LiMnOF2 crystallizes in the orthorhombic Pca2_1 space group. There are two 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 distorted LiO2F2 tetrahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with three equivalent Mn(2)O3F3 octahedra, corners with two equivalent Li(1)O2F2 tetrahedra, and  an edgeedge with one Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 35-76°. In the second Li site, Li(2) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form distorted LiF4 tetrahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with three equivalent Mn(2)O3F3 octahedra, corners with two equivalent Li(2)F4 tetrahedra, and  an edgeedge with one Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 20-69°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(1)O2F2 tetrahedra, edges with three equivalent Mn(2)O3F3 octahedra,  an edgeedge with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(1)O2F2 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(2), two equivalent O(1), one F(3), and two equivalent F(2) atoms to form distorted MnO3F3 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Mn(2)O3F3 octahedra, and edges with three equivalent Mn(1)O2F4 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(1), and two equivalent Mn(2) atoms to form corner-sharing OLiMn3 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom. There are four inequivalent F sites. In the first F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(2) and one Mn(1) atom. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom. In the third F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(1), and two equivalent Mn(2) atoms. In the fourth F site, F(3) is bonded in a T-shaped geometry to one Li(2), one Mn(1), and one Mn(2) atom.
LiMnOF2 crystallizes in the orthorhombic Pca2_1 space group. There are two 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 distorted LiO2F2 tetrahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with three equivalent Mn(2)O3F3 octahedra, corners with two equivalent Li(1)O2F2 tetrahedra, and  an edgeedge with one Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 35-76°. The Li(1)-O(1) bond length is 2.05 Å. The Li(1)-O(2) bond length is 2.01 Å. There is one shorter (1.84 Å) and one longer (1.93 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form distorted LiF4 tetrahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with three equivalent Mn(2)O3F3 octahedra, corners with two equivalent Li(2)F4 tetrahedra, and  an edgeedge with one Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 20-69°. The Li(2)-F(2) bond length is 1.92 Å. The Li(2)-F(3) bond length is 1.95 Å. There is one shorter (1.86 Å) and one longer (1.96 Å) Li(2)-F(4) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(1)O2F2 tetrahedra, edges with three equivalent Mn(2)O3F3 octahedra,  an edgeedge with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(1)O2F2 tetrahedra. The Mn(1)-O(1) bond length is 1.96 Å. The Mn(1)-O(2) bond length is 1.86 Å. The Mn(1)-F(1) bond length is 2.06 Å. The Mn(1)-F(2) bond length is 2.37 Å. The Mn(1)-F(3) bond length is 2.05 Å. The Mn(1)-F(4) bond length is 1.99 Å. In the second Mn site, Mn(2) is bonded to one O(2), two equivalent O(1), one F(3), and two equivalent F(2) atoms to form distorted MnO3F3 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Mn(2)O3F3 octahedra, and edges with three equivalent Mn(1)O2F4 octahedra. The Mn(2)-O(2) bond length is 1.85 Å. There is one shorter (1.91 Å) and one longer (2.13 Å) Mn(2)-O(1) bond length. The Mn(2)-F(3) bond length is 2.01 Å. There is one shorter (2.09 Å) and one longer (2.47 Å) Mn(2)-F(2) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(1), and two equivalent Mn(2) atoms to form corner-sharing OLiMn3 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom. There are four inequivalent F sites. In the first F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(2) and one Mn(1) atom. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom. In the third F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(1), and two equivalent Mn(2) atoms. In the fourth F site, F(3) is bonded in a T-shaped geometry to one Li(2), one Mn(1), and one Mn(2) atom.