Li3Fe3O8 is Spinel-like structured and crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, and corners with three equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-70°. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(8) atom. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the second Fe site, Fe(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the third Fe site, Fe(3) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom. In the second O site, O(1) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi2Fe2 trigonal pyramids. In the third O site, O(2) is bonded to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom to form a mixture of distorted corner and edge-sharing OLi2Fe2 tetrahedra. In the fourth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Fe(1), one Fe(2), and one Fe(3) atom. In the fifth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Fe(1), one Fe(2), and one Fe(3) atom. In the sixth O site, O(5) is bonded to one Li(1), one Li(3), one Fe(2), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi2Fe2 trigonal pyramids. In the seventh O site, O(6) is bonded to one Li(1), one Li(2), one Fe(1), and one Fe(3) atom to form a mixture of distorted corner and edge-sharing OLi2Fe2 tetrahedra. In the eighth O site, O(7) is bonded to one Li(1), one Li(2), one Fe(2), and one Fe(3) atom to form a mixture of distorted corner and edge-sharing OLi2Fe2 tetrahedra.
Li3Fe3O8 is Spinel-like structured and crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. The Li(1)-O(1) bond length is 2.12 Å. The Li(1)-O(2) bond length is 2.31 Å. The Li(1)-O(5) bond length is 2.15 Å. The Li(1)-O(6) bond length is 2.34 Å. The Li(1)-O(7) bond length is 2.30 Å. The Li(1)-O(8) bond length is 2.14 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, and corners with three equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-70°. The Li(2)-O(2) bond length is 1.97 Å. The Li(2)-O(3) bond length is 2.12 Å. The Li(2)-O(6) bond length is 1.98 Å. The Li(2)-O(7) bond length is 1.96 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(8) atom. The Li(3)-O(1) bond length is 1.90 Å. The Li(3)-O(4) bond length is 1.79 Å. The Li(3)-O(5) bond length is 1.93 Å. The Li(3)-O(8) bond length is 1.91 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Fe(1)-O(1) bond length is 1.92 Å. The Fe(1)-O(2) bond length is 1.90 Å. The Fe(1)-O(3) bond length is 1.91 Å. The Fe(1)-O(4) bond length is 1.90 Å. The Fe(1)-O(6) bond length is 1.91 Å. The Fe(1)-O(8) bond length is 1.92 Å. In the second Fe site, Fe(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Fe(2)-O(2) bond length is 1.91 Å. The Fe(2)-O(3) bond length is 2.08 Å. The Fe(2)-O(4) bond length is 2.05 Å. The Fe(2)-O(5) bond length is 1.92 Å. The Fe(2)-O(7) bond length is 1.90 Å. The Fe(2)-O(8) bond length is 1.94 Å. In the third Fe site, Fe(3) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Fe(3)-O(1) bond length is 1.95 Å. The Fe(3)-O(3) bond length is 2.08 Å. The Fe(3)-O(4) bond length is 2.06 Å. The Fe(3)-O(5) bond length is 1.92 Å. The Fe(3)-O(6) bond length is 1.92 Å. The Fe(3)-O(7) bond length is 1.90 Å. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Fe(1), and one Fe(2) atom. In the second O site, O(1) is bonded to one Li(1), one Li(3), one Fe(1), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi2Fe2 trigonal pyramids. In the third O site, O(2) is bonded to one Li(1), one Li(2), one Fe(1), and one Fe(2) atom to form a mixture of distorted corner and edge-sharing OLi2Fe2 tetrahedra. In the fourth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Fe(1), one Fe(2), and one Fe(3) atom. In the fifth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Fe(1), one Fe(2), and one Fe(3) atom. In the sixth O site, O(5) is bonded to one Li(1), one Li(3), one Fe(2), and one Fe(3) atom to form a mixture of corner and edge-sharing OLi2Fe2 trigonal pyramids. In the seventh O site, O(6) is bonded to one Li(1), one Li(2), one Fe(1), and one Fe(3) atom to form a mixture of distorted corner and edge-sharing OLi2Fe2 tetrahedra. In the eighth O site, O(7) is bonded to one Li(1), one Li(2), one Fe(2), and one Fe(3) atom to form a mixture of distorted corner and edge-sharing OLi2Fe2 tetrahedra.