Li8Mn(O2F)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with three equivalent Li(2)O3F tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O2F2 tetrahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(3)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 17-51°. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O2F2 tetrahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(3)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 28-52°. In the third Li site, Li(3) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O2F2 tetrahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(3)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 19-58°. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to two equivalent O(1), two equivalent O(2), and one F(1) atom. Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with four equivalent Li(1)O2F2 tetrahedra, corners with four equivalent Li(2)O3F tetrahedra, corners with four equivalent Li(3)O3F tetrahedra, edges with two equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Li(2)O3F tetrahedra, and edges with two equivalent Li(3)O3F tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), two equivalent Li(4), and one Mn(1) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), two equivalent Li(4), and one Mn(1) atom. F(1) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), two equivalent Li(1), and one Mn(1) atom.
Li8Mn(O2F)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with three equivalent Li(2)O3F tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O2F2 tetrahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(3)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 17-51°. The Li(1)-O(1) bond length is 1.93 Å. The Li(1)-O(2) bond length is 1.89 Å. There is one shorter (1.94 Å) and one longer (1.97 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O2F2 tetrahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(3)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 28-52°. The Li(2)-O(2) bond length is 1.93 Å. There is one shorter (1.92 Å) and one longer (2.11 Å) Li(2)-O(1) bond length. The Li(2)-F(1) bond length is 1.92 Å. In the third Li site, Li(3) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O2F2 tetrahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(3)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 19-58°. The Li(3)-O(1) bond length is 1.89 Å. There is one shorter (1.94 Å) and one longer (2.10 Å) Li(3)-O(2) bond length. The Li(3)-F(1) bond length is 2.02 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to two equivalent O(1), two equivalent O(2), and one F(1) atom. There is one shorter (2.00 Å) and one longer (2.48 Å) Li(4)-O(1) bond length. There is one shorter (2.02 Å) and one longer (2.24 Å) Li(4)-O(2) bond length. The Li(4)-F(1) bond length is 2.55 Å. Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with four equivalent Li(1)O2F2 tetrahedra, corners with four equivalent Li(2)O3F tetrahedra, corners with four equivalent Li(3)O3F tetrahedra, edges with two equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Li(2)O3F tetrahedra, and edges with two equivalent Li(3)O3F tetrahedra. Both Mn(1)-O(1) bond lengths are 2.15 Å. Both Mn(1)-O(2) bond lengths are 2.23 Å. Both Mn(1)-F(1) bond lengths are 2.39 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to one Li(1), one Li(3), two equivalent Li(2), two equivalent Li(4), and one Mn(1) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), two equivalent Li(4), and one Mn(1) atom. F(1) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), two equivalent Li(1), and one Mn(1) atom.