LiMnF4 is zeta iron carbide-derived structured and crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with six equivalent Mn(1)F6 octahedra, and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. Mn(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom.
LiMnF4 is zeta iron carbide-derived structured and crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with six equivalent Mn(1)F6 octahedra, and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. Both Li(1)-F(1) bond lengths are 2.05 Å. There are two shorter (2.08 Å) and two longer (2.25 Å) Li(1)-F(2) bond lengths. Mn(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. Both Mn(1)-F(2) bond lengths are 1.86 Å. There are two shorter (1.93 Å) and two longer (2.18 Å) Mn(1)-F(1) bond lengths. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom.