Li8Mn(O2F)2 crystallizes in the orthorhombic Cmc2_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), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(5)O3F tetrahedra, corners with two equivalent Mn(1)O2F2 tetrahedra, corners with six equivalent Li(4)O3F tetrahedra, edges with two equivalent Li(3)O2F2 tetrahedra, and edges with two equivalent Li(5)O3F tetrahedra. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one O(1), one O(3), and two equivalent O(2) atoms. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share corners with three equivalent Li(3)O2F2 tetrahedra, corners with three equivalent Mn(1)O2F2 tetrahedra, corners with four equivalent Li(5)O3F tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Li(4)O3F tetrahedra. In the fourth Li site, Li(4) is bonded to one O(3), two equivalent O(2), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent Mn(1)O2F2 tetrahedra, corners with three equivalent Li(4)O3F tetrahedra, corners with three equivalent Li(5)O3F tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(3)O2F2 tetrahedra, and edges with two equivalent Li(5)O3F tetrahedra. In the fifth Li site, Li(5) is bonded to one O(3), two equivalent O(2), and one F(1) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with three equivalent Li(4)O3F tetrahedra, corners with three equivalent Li(5)O3F tetrahedra, corners with four equivalent Li(3)O2F2 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Mn(1)O2F2 tetrahedra, and edges with two equivalent Li(4)O3F tetrahedra. Mn(1) is bonded to one O(1), one O(3), and two equivalent F(1) atoms to form MnO2F2 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(4)O3F tetrahedra, corners with six equivalent Li(3)O2F2 tetrahedra, and edges with two equivalent Li(5)O3F tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Mn(1) atom to form OLi4Mn trigonal bipyramids that share corners with six equivalent F(1)Li4Mn trigonal 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), two equivalent Li(4), and two equivalent Li(5) atoms. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(4), two equivalent Li(5), and one Mn(1) atom. F(1) is bonded to one Li(4), one Li(5), two equivalent Li(3), and one Mn(1) atom to form FLi4Mn trigonal bipyramids that share corners with three equivalent O(1)Li4Mn trigonal bipyramids and corners with three equivalent F(1)Li4Mn trigonal bipyramids.
Li8Mn(O2F)2 crystallizes in the orthorhombic Cmc2_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), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(5)O3F tetrahedra, corners with two equivalent Mn(1)O2F2 tetrahedra, corners with six equivalent Li(4)O3F tetrahedra, edges with two equivalent Li(3)O2F2 tetrahedra, and edges with two equivalent Li(5)O3F tetrahedra. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-O(3) bond length is 1.96 Å. Both Li(1)-O(2) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Li(2)-O(1) bond length is 1.95 Å. The Li(2)-O(3) bond length is 2.51 Å. Both Li(2)-O(2) bond lengths are 2.00 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share corners with three equivalent Li(3)O2F2 tetrahedra, corners with three equivalent Mn(1)O2F2 tetrahedra, corners with four equivalent Li(5)O3F tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Li(4)O3F tetrahedra. The Li(3)-O(1) bond length is 1.86 Å. The Li(3)-O(2) bond length is 2.01 Å. Both Li(3)-F(1) bond lengths are 1.96 Å. In the fourth Li site, Li(4) is bonded to one O(3), two equivalent O(2), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent Mn(1)O2F2 tetrahedra, corners with three equivalent Li(4)O3F tetrahedra, corners with three equivalent Li(5)O3F tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(3)O2F2 tetrahedra, and edges with two equivalent Li(5)O3F tetrahedra. The Li(4)-O(3) bond length is 1.98 Å. Both Li(4)-O(2) bond lengths are 2.03 Å. The Li(4)-F(1) bond length is 2.05 Å. In the fifth Li site, Li(5) is bonded to one O(3), two equivalent O(2), and one F(1) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with three equivalent Li(4)O3F tetrahedra, corners with three equivalent Li(5)O3F tetrahedra, corners with four equivalent Li(3)O2F2 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Mn(1)O2F2 tetrahedra, and edges with two equivalent Li(4)O3F tetrahedra. The Li(5)-O(3) bond length is 2.18 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) Li(5)-O(2) bond length. The Li(5)-F(1) bond length is 2.06 Å. Mn(1) is bonded to one O(1), one O(3), and two equivalent F(1) atoms to form MnO2F2 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(4)O3F tetrahedra, corners with six equivalent Li(3)O2F2 tetrahedra, and edges with two equivalent Li(5)O3F tetrahedra. The Mn(1)-O(1) bond length is 1.93 Å. The Mn(1)-O(3) bond length is 2.02 Å. Both Mn(1)-F(1) bond lengths are 2.14 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Mn(1) atom to form OLi4Mn trigonal bipyramids that share corners with six equivalent F(1)Li4Mn trigonal 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), two equivalent Li(4), and two equivalent Li(5) atoms. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Li(1), one Li(2), two equivalent Li(4), two equivalent Li(5), and one Mn(1) atom. F(1) is bonded to one Li(4), one Li(5), two equivalent Li(3), and one Mn(1) atom to form FLi4Mn trigonal bipyramids that share corners with three equivalent O(1)Li4Mn trigonal bipyramids and corners with three equivalent F(1)Li4Mn trigonal bipyramids.