Li2MnF6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. Mn(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with eight equivalent Li(1)F6 octahedra and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 45°. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) 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.
Li2MnF6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. Both Li(1)-F(2) bond lengths are 1.98 Å. There are two shorter (1.98 Å) and two longer (2.02 Å) Li(1)-F(1) 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 eight equivalent Li(1)F6 octahedra and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 45°. Both Mn(1)-F(2) bond lengths are 1.82 Å. All Mn(1)-F(1) bond lengths are 1.81 Å. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) 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.