Li3FeO4 crystallizes in the orthorhombic Aea2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2) and four equivalent O(1) atoms to form LiO5 square pyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-85°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, edges with four equivalent Li(2)O6 octahedra, edges with four equivalent Fe(1)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 10-24°. Fe(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form FeO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid, edges with eight equivalent Li(2)O6 octahedra, and edges with four equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 7°. There are three 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 OLi4Fe2 octahedra that share corners with six equivalent O(1)Li4Fe2 octahedra, corners with two equivalent O(3)Li4Fe square pyramids, edges with four equivalent O(1)Li4Fe2 octahedra, edges with four equivalent O(2)Li5Fe octahedra, and edges with two equivalent O(3)Li4Fe square pyramids. The corner-sharing octahedral tilt angles range from 7-14°. In the second O site, O(2) is bonded to one Li(1), four equivalent Li(2), and one Fe(1) atom to form OLi5Fe octahedra that share corners with four equivalent O(2)Li5Fe octahedra,  a cornercorner with one O(3)Li4Fe square pyramid, edges with eight equivalent O(1)Li4Fe2 octahedra, and edges with four equivalent O(3)Li4Fe square pyramids. The corner-sharing octahedral tilt angles are 14°. In the third O site, O(3) is bonded to four equivalent Li(2) and one Fe(1) atom to form distorted OLi4Fe square pyramids that share  a cornercorner with one O(2)Li5Fe octahedra, corners with four equivalent O(1)Li4Fe2 octahedra, corners with four equivalent O(3)Li4Fe square pyramids, edges with four equivalent O(1)Li4Fe2 octahedra, and edges with four equivalent O(2)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 0-80°.
Li3FeO4 crystallizes in the orthorhombic Aea2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2) and four equivalent O(1) atoms to form LiO5 square pyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-85°. The Li(1)-O(2) bond length is 2.15 Å. All Li(1)-O(1) bond lengths are 2.06 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, edges with four equivalent Li(2)O6 octahedra, edges with four equivalent Fe(1)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 10-24°. There is one shorter (2.15 Å) and one longer (2.20 Å) Li(2)-O(1) bond length. There is one shorter (2.04 Å) and one longer (2.08 Å) Li(2)-O(2) bond length. There is one shorter (2.03 Å) and one longer (2.14 Å) Li(2)-O(3) bond length. Fe(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form FeO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid, edges with eight equivalent Li(2)O6 octahedra, and edges with four equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 7°. The Fe(1)-O(2) bond length is 1.81 Å. The Fe(1)-O(3) bond length is 1.84 Å. There are two shorter (1.88 Å) and two longer (2.21 Å) Fe(1)-O(1) bond lengths. There are three 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 OLi4Fe2 octahedra that share corners with six equivalent O(1)Li4Fe2 octahedra, corners with two equivalent O(3)Li4Fe square pyramids, edges with four equivalent O(1)Li4Fe2 octahedra, edges with four equivalent O(2)Li5Fe octahedra, and edges with two equivalent O(3)Li4Fe square pyramids. The corner-sharing octahedral tilt angles range from 7-14°. In the second O site, O(2) is bonded to one Li(1), four equivalent Li(2), and one Fe(1) atom to form OLi5Fe octahedra that share corners with four equivalent O(2)Li5Fe octahedra,  a cornercorner with one O(3)Li4Fe square pyramid, edges with eight equivalent O(1)Li4Fe2 octahedra, and edges with four equivalent O(3)Li4Fe square pyramids. The corner-sharing octahedral tilt angles are 14°. In the third O site, O(3) is bonded to four equivalent Li(2) and one Fe(1) atom to form distorted OLi4Fe square pyramids that share  a cornercorner with one O(2)Li5Fe octahedra, corners with four equivalent O(1)Li4Fe2 octahedra, corners with four equivalent O(3)Li4Fe square pyramids, edges with four equivalent O(1)Li4Fe2 octahedra, and edges with four equivalent O(2)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 0-80°.