Li4MnFe5O12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, corners with two equivalent Fe(5)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-73°. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. Mn(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Fe(2)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. There are five 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 edges with three equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(5)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share edges with three equivalent Mn(1)O6 octahedra, edges with three equivalent Fe(2)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. In the fourth Fe site, Fe(4) 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 four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Fe(1)O6 octahedra, and edges with three equivalent Fe(5)O6 octahedra. In the fifth Fe site, Fe(5) 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 four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Fe(1)O6 octahedra, and edges with three equivalent Fe(4)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(1), one Fe(2), and one Fe(3) atom to form distorted OLi2MnFe2 trigonal bipyramids that share  a cornercorner with one O(1)Li2MnFe2 trigonal bipyramid, corners with two equivalent O(3)Li2Fe3 trigonal bipyramids, corners with two equivalent O(5)Li2MnFe2 trigonal bipyramids,  an edgeedge with one O(2)Li2Fe3 trigonal bipyramid,  an edgeedge with one O(1)Li2MnFe2 trigonal bipyramid, and edges with three equivalent O(5)Li2MnFe2 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Fe(1), one Fe(4), and one Fe(5) atom to form OLi2Fe3 trigonal bipyramids that share  a cornercorner with one O(2)Li2Fe3 trigonal bipyramid, corners with two equivalent O(3)Li2Fe3 trigonal bipyramids, corners with two equivalent O(5)Li2MnFe2 trigonal bipyramids,  an edgeedge with one O(2)Li2Fe3 trigonal bipyramid,  an edgeedge with one O(1)Li2MnFe2 trigonal bipyramid, and edges with three equivalent O(3)Li2Fe3 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Fe(1), one Fe(4), and one Fe(5) atom to form distorted OLi2Fe3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Fe3 trigonal bipyramid, corners with two equivalent O(2)Li2Fe3 trigonal bipyramids, corners with two equivalent O(1)Li2MnFe2 trigonal bipyramids,  an edgeedge with one O(3)Li2Fe3 trigonal bipyramid,  an edgeedge with one O(5)Li2MnFe2 trigonal bipyramid, and edges with three equivalent O(2)Li2Fe3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(4), and one Fe(5) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Mn(1), one Fe(2), and one Fe(3) atom to form distorted OLi2MnFe2 trigonal bipyramids that share  a cornercorner with one O(5)Li2MnFe2 trigonal bipyramid, corners with two equivalent O(2)Li2Fe3 trigonal bipyramids, corners with two equivalent O(1)Li2MnFe2 trigonal bipyramids,  an edgeedge with one O(3)Li2Fe3 trigonal bipyramid,  an edgeedge with one O(5)Li2MnFe2 trigonal bipyramid, and edges with three equivalent O(1)Li2MnFe2 trigonal bipyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Mn(1), one Fe(2), and one Fe(3) atom.
Li4MnFe5O12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(4)O6 octahedra, corners with two equivalent Fe(5)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-73°. The Li(1)-O(1) bond length is 2.15 Å. The Li(1)-O(2) bond length is 2.14 Å. The Li(1)-O(3) bond length is 2.08 Å. The Li(1)-O(5) bond length is 2.01 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The Li(2)-O(1) bond length is 2.06 Å. The Li(2)-O(2) bond length is 2.00 Å. The Li(2)-O(3) bond length is 2.05 Å. The Li(2)-O(5) bond length is 2.13 Å. Mn(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Fe(2)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. Both Mn(1)-O(1) bond lengths are 1.99 Å. Both Mn(1)-O(5) bond lengths are 1.99 Å. Both Mn(1)-O(6) bond lengths are 1.92 Å. There are five 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 edges with three equivalent Fe(4)O6 octahedra, edges with three equivalent Fe(5)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. Both Fe(1)-O(2) bond lengths are 2.02 Å. Both Fe(1)-O(3) bond lengths are 2.08 Å. Both Fe(1)-O(4) bond lengths are 2.02 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Fe(3)O6 octahedra. Both Fe(2)-O(1) bond lengths are 2.09 Å. Both Fe(2)-O(5) bond lengths are 2.04 Å. Both Fe(2)-O(6) bond lengths are 1.99 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share edges with three equivalent Mn(1)O6 octahedra, edges with three equivalent Fe(2)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. Both Fe(3)-O(1) bond lengths are 2.04 Å. Both Fe(3)-O(5) bond lengths are 2.08 Å. Both Fe(3)-O(6) bond lengths are 2.00 Å. In the fourth Fe site, Fe(4) 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 four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Fe(1)O6 octahedra, and edges with three equivalent Fe(5)O6 octahedra. Both Fe(4)-O(2) bond lengths are 1.99 Å. Both Fe(4)-O(3) bond lengths are 1.92 Å. Both Fe(4)-O(4) bond lengths are 1.90 Å. In the fifth Fe site, Fe(5) 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 four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Fe(1)O6 octahedra, and edges with three equivalent Fe(4)O6 octahedra. Both Fe(5)-O(2) bond lengths are 2.06 Å. Both Fe(5)-O(3) bond lengths are 2.08 Å. Both Fe(5)-O(4) bond lengths are 1.99 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(1), one Fe(2), and one Fe(3) atom to form distorted OLi2MnFe2 trigonal bipyramids that share  a cornercorner with one O(1)Li2MnFe2 trigonal bipyramid, corners with two equivalent O(3)Li2Fe3 trigonal bipyramids, corners with two equivalent O(5)Li2MnFe2 trigonal bipyramids,  an edgeedge with one O(2)Li2Fe3 trigonal bipyramid,  an edgeedge with one O(1)Li2MnFe2 trigonal bipyramid, and edges with three equivalent O(5)Li2MnFe2 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Fe(1), one Fe(4), and one Fe(5) atom to form OLi2Fe3 trigonal bipyramids that share  a cornercorner with one O(2)Li2Fe3 trigonal bipyramid, corners with two equivalent O(3)Li2Fe3 trigonal bipyramids, corners with two equivalent O(5)Li2MnFe2 trigonal bipyramids,  an edgeedge with one O(2)Li2Fe3 trigonal bipyramid,  an edgeedge with one O(1)Li2MnFe2 trigonal bipyramid, and edges with three equivalent O(3)Li2Fe3 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Fe(1), one Fe(4), and one Fe(5) atom to form distorted OLi2Fe3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Fe3 trigonal bipyramid, corners with two equivalent O(2)Li2Fe3 trigonal bipyramids, corners with two equivalent O(1)Li2MnFe2 trigonal bipyramids,  an edgeedge with one O(3)Li2Fe3 trigonal bipyramid,  an edgeedge with one O(5)Li2MnFe2 trigonal bipyramid, and edges with three equivalent O(2)Li2Fe3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(4), and one Fe(5) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Mn(1), one Fe(2), and one Fe(3) atom to form distorted OLi2MnFe2 trigonal bipyramids that share  a cornercorner with one O(5)Li2MnFe2 trigonal bipyramid, corners with two equivalent O(2)Li2Fe3 trigonal bipyramids, corners with two equivalent O(1)Li2MnFe2 trigonal bipyramids,  an edgeedge with one O(3)Li2Fe3 trigonal bipyramid,  an edgeedge with one O(5)Li2MnFe2 trigonal bipyramid, and edges with three equivalent O(1)Li2MnFe2 trigonal bipyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Mn(1), one Fe(2), and one Fe(3) atom.