pyramids, edges with four equivalent O(3)Li3MnFe2 octahedra, edges with two equivalent O(1)Li2MnFe2 square pyramids, and edges with two equivalent O(2)Li2MnFe2 square pyramids.
Li3MnFe3O8 crystallizes in the triclinic P-1 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 Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both Li(1)-O(1) bond lengths are 2.30 Å. Both Li(1)-O(2) bond lengths are 2.10 Å. Both Li(1)-O(3) bond lengths are 2.32 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Fe(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-15°. Both Li(2)-O(2) bond lengths are 2.23 Å. Both Li(2)-O(3) bond lengths are 2.07 Å. Both Li(2)-O(4) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) 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 Mn(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. Both Li(3)-O(1) bond lengths are 2.22 Å. Both Li(3)-O(3) bond lengths are 2.27 Å. Both Li(3)-O(4) bond lengths are 2.22 Å. Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with six 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 Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both Mn(1)-O(1) bond lengths are 1.90 Å. Both Mn(1)-O(2) bond lengths are 2.27 Å. Both Mn(1)-O(3) bond lengths are 1.87 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-15°. Both Fe(1)-O(2) bond lengths are 1.97 Å. Both Fe(1)-O(3) bond lengths are 2.31 Å. Both Fe(1)-O(4) bond lengths are 2.09 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. Both Fe(2)-O(1) bond lengths are 1.97 Å. Both Fe(2)-O(3) bond lengths are 1.94 Å. Both Fe(2)-O(4) bond lengths are 2.13 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form FeO6 octahedra that share 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 Mn(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. Both Fe(3)-O(1) bond lengths are 2.28 Å. Both Fe(3)-O(2) bond lengths are 1.89 Å. Both Fe(3)-O(4) bond lengths are 1.96 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Mn(1), one Fe(2), and one Fe(3) atom to form OLi2MnFe2 square pyramids that share corners with two equivalent O(4)Li2Fe3 square pyramids, corners with two equivalent O(2)Li2MnFe2 square pyramids, corners with five equivalent O(1)Li2MnFe2 square pyramids, edges with four equivalent O(3)Li3MnFe2 octahedra, edges with two equivalent O(4)Li2Fe3 square pyramids, and edges with two equivalent O(2)Li2MnFe2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Fe(1), and one Fe(3) atom to form OLi2MnFe2 square pyramids that share corners with two equivalent O(4)Li2Fe3 square pyramids, corners with two equivalent O(1)Li2MnFe2 square pyramids, corners with five equivalent O(2)Li2MnFe2 square pyramids, edges with four equivalent O(3)Li3MnFe2 octahedra, edges with two equivalent O(4)Li2Fe3 square pyramids, and edges with two equivalent O(1)Li2MnFe2 square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Fe(1), and one Fe(2) atom to form distorted OLi3MnFe2 octahedra that share corners with six equivalent O(3)Li3MnFe2 octahedra, edges with four equivalent O(4)Li2Fe3 square pyramids, edges with four equivalent O(1)Li2MnFe2 square pyramids, and edges with four equivalent O(2)Li2MnFe2 square pyramids. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Fe(1), one Fe(2), and one Fe(3) atom to form OLi2Fe3 square pyramids that share corners with two equivalent O(1)Li2MnFe2 square pyramids, corners with two equivalent O(2)Li2MnFe2 square pyramids, corners with five equivalent O(4)Li2Fe3 square pyramids, edges with four equivalent O(3)Li3MnFe2 octahedra, edges with two equivalent O(1)Li2MnFe2 square pyramids, and edges with two equivalent O(2)Li2MnFe2 square pyramids.