Li3Fe5O9 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with four equivalent Fe(2)O4 tetrahedra, and  an edgeedge with one Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 81°. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one O(5) and two equivalent O(3) atoms. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form FeO4 tetrahedra that share corners with three equivalent Fe(3)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Fe(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-66°. In the second Fe site, Fe(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form FeO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(2)O4 tetrahedra, corners with three equivalent Fe(1)O4 tetrahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. In the third Fe site, Fe(3) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra, corners with six equivalent Fe(1)O4 tetrahedra, and edges with two equivalent Fe(3)O6 octahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1) and two equivalent Fe(3) atoms. In the second O site, O(2) is bonded to two equivalent Li(1), one Fe(1), and one Fe(2) atom to form OLi2Fe2 tetrahedra that share corners with two equivalent O(2)Li2Fe2 tetrahedra, corners with four equivalent O(3)Li2Fe2 tetrahedra, corners with two equivalent O(4)LiFe3 trigonal pyramids, and  an edgeedge with one O(4)LiFe3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom to form OLi2Fe2 tetrahedra that share  a cornercorner with one O(3)Li2Fe2 tetrahedra, corners with four equivalent O(2)Li2Fe2 tetrahedra, and corners with three equivalent O(4)LiFe3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Fe(1), one Fe(2), and one Fe(3) atom to form distorted OLiFe3 trigonal pyramids that share corners with two equivalent O(2)Li2Fe2 tetrahedra, corners with three equivalent O(3)Li2Fe2 tetrahedra,  a cornercorner with one O(4)LiFe3 trigonal pyramid, and  an edgeedge with one O(2)Li2Fe2 tetrahedra. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Fe(2) atoms.
Li3Fe5O9 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with four equivalent Fe(2)O4 tetrahedra, and  an edgeedge with one Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 81°. The Li(1)-O(3) bond length is 2.04 Å. The Li(1)-O(4) bond length is 2.43 Å. Both Li(1)-O(2) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded in a trigonal planar geometry to one O(5) and two equivalent O(3) atoms. The Li(2)-O(5) bond length is 1.95 Å. Both Li(2)-O(3) bond lengths are 2.14 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form FeO4 tetrahedra that share corners with three equivalent Fe(3)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Fe(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-66°. The Fe(1)-O(1) bond length is 1.86 Å. The Fe(1)-O(2) bond length is 1.93 Å. The Fe(1)-O(3) bond length is 1.92 Å. The Fe(1)-O(4) bond length is 1.94 Å. In the second Fe site, Fe(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form FeO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one Fe(2)O4 tetrahedra, corners with three equivalent Fe(1)O4 tetrahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. The Fe(2)-O(2) bond length is 1.90 Å. The Fe(2)-O(3) bond length is 1.93 Å. The Fe(2)-O(4) bond length is 1.93 Å. The Fe(2)-O(5) bond length is 1.90 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form FeO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra, corners with six equivalent Fe(1)O4 tetrahedra, and edges with two equivalent Fe(3)O6 octahedra. Both Fe(3)-O(4) bond lengths are 2.03 Å. There are two shorter (2.03 Å) and two longer (2.04 Å) Fe(3)-O(1) bond lengths. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1) and two equivalent Fe(3) atoms. In the second O site, O(2) is bonded to two equivalent Li(1), one Fe(1), and one Fe(2) atom to form OLi2Fe2 tetrahedra that share corners with two equivalent O(2)Li2Fe2 tetrahedra, corners with four equivalent O(3)Li2Fe2 tetrahedra, corners with two equivalent O(4)LiFe3 trigonal pyramids, and  an edgeedge with one O(4)LiFe3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom to form OLi2Fe2 tetrahedra that share  a cornercorner with one O(3)Li2Fe2 tetrahedra, corners with four equivalent O(2)Li2Fe2 tetrahedra, and corners with three equivalent O(4)LiFe3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Fe(1), one Fe(2), and one Fe(3) atom to form distorted OLiFe3 trigonal pyramids that share corners with two equivalent O(2)Li2Fe2 tetrahedra, corners with three equivalent O(3)Li2Fe2 tetrahedra,  a cornercorner with one O(4)LiFe3 trigonal pyramid, and  an edgeedge with one O(2)Li2Fe2 tetrahedra. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Fe(2) atoms.