Li4Mn(OF)2 is Aluminum carbonitride-derived structured and crystallizes in the monoclinic P2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), two equivalent O(1), and one F(2) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with three equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(4)OF3 tetrahedra. The corner-sharing octahedral tilt angles are 49°. In the second Li site, Li(2) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Li(3)OF3 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with three equivalent Li(4)OF3 tetrahedra, edges with three equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles are 49°. In the third Li site, Li(3) is bonded to one O(1), one F(2), and two equivalent F(1) atoms to form LiOF3 tetrahedra that share corners with three equivalent Mn(1)O4F2 octahedra,  a cornercorner with one Li(2)O3F tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra, corners with three equivalent Li(1)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(4)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 42-72°. In the fourth Li site, Li(4) is bonded to one O(2), one F(1), and two equivalent F(2) atoms to form LiOF3 tetrahedra that share corners with three equivalent Mn(1)O4F2 octahedra,  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 42-72°. Mn(1) is bonded to two equivalent O(1), two equivalent O(2), one F(1), and one F(2) atom to form distorted MnO4F2 octahedra that share corners with four equivalent Mn(1)O4F2 octahedra,  a cornercorner with one Li(1)O3F tetrahedra,  a cornercorner with one Li(2)O3F tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, corners with three equivalent Li(4)OF3 tetrahedra,  an edgeedge with one Li(3)OF3 tetrahedra,  an edgeedge with one Li(4)OF3 tetrahedra, edges with three equivalent Li(1)O3F tetrahedra, and edges with three equivalent Li(2)O3F tetrahedra. The corner-sharing octahedral tilt angles are 47°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(4), two equivalent Li(2), and two equivalent Mn(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), two equivalent Li(3), and one Mn(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), two equivalent Li(4), and one Mn(1) atom.
Li4Mn(OF)2 is Aluminum carbonitride-derived structured and crystallizes in the monoclinic P2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), two equivalent O(1), and one F(2) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Li(4)OF3 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with three equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(4)OF3 tetrahedra. The corner-sharing octahedral tilt angles are 49°. The Li(1)-O(2) bond length is 1.98 Å. There is one shorter (1.97 Å) and one longer (2.04 Å) Li(1)-O(1) bond length. The Li(1)-F(2) bond length is 2.02 Å. In the second Li site, Li(2) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Li(3)OF3 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with two equivalent Li(2)O3F tetrahedra, corners with three equivalent Li(4)OF3 tetrahedra, edges with three equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles are 49°. The Li(2)-O(1) bond length is 1.98 Å. There is one shorter (1.97 Å) and one longer (2.04 Å) Li(2)-O(2) bond length. The Li(2)-F(1) bond length is 2.02 Å. In the third Li site, Li(3) is bonded to one O(1), one F(2), and two equivalent F(1) atoms to form LiOF3 tetrahedra that share corners with three equivalent Mn(1)O4F2 octahedra,  a cornercorner with one Li(2)O3F tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra, corners with three equivalent Li(1)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(2)O3F tetrahedra, and  an edgeedge with one Li(4)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 42-72°. The Li(3)-O(1) bond length is 1.92 Å. The Li(3)-F(2) bond length is 1.95 Å. Both Li(3)-F(1) bond lengths are 1.96 Å. In the fourth Li site, Li(4) is bonded to one O(2), one F(1), and two equivalent F(2) atoms to form LiOF3 tetrahedra that share corners with three equivalent Mn(1)O4F2 octahedra,  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Li(3)OF3 tetrahedra, corners with two equivalent Li(4)OF3 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O3F tetrahedra, and  an edgeedge with one Li(3)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 42-72°. The Li(4)-O(2) bond length is 1.92 Å. The Li(4)-F(1) bond length is 1.95 Å. Both Li(4)-F(2) bond lengths are 1.96 Å. Mn(1) is bonded to two equivalent O(1), two equivalent O(2), one F(1), and one F(2) atom to form distorted MnO4F2 octahedra that share corners with four equivalent Mn(1)O4F2 octahedra,  a cornercorner with one Li(1)O3F tetrahedra,  a cornercorner with one Li(2)O3F tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, corners with three equivalent Li(4)OF3 tetrahedra,  an edgeedge with one Li(3)OF3 tetrahedra,  an edgeedge with one Li(4)OF3 tetrahedra, edges with three equivalent Li(1)O3F tetrahedra, and edges with three equivalent Li(2)O3F tetrahedra. The corner-sharing octahedral tilt angles are 47°. There is one shorter (2.07 Å) and one longer (2.25 Å) Mn(1)-O(1) bond length. There is one shorter (2.07 Å) and one longer (2.25 Å) Mn(1)-O(2) bond length. The Mn(1)-F(1) bond length is 2.55 Å. The Mn(1)-F(2) bond length is 2.56 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(4), two equivalent Li(2), and two equivalent Mn(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), two equivalent Li(3), and one Mn(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(3), two equivalent Li(4), and one Mn(1) atom.