Li3FeO3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted T-shaped geometry to one O(3) and two equivalent O(1) atoms. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with four equivalent Fe(1)O4 tetrahedra and edges with two equivalent Li(2)O4 tetrahedra. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. Fe(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted FeO4 tetrahedra that share corners with two equivalent Fe(1)O4 tetrahedra and corners with four equivalent Li(2)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Fe(1) atom to form OLi5Fe octahedra that share corners with two equivalent O(1)Li5Fe octahedra, corners with six equivalent O(2)Li3Fe tetrahedra, corners with two equivalent O(3)Li3Fe2 trigonal bipyramids,  an edgeedge with one O(1)Li5Fe octahedra, and edges with two equivalent O(3)Li3Fe2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 21°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), and one Fe(1) atom to form OLi3Fe tetrahedra that share corners with six equivalent O(1)Li5Fe octahedra, corners with four equivalent O(3)Li3Fe2 trigonal bipyramids, and  an edgeedge with one O(2)Li3Fe tetrahedra. The corner-sharing octahedral tilt angles range from 50-67°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(3), and two equivalent Fe(1) atoms to form distorted OLi3Fe2 trigonal bipyramids that share corners with two equivalent O(1)Li5Fe octahedra, corners with four equivalent O(2)Li3Fe tetrahedra, edges with two equivalent O(1)Li5Fe octahedra, and edges with two equivalent O(3)Li3Fe2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 73-77°.
Li3FeO3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted T-shaped geometry to one O(3) and two equivalent O(1) atoms. The Li(1)-O(3) bond length is 1.98 Å. There is one shorter (1.97 Å) and one longer (2.01 Å) Li(1)-O(1) bond length. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with four equivalent Fe(1)O4 tetrahedra and edges with two equivalent Li(2)O4 tetrahedra. There is one shorter (2.03 Å) and one longer (2.25 Å) Li(2)-O(1) bond length. Both Li(2)-O(2) bond lengths are 2.00 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Li(3)-O(1) bond length is 2.04 Å. The Li(3)-O(2) bond length is 1.96 Å. There is one shorter (2.03 Å) and one longer (2.04 Å) Li(3)-O(3) bond length. Fe(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted FeO4 tetrahedra that share corners with two equivalent Fe(1)O4 tetrahedra and corners with four equivalent Li(2)O4 tetrahedra. The Fe(1)-O(1) bond length is 1.89 Å. The Fe(1)-O(2) bond length is 1.86 Å. There is one shorter (1.94 Å) and one longer (1.96 Å) Fe(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Fe(1) atom to form OLi5Fe octahedra that share corners with two equivalent O(1)Li5Fe octahedra, corners with six equivalent O(2)Li3Fe tetrahedra, corners with two equivalent O(3)Li3Fe2 trigonal bipyramids,  an edgeedge with one O(1)Li5Fe octahedra, and edges with two equivalent O(3)Li3Fe2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 21°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), and one Fe(1) atom to form OLi3Fe tetrahedra that share corners with six equivalent O(1)Li5Fe octahedra, corners with four equivalent O(3)Li3Fe2 trigonal bipyramids, and  an edgeedge with one O(2)Li3Fe tetrahedra. The corner-sharing octahedral tilt angles range from 50-67°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(3), and two equivalent Fe(1) atoms to form distorted OLi3Fe2 trigonal bipyramids that share corners with two equivalent O(1)Li5Fe octahedra, corners with four equivalent O(2)Li3Fe tetrahedra, edges with two equivalent O(1)Li5Fe octahedra, and edges with two equivalent O(3)Li3Fe2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 73-77°.