Li5Fe3O8 is Caswellsilverite-like structured and crystallizes in the monoclinic P2_1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and  a faceface with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-54°. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form 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(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and  a faceface with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-53°. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-54°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and  a faceface with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-51°. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-49°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), 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 two equivalent Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with three equivalent Li(5)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Li(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-51°. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-51°. 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(8) atom to form FeO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-53°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Li(5), one Fe(1), one Fe(2), and one Fe(3) atom to form OLi3Fe3 octahedra that share corners with six equivalent O(4)Li3Fe3 pentagonal pyramids, edges with two equivalent O(3)Li4Fe2 octahedra, edges with two equivalent O(6)Li4Fe2 octahedra, and edges with two equivalent O(7)Li4Fe2 octahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), one Fe(1), and one Fe(2) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Fe(2), and one Fe(3) atom to form OLi4Fe2 octahedra that share edges with two equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(6)Li4Fe2 octahedra, edges with two equivalent O(7)Li4Fe2 octahedra, and edges with two equivalent O(4)Li3Fe3 pentagonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Li(5), one Fe(1), one Fe(2), and one Fe(3) atom to form distorted OLi3Fe3 pentagonal pyramids that share corners with six equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(3)Li4Fe2 octahedra, edges with two equivalent O(6)Li4Fe2 octahedra, and edges with two equivalent O(7)Li4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), one Fe(1), and one Fe(3) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Fe(1), and one Fe(3) atom to form OLi4Fe2 octahedra that share edges with two equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(3)Li4Fe2 octahedra, edges with two equivalent O(7)Li4Fe2 octahedra, and edges with two equivalent O(4)Li3Fe3 pentagonal pyramids. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Fe(1), and one Fe(2) atom to form OLi4Fe2 octahedra that share edges with two equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(3)Li4Fe2 octahedra, edges with two equivalent O(6)Li4Fe2 octahedra, and edges with two equivalent O(4)Li3Fe3 pentagonal pyramids. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Fe(2), and one Fe(3) atom.
Li5Fe3O8 is Caswellsilverite-like structured and crystallizes in the monoclinic P2_1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and  a faceface with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-54°. The Li(1)-O(1) bond length is 2.09 Å. The Li(1)-O(3) bond length is 2.08 Å. The Li(1)-O(4) bond length is 2.11 Å. The Li(1)-O(5) bond length is 2.37 Å. The Li(1)-O(6) bond length is 2.05 Å. The Li(1)-O(8) bond length is 2.30 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form 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(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and  a faceface with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-53°. The Li(2)-O(2) bond length is 2.23 Å. The Li(2)-O(3) bond length is 2.13 Å. The Li(2)-O(5) bond length is 2.19 Å. The Li(2)-O(6) bond length is 2.14 Å. The Li(2)-O(7) bond length is 2.11 Å. The Li(2)-O(8) bond length is 2.28 Å. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-54°. The Li(3)-O(2) bond length is 2.07 Å. The Li(3)-O(3) bond length is 2.08 Å. The Li(3)-O(5) bond length is 2.11 Å. The Li(3)-O(6) bond length is 2.08 Å. The Li(3)-O(7) bond length is 2.03 Å. The Li(3)-O(8) bond length is 2.10 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and  a faceface with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-51°. The Li(4)-O(1) bond length is 2.06 Å. The Li(4)-O(2) bond length is 2.30 Å. The Li(4)-O(3) bond length is 2.20 Å. The Li(4)-O(4) bond length is 2.17 Å. The Li(4)-O(7) bond length is 2.15 Å. The Li(4)-O(8) bond length is 2.14 Å. In the fifth Li site, Li(5) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Fe(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-49°. The Li(5)-O(1) bond length is 2.03 Å. The Li(5)-O(2) bond length is 2.24 Å. The Li(5)-O(4) bond length is 2.25 Å. The Li(5)-O(5) bond length is 2.18 Å. The Li(5)-O(6) bond length is 2.16 Å. The Li(5)-O(7) bond length is 2.14 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(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 two equivalent Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with three equivalent Li(5)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Li(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-51°. The Fe(1)-O(1) bond length is 2.10 Å. The Fe(1)-O(2) bond length is 1.98 Å. The Fe(1)-O(4) bond length is 2.08 Å. The Fe(1)-O(5) bond length is 1.92 Å. The Fe(1)-O(6) bond length is 1.93 Å. The Fe(1)-O(7) bond length is 2.00 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form FeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(3)O6 octahedra, and  a faceface with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-51°. The Fe(2)-O(1) bond length is 2.09 Å. The Fe(2)-O(2) bond length is 1.95 Å. The Fe(2)-O(3) bond length is 1.92 Å. The Fe(2)-O(4) bond length is 2.09 Å. The Fe(2)-O(7) bond length is 1.96 Å. The Fe(2)-O(8) bond length is 1.90 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(8) atom to form FeO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-53°. The Fe(3)-O(1) bond length is 2.02 Å. The Fe(3)-O(3) bond length is 2.02 Å. The Fe(3)-O(4) bond length is 2.02 Å. The Fe(3)-O(5) bond length is 2.02 Å. The Fe(3)-O(6) bond length is 2.03 Å. The Fe(3)-O(8) bond length is 2.03 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(4), one Li(5), one Fe(1), one Fe(2), and one Fe(3) atom to form OLi3Fe3 octahedra that share corners with six equivalent O(4)Li3Fe3 pentagonal pyramids, edges with two equivalent O(3)Li4Fe2 octahedra, edges with two equivalent O(6)Li4Fe2 octahedra, and edges with two equivalent O(7)Li4Fe2 octahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), one Fe(1), and one Fe(2) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Fe(2), and one Fe(3) atom to form OLi4Fe2 octahedra that share edges with two equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(6)Li4Fe2 octahedra, edges with two equivalent O(7)Li4Fe2 octahedra, and edges with two equivalent O(4)Li3Fe3 pentagonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Li(5), one Fe(1), one Fe(2), and one Fe(3) atom to form distorted OLi3Fe3 pentagonal pyramids that share corners with six equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(3)Li4Fe2 octahedra, edges with two equivalent O(6)Li4Fe2 octahedra, and edges with two equivalent O(7)Li4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(5), one Fe(1), and one Fe(3) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Fe(1), and one Fe(3) atom to form OLi4Fe2 octahedra that share edges with two equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(3)Li4Fe2 octahedra, edges with two equivalent O(7)Li4Fe2 octahedra, and edges with two equivalent O(4)Li3Fe3 pentagonal pyramids. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Fe(1), and one Fe(2) atom to form OLi4Fe2 octahedra that share edges with two equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(3)Li4Fe2 octahedra, edges with two equivalent O(6)Li4Fe2 octahedra, and edges with two equivalent O(4)Li3Fe3 pentagonal pyramids. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Fe(2), and one Fe(3) atom.