Li4MnF8 crystallizes in the tetragonal I4/mmm space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with six equivalent Li(1)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. Mn(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form MnF6 octahedra that share edges with eight equivalent Li(1)F6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to four equivalent Li(1) atoms. In the second F site, F(2) is bonded to four equivalent Li(1) and one Mn(1) atom to form corner-sharing FLi4Mn square pyramids. In the third F site, F(3) is bonded in a T-shaped geometry to two equivalent Li(1) and one Mn(1) atom.
Li4MnF8 crystallizes in the tetragonal I4/mmm space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with six equivalent Li(1)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. Both Li(1)-F(1) bond lengths are 2.02 Å. Both Li(1)-F(2) bond lengths are 2.04 Å. Both Li(1)-F(3) bond lengths are 2.19 Å. Mn(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form MnF6 octahedra that share edges with eight equivalent Li(1)F6 octahedra. Both Mn(1)-F(2) bond lengths are 1.89 Å. All Mn(1)-F(3) bond lengths are 1.82 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to four equivalent Li(1) atoms. In the second F site, F(2) is bonded to four equivalent Li(1) and one Mn(1) atom to form corner-sharing FLi4Mn square pyramids. In the third F site, F(3) is bonded in a T-shaped geometry to two equivalent Li(1) and one Mn(1) atom.