Li4Fe3O8 crystallizes in the trigonal R-3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra and edges with six equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1) and three equivalent O(2) atoms. In the third Li site, Li(3) is bonded to six equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra and edges with six equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. Fe(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form FeO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2) and three equivalent Fe(1) atoms. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing OLi3Fe2 square pyramids.
Li4Fe3O8 crystallizes in the trigonal R-3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra and edges with six equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. All Li(1)-O(2) bond lengths are 2.18 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1) and three equivalent O(2) atoms. The Li(2)-O(1) bond length is 1.86 Å. All Li(2)-O(2) bond lengths are 2.08 Å. In the third Li site, Li(3) is bonded to six equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra and edges with six equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. All Li(3)-O(2) bond lengths are 2.07 Å. Fe(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form FeO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. Both Fe(1)-O(1) bond lengths are 2.02 Å. All Fe(1)-O(2) bond lengths are 1.96 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2) and three equivalent Fe(1) atoms. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing OLi3Fe2 square pyramids.