Li3FeO3 crystallizes in the tetragonal P4_2/mnm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing LiO4 trigonal pyramids. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing LiO4 tetrahedra. Fe(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms to form distorted OLi4Fe2 octahedra that share corners with two equivalent O(1)Li4Fe2 octahedra, corners with two equivalent O(2)Li4Fe trigonal bipyramids,  an edgeedge with one O(1)Li4Fe2 octahedra, and edges with six equivalent O(2)Li4Fe trigonal bipyramids. The corner-sharing octahedral tilt angles are 49°. In the second O site, O(2) is bonded to one Li(2), three equivalent Li(1), and one Fe(1) atom to form OLi4Fe trigonal bipyramids that share  a cornercorner with one O(1)Li4Fe2 octahedra, corners with six equivalent O(2)Li4Fe trigonal bipyramids, edges with three equivalent O(1)Li4Fe2 octahedra, and  an edgeedge with one O(2)Li4Fe trigonal bipyramid. The corner-sharing octahedral tilt angles are 5°.
Li3FeO3 crystallizes in the tetragonal P4_2/mnm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing LiO4 trigonal pyramids. The Li(1)-O(1) bond length is 2.29 Å. There is one shorter (1.92 Å) and two longer (1.96 Å) Li(1)-O(2) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing LiO4 tetrahedra. Both Li(2)-O(1) bond lengths are 2.00 Å. Both Li(2)-O(2) bond lengths are 1.96 Å. Fe(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Fe(1)-O(1) bond lengths are 1.93 Å. Both Fe(1)-O(2) bond lengths are 1.84 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms to form distorted OLi4Fe2 octahedra that share corners with two equivalent O(1)Li4Fe2 octahedra, corners with two equivalent O(2)Li4Fe trigonal bipyramids,  an edgeedge with one O(1)Li4Fe2 octahedra, and edges with six equivalent O(2)Li4Fe trigonal bipyramids. The corner-sharing octahedral tilt angles are 49°. In the second O site, O(2) is bonded to one Li(2), three equivalent Li(1), and one Fe(1) atom to form OLi4Fe trigonal bipyramids that share  a cornercorner with one O(1)Li4Fe2 octahedra, corners with six equivalent O(2)Li4Fe trigonal bipyramids, edges with three equivalent O(1)Li4Fe2 octahedra, and  an edgeedge with one O(2)Li4Fe trigonal bipyramid. The corner-sharing octahedral tilt angles are 5°.