Li2MnF4 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with six equivalent Mn(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-66°. In the second Li site, Li(2) is bonded to one F(2), one F(4), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with six equivalent Mn(1)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-66°. Mn(1) is bonded to one F(1), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, corners with six equivalent Li(2)F4 tetrahedra, and edges with two equivalent Mn(1)F6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Mn2 tetrahedra. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Mn(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Mn2 tetrahedra.
Li2MnF4 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with six equivalent Mn(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-66°. The Li(1)-F(2) bond length is 1.97 Å. The Li(1)-F(4) bond length is 1.97 Å. Both Li(1)-F(1) bond lengths are 1.87 Å. In the second Li site, Li(2) is bonded to one F(2), one F(4), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with six equivalent Mn(1)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-66°. The Li(2)-F(2) bond length is 1.98 Å. The Li(2)-F(4) bond length is 1.96 Å. There is one shorter (1.87 Å) and one longer (1.88 Å) Li(2)-F(3) bond length. Mn(1) is bonded to one F(1), one F(3), two equivalent F(2), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, corners with six equivalent Li(2)F4 tetrahedra, and edges with two equivalent Mn(1)F6 octahedra. The Mn(1)-F(1) bond length is 2.08 Å. The Mn(1)-F(3) bond length is 2.08 Å. Both Mn(1)-F(2) bond lengths are 2.20 Å. There is one shorter (2.20 Å) and one longer (2.21 Å) Mn(1)-F(4) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Mn2 tetrahedra. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Mn(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLi2Mn2 tetrahedra.