LiTiFe5O8 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Ti(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Fe(1)O4 tetrahedra, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with two equivalent Fe(4)O6 octahedra. There are four 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 distorted FeO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra, and corners with three equivalent Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-65°. 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 Fe(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with two equivalent Fe(4)O6 octahedra. 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 corners with six equivalent Fe(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(4)O6 octahedra. In the fourth Fe site, Fe(4) 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 Fe(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(2), one Fe(3), and one Fe(4) atom to form distorted OFe4 tetrahedra that share corners with three equivalent O(2)LiTiFe3 square pyramids, corners with three equivalent O(3)LiTiFe3 square pyramids, corners with three equivalent O(4)LiTiFe3 square pyramids, corners with three equivalent O(1)Fe4 tetrahedra,  an edgeedge with one O(2)LiTiFe3 square pyramid,  an edgeedge with one O(3)LiTiFe3 square pyramid, and  an edgeedge with one O(4)LiTiFe3 square pyramid. In the second O site, O(2) is bonded to one Li(1), one Ti(1), one Fe(1), one Fe(3), and one Fe(4) atom to form distorted OLiTiFe3 square pyramids that share  a cornercorner with one O(3)LiTiFe3 square pyramid,  a cornercorner with one O(4)LiTiFe3 square pyramid, corners with four equivalent O(2)LiTiFe3 square pyramids, corners with three equivalent O(1)Fe4 tetrahedra, edges with three equivalent O(3)LiTiFe3 square pyramids, edges with three equivalent O(4)LiTiFe3 square pyramids, and  an edgeedge with one O(1)Fe4 tetrahedra. In the third O site, O(3) is bonded to one Li(1), one Ti(1), one Fe(1), one Fe(2), and one Fe(4) atom to form distorted OLiTiFe3 square pyramids that share  a cornercorner with one O(2)LiTiFe3 square pyramid,  a cornercorner with one O(4)LiTiFe3 square pyramid, corners with four equivalent O(3)LiTiFe3 square pyramids, corners with three equivalent O(1)Fe4 tetrahedra, edges with three equivalent O(2)LiTiFe3 square pyramids, edges with three equivalent O(4)LiTiFe3 square pyramids, and  an edgeedge with one O(1)Fe4 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Ti(1), one Fe(1), one Fe(2), and one Fe(3) atom to form distorted OLiTiFe3 square pyramids that share  a cornercorner with one O(2)LiTiFe3 square pyramid,  a cornercorner with one O(3)LiTiFe3 square pyramid, corners with four equivalent O(4)LiTiFe3 square pyramids, corners with three equivalent O(1)Fe4 tetrahedra, edges with three equivalent O(2)LiTiFe3 square pyramids, edges with three equivalent O(3)LiTiFe3 square pyramids, and  an edgeedge with one O(1)Fe4 tetrahedra.
LiTiFe5O8 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Both Li(1)-O(2) bond lengths are 2.31 Å. Both Li(1)-O(3) bond lengths are 2.28 Å. Both Li(1)-O(4) bond lengths are 2.37 Å. Ti(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Fe(1)O4 tetrahedra, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with two equivalent Fe(4)O6 octahedra. Both Ti(1)-O(2) bond lengths are 2.05 Å. Both Ti(1)-O(3) bond lengths are 2.05 Å. Both Ti(1)-O(4) bond lengths are 2.03 Å. There are four 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 distorted FeO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra, and corners with three equivalent Fe(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-65°. The Fe(1)-O(1) bond length is 1.90 Å. The Fe(1)-O(2) bond length is 1.98 Å. The Fe(1)-O(3) bond length is 2.04 Å. The Fe(1)-O(4) bond length is 2.03 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 Fe(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with two equivalent Fe(4)O6 octahedra. Both Fe(2)-O(1) bond lengths are 2.00 Å. Both Fe(2)-O(3) bond lengths are 2.27 Å. Both Fe(2)-O(4) bond lengths are 2.25 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 corners with six equivalent Fe(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(4)O6 octahedra. Both Fe(3)-O(1) bond lengths are 1.99 Å. Both Fe(3)-O(2) bond lengths are 2.24 Å. Both Fe(3)-O(4) bond lengths are 2.27 Å. In the fourth Fe site, Fe(4) 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 Fe(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. Both Fe(4)-O(1) bond lengths are 2.00 Å. Both Fe(4)-O(2) bond lengths are 2.23 Å. Both Fe(4)-O(3) bond lengths are 2.26 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(2), one Fe(3), and one Fe(4) atom to form distorted OFe4 tetrahedra that share corners with three equivalent O(2)LiTiFe3 square pyramids, corners with three equivalent O(3)LiTiFe3 square pyramids, corners with three equivalent O(4)LiTiFe3 square pyramids, corners with three equivalent O(1)Fe4 tetrahedra,  an edgeedge with one O(2)LiTiFe3 square pyramid,  an edgeedge with one O(3)LiTiFe3 square pyramid, and  an edgeedge with one O(4)LiTiFe3 square pyramid. In the second O site, O(2) is bonded to one Li(1), one Ti(1), one Fe(1), one Fe(3), and one Fe(4) atom to form distorted OLiTiFe3 square pyramids that share  a cornercorner with one O(3)LiTiFe3 square pyramid,  a cornercorner with one O(4)LiTiFe3 square pyramid, corners with four equivalent O(2)LiTiFe3 square pyramids, corners with three equivalent O(1)Fe4 tetrahedra, edges with three equivalent O(3)LiTiFe3 square pyramids, edges with three equivalent O(4)LiTiFe3 square pyramids, and  an edgeedge with one O(1)Fe4 tetrahedra. In the third O site, O(3) is bonded to one Li(1), one Ti(1), one Fe(1), one Fe(2), and one Fe(4) atom to form distorted OLiTiFe3 square pyramids that share  a cornercorner with one O(2)LiTiFe3 square pyramid,  a cornercorner with one O(4)LiTiFe3 square pyramid, corners with four equivalent O(3)LiTiFe3 square pyramids, corners with three equivalent O(1)Fe4 tetrahedra, edges with three equivalent O(2)LiTiFe3 square pyramids, edges with three equivalent O(4)LiTiFe3 square pyramids, and  an edgeedge with one O(1)Fe4 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Ti(1), one Fe(1), one Fe(2), and one Fe(3) atom to form distorted OLiTiFe3 square pyramids that share  a cornercorner with one O(2)LiTiFe3 square pyramid,  a cornercorner with one O(3)LiTiFe3 square pyramid, corners with four equivalent O(4)LiTiFe3 square pyramids, corners with three equivalent O(1)Fe4 tetrahedra, edges with three equivalent O(2)LiTiFe3 square pyramids, edges with three equivalent O(3)LiTiFe3 square pyramids, and  an edgeedge with one O(1)Fe4 tetrahedra.