Li5FeO4F crystallizes in the monoclinic P2_1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one F(1) atom. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent Li(5)O3F tetrahedra, edges with two equivalent Li(4)O4F square pyramids, and  an edgeedge with one Li(5)O3F tetrahedra. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(3)O4F square pyramid, edges with two equivalent Li(3)O4F square pyramids, and edges with two equivalent Li(5)O3F tetrahedra. In the fifth Li site, Li(5) is bonded to one O(1), one O(3), one O(4), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F tetrahedra. Fe(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and one Fe(1) atom to form a mixture of corner and edge-sharing OLi4Fe trigonal bipyramids. The corner-sharing octahedral tilt angles are 30°. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom. In the third O site, O(3) 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 corner and edge-sharing OLi5Fe octahedra. In the fourth O site, O(4) 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. F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Li(5) atom.
Li5FeO4F crystallizes in the monoclinic P2_1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(2) bond length is 1.95 Å. The Li(1)-O(3) bond length is 2.06 Å. The Li(1)-O(4) bond length is 2.05 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one F(1) atom. The Li(2)-O(2) bond length is 1.98 Å. The Li(2)-O(3) bond length is 2.05 Å. The Li(2)-O(4) bond length is 2.02 Å. The Li(2)-F(1) bond length is 1.89 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent Li(5)O3F tetrahedra, edges with two equivalent Li(4)O4F square pyramids, and  an edgeedge with one Li(5)O3F tetrahedra. The Li(3)-O(1) bond length is 2.07 Å. The Li(3)-O(2) bond length is 1.99 Å. The Li(3)-O(3) bond length is 2.05 Å. The Li(3)-O(4) bond length is 2.37 Å. The Li(3)-F(1) bond length is 1.93 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(3)O4F square pyramid, edges with two equivalent Li(3)O4F square pyramids, and edges with two equivalent Li(5)O3F tetrahedra. The Li(4)-O(1) bond length is 1.99 Å. The Li(4)-O(2) bond length is 2.27 Å. The Li(4)-O(3) bond length is 2.13 Å. The Li(4)-O(4) bond length is 2.05 Å. The Li(4)-F(1) bond length is 2.00 Å. In the fifth Li site, Li(5) is bonded to one O(1), one O(3), one O(4), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO3F tetrahedra. The Li(5)-O(1) bond length is 2.04 Å. The Li(5)-O(3) bond length is 2.01 Å. The Li(5)-O(4) bond length is 1.96 Å. The Li(5)-F(1) bond length is 1.88 Å. Fe(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Fe(1)-O(1) bond length is 1.81 Å. The Fe(1)-O(2) bond length is 1.81 Å. The Fe(1)-O(3) bond length is 1.88 Å. The Fe(1)-O(4) bond length is 1.83 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and one Fe(1) atom to form a mixture of corner and edge-sharing OLi4Fe trigonal bipyramids. The corner-sharing octahedral tilt angles are 30°. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one Fe(1) atom. In the third O site, O(3) 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 corner and edge-sharing OLi5Fe octahedra. In the fourth O site, O(4) 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. F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Li(5) atom.