Li5FeO4 is Ilmenite-like structured and crystallizes in the monoclinic P2_1/c space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra,  an edgeedge with one Fe(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with four equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Fe(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(5)O4 tetrahedra. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra,  an edgeedge with one Fe(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra,  an edgeedge with one Fe(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. Fe(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form FeO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with four equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(5)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Fe(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OLi5Fe octahedra. The corner-sharing octahedral tilt angles range from 56-70°. In the third O site, O(3) is bonded to one Li(1), one Li(3), one Li(5), two equivalent Li(4), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OLi5Fe octahedra. The corner-sharing octahedral tilt angles range from 56-70°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(5), two equivalent Li(2), and one Fe(1) atom.
Li5FeO4 is Ilmenite-like structured and crystallizes in the monoclinic P2_1/c space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra,  an edgeedge with one Fe(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The Li(1)-O(1) bond length is 1.88 Å. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(3) bond length is 1.96 Å. The Li(1)-O(4) bond length is 2.18 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with four equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Fe(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The Li(2)-O(1) bond length is 2.09 Å. The Li(2)-O(2) bond length is 2.01 Å. There is one shorter (1.95 Å) and one longer (2.18 Å) Li(2)-O(4) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(5)O4 tetrahedra. The Li(3)-O(1) bond length is 2.18 Å. The Li(3)-O(2) bond length is 2.07 Å. The Li(3)-O(3) bond length is 1.99 Å. The Li(3)-O(4) bond length is 2.05 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra,  an edgeedge with one Fe(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The Li(4)-O(1) bond length is 1.99 Å. The Li(4)-O(2) bond length is 1.93 Å. There is one shorter (1.95 Å) and one longer (2.01 Å) Li(4)-O(3) bond length. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra,  an edgeedge with one Fe(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The Li(5)-O(1) bond length is 2.13 Å. The Li(5)-O(2) bond length is 2.10 Å. The Li(5)-O(3) bond length is 1.96 Å. The Li(5)-O(4) bond length is 1.96 Å. Fe(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form FeO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with four equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(5)O4 tetrahedra. The Fe(1)-O(1) bond length is 1.91 Å. The Fe(1)-O(2) bond length is 1.92 Å. The Fe(1)-O(3) bond length is 1.95 Å. The Fe(1)-O(4) bond length is 1.90 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Fe(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OLi5Fe octahedra. The corner-sharing octahedral tilt angles range from 56-70°. In the third O site, O(3) is bonded to one Li(1), one Li(3), one Li(5), two equivalent Li(4), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OLi5Fe octahedra. The corner-sharing octahedral tilt angles range from 56-70°. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(5), two equivalent Li(2), and one Fe(1) atom.