Li6FeO4F crystallizes in the monoclinic P2_1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one F(1) atom. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO4F trigonal bipyramids. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent Li(2)O4F trigonal bipyramids, edges with two equivalent Li(4)O3F tetrahedra, and  an edgeedge with one Li(2)O4F trigonal bipyramid. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with two equivalent Li(2)O4F trigonal bipyramids, edges with two equivalent Li(3)O3F tetrahedra, and  an edgeedge with one Li(2)O4F trigonal bipyramid. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one F(1) atom. Fe(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one F(1) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OLi6Fe pentagonal bipyramids. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Fe(1) atom. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Fe(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(5), one Li(6), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OLi4Fe trigonal bipyramids. F(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(6), and one Fe(1) atom.
Li6FeO4F crystallizes in the monoclinic P2_1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one F(1) atom. The Li(1)-O(1) bond length is 2.24 Å. The Li(1)-O(2) bond length is 2.36 Å. The Li(1)-O(3) bond length is 2.08 Å. The Li(1)-O(4) bond length is 2.06 Å. The Li(1)-F(1) bond length is 2.27 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO4F trigonal bipyramids. The Li(2)-O(1) bond length is 2.15 Å. The Li(2)-O(2) bond length is 2.25 Å. The Li(2)-O(3) bond length is 2.13 Å. The Li(2)-O(4) bond length is 2.06 Å. The Li(2)-F(1) bond length is 2.12 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent Li(2)O4F trigonal bipyramids, edges with two equivalent Li(4)O3F tetrahedra, and  an edgeedge with one Li(2)O4F trigonal bipyramid. The Li(3)-O(1) bond length is 1.93 Å. The Li(3)-O(2) bond length is 1.92 Å. The Li(3)-O(3) bond length is 1.89 Å. The Li(3)-F(1) bond length is 1.90 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with two equivalent Li(2)O4F trigonal bipyramids, edges with two equivalent Li(3)O3F tetrahedra, and  an edgeedge with one Li(2)O4F trigonal bipyramid. The Li(4)-O(1) bond length is 1.89 Å. The Li(4)-O(2) bond length is 1.98 Å. The Li(4)-O(3) bond length is 1.97 Å. The Li(4)-F(1) bond length is 1.89 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(5)-O(1) bond length is 2.06 Å. The Li(5)-O(2) bond length is 2.39 Å. The Li(5)-O(3) bond length is 2.14 Å. The Li(5)-O(4) bond length is 1.94 Å. In the sixth Li site, Li(6) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one F(1) atom. The Li(6)-O(1) bond length is 2.24 Å. The Li(6)-O(2) bond length is 2.02 Å. The Li(6)-O(3) bond length is 2.45 Å. The Li(6)-O(4) bond length is 1.93 Å. The Li(6)-F(1) bond length is 2.29 Å. Fe(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one F(1) atom. The Fe(1)-O(1) bond length is 1.96 Å. The Fe(1)-O(2) bond length is 1.95 Å. The Fe(1)-O(3) bond length is 1.94 Å. The Fe(1)-O(4) bond length is 1.92 Å. The Fe(1)-F(1) bond length is 2.29 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OLi6Fe pentagonal bipyramids. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Fe(1) atom. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Fe(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(5), one Li(6), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OLi4Fe trigonal bipyramids. F(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(6), and one Fe(1) atom.