Li6MnO4F 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 4-coordinate 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 5-coordinate geometry to one O(1), 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), and one F(1) atom to form LiO3F tetrahedra that share corners with four equivalent Mn(1)O4F trigonal bipyramids and edges with two equivalent Li(4)O3F tetrahedra. 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 LiO3F tetrahedra that share corners with four equivalent Mn(1)O4F trigonal bipyramids and edges with two equivalent Li(3)O3F tetrahedra. In the fifth Li site, Li(5) is bonded in a 3-coordinate geometry to 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. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form distorted MnO4F trigonal bipyramids that share corners with four equivalent Li(3)O3F tetrahedra and corners with four equivalent Li(4)O3F 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(6), and one Mn(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), one Li(6), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing OLi6Mn pentagonal bipyramids. 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 Mn(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 Mn(1) atom to form a mixture of corner and edge-sharing OLi4Mn trigonal bipyramids. F(1) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(6), and one Mn(1) atom.
Li6MnO4F 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 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(2) bond length is 2.21 Å. The Li(1)-O(3) bond length is 2.21 Å. The Li(1)-O(4) bond length is 1.98 Å. In the second Li site, Li(2) 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(2)-O(1) bond length is 2.41 Å. The Li(2)-O(2) bond length is 2.12 Å. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(4) bond length is 2.00 Å. The Li(2)-F(1) bond length is 2.20 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 four equivalent Mn(1)O4F trigonal bipyramids and edges with two equivalent Li(4)O3F tetrahedra. The Li(3)-O(1) bond length is 1.91 Å. The Li(3)-O(2) bond length is 1.94 Å. The Li(3)-O(3) bond length is 1.90 Å. The Li(3)-F(1) bond length is 1.88 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 LiO3F tetrahedra that share corners with four equivalent Mn(1)O4F trigonal bipyramids and edges with two equivalent Li(3)O3F tetrahedra. The Li(4)-O(1) bond length is 1.90 Å. The Li(4)-O(2) bond length is 1.87 Å. The Li(4)-O(3) bond length is 1.92 Å. The Li(4)-F(1) bond length is 1.90 Å. In the fifth Li site, Li(5) is bonded in a 3-coordinate geometry to one O(2), one O(3), and one O(4) atom. The Li(5)-O(2) bond length is 2.02 Å. The Li(5)-O(3) bond length is 2.08 Å. The Li(5)-O(4) bond length is 1.90 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 2.10 Å. The Li(6)-O(2) bond length is 2.19 Å. The Li(6)-O(3) bond length is 2.39 Å. The Li(6)-O(4) bond length is 1.95 Å. The Li(6)-F(1) bond length is 2.22 Å. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form distorted MnO4F trigonal bipyramids that share corners with four equivalent Li(3)O3F tetrahedra and corners with four equivalent Li(4)O3F tetrahedra. The Mn(1)-O(1) bond length is 1.92 Å. The Mn(1)-O(2) bond length is 1.94 Å. The Mn(1)-O(3) bond length is 1.92 Å. The Mn(1)-O(4) bond length is 2.06 Å. The Mn(1)-F(1) bond length is 2.16 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(6), and one Mn(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), one Li(6), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing OLi6Mn pentagonal bipyramids. 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 Mn(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 Mn(1) atom to form a mixture of corner and edge-sharing OLi4Mn trigonal bipyramids. F(1) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(6), and one Mn(1) atom.