LiFeTiO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 5-coordinate geometry to one O(3), two equivalent O(2), and two equivalent O(4) atoms. Ti(1) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form TiO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. Fe(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(4) atoms to form FeO6 octahedra that share corners with four equivalent Ti(1)O6 octahedra and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Fe(1) atoms. In the second O site, O(2) is bonded to two equivalent Li(1) and three equivalent Ti(1) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(4)Li2Fe3 trigonal bipyramids, corners with two equivalent O(3)LiTi2Fe trigonal pyramids, edges with four equivalent O(2)Li2Ti3 square pyramids,  an edgeedge with one O(4)Li2Fe3 trigonal bipyramid, and edges with three equivalent O(3)LiTi2Fe trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent Ti(1), and one Fe(1) atom to form distorted OLiTi2Fe trigonal pyramids that share corners with two equivalent O(2)Li2Ti3 square pyramids, corners with five equivalent O(4)Li2Fe3 trigonal bipyramids, corners with two equivalent O(3)LiTi2Fe trigonal pyramids, and edges with three equivalent O(2)Li2Ti3 square pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(1) and three equivalent Fe(1) atoms to form OLi2Fe3 trigonal bipyramids that share corners with two equivalent O(2)Li2Ti3 square pyramids, corners with five equivalent O(3)LiTi2Fe trigonal pyramids,  an edgeedge with one O(2)Li2Ti3 square pyramid, and edges with four equivalent O(4)Li2Fe3 trigonal bipyramids.
LiFeTiO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 5-coordinate geometry to one O(3), two equivalent O(2), and two equivalent O(4) atoms. The Li(1)-O(3) bond length is 2.49 Å. Both Li(1)-O(2) bond lengths are 2.24 Å. Both Li(1)-O(4) bond lengths are 2.19 Å. Ti(1) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form TiO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The Ti(1)-O(1) bond length is 1.89 Å. Both Ti(1)-O(3) bond lengths are 1.94 Å. There are two shorter (2.02 Å) and one longer (2.08 Å) Ti(1)-O(2) bond length. Fe(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(4) atoms to form FeO6 octahedra that share corners with four equivalent Ti(1)O6 octahedra and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The Fe(1)-O(3) bond length is 2.06 Å. Both Fe(1)-O(1) bond lengths are 2.05 Å. There are two shorter (2.03 Å) and one longer (2.04 Å) Fe(1)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Fe(1) atoms. In the second O site, O(2) is bonded to two equivalent Li(1) and three equivalent Ti(1) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(4)Li2Fe3 trigonal bipyramids, corners with two equivalent O(3)LiTi2Fe trigonal pyramids, edges with four equivalent O(2)Li2Ti3 square pyramids,  an edgeedge with one O(4)Li2Fe3 trigonal bipyramid, and edges with three equivalent O(3)LiTi2Fe trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent Ti(1), and one Fe(1) atom to form distorted OLiTi2Fe trigonal pyramids that share corners with two equivalent O(2)Li2Ti3 square pyramids, corners with five equivalent O(4)Li2Fe3 trigonal bipyramids, corners with two equivalent O(3)LiTi2Fe trigonal pyramids, and edges with three equivalent O(2)Li2Ti3 square pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(1) and three equivalent Fe(1) atoms to form OLi2Fe3 trigonal bipyramids that share corners with two equivalent O(2)Li2Ti3 square pyramids, corners with five equivalent O(3)LiTi2Fe trigonal pyramids,  an edgeedge with one O(2)Li2Ti3 square pyramid, and edges with four equivalent O(4)Li2Fe3 trigonal bipyramids.