Li5MnF8 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Li sites. In the first Li site, 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 Li(2)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 6-12°. In the second Li site, Li(2) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form LiF6 octahedra that share edges with two equivalent Mn(1)F6 octahedra and edges with eight equivalent Li(1)F6 octahedra. Mn(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form MnF6 octahedra that share edges with two equivalent Li(2)F6 octahedra and edges with eight equivalent Li(1)F6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2) and four equivalent Li(1) atoms to form FLi5 square pyramids that share  a cornercorner with one F(1)Li5 square pyramid, corners with four equivalent F(2)Li4Mn square pyramids, edges with two equivalent F(2)Li4Mn square pyramids, and edges with two equivalent F(1)Li5 square pyramids. In the second F site, F(2) is bonded to four equivalent Li(1) and one Mn(1) atom to form FLi4Mn square pyramids that share  a cornercorner with one F(2)Li4Mn square pyramid, corners with four equivalent F(1)Li5 square pyramids, edges with two equivalent F(2)Li4Mn square pyramids, and edges with two equivalent F(1)Li5 square pyramids. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Mn(1) atom.
Li5MnF8 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Li sites. In the first Li site, 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 Li(2)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 6-12°. Both Li(1)-F(1) bond lengths are 1.99 Å. Both Li(1)-F(2) bond lengths are 2.10 Å. Both Li(1)-F(3) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form LiF6 octahedra that share edges with two equivalent Mn(1)F6 octahedra and edges with eight equivalent Li(1)F6 octahedra. Both Li(2)-F(1) bond lengths are 2.01 Å. All Li(2)-F(3) bond lengths are 2.01 Å. Mn(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form MnF6 octahedra that share edges with two equivalent Li(2)F6 octahedra and edges with eight equivalent Li(1)F6 octahedra. Both Mn(1)-F(2) bond lengths are 2.10 Å. All Mn(1)-F(3) bond lengths are 1.89 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2) and four equivalent Li(1) atoms to form FLi5 square pyramids that share  a cornercorner with one F(1)Li5 square pyramid, corners with four equivalent F(2)Li4Mn square pyramids, edges with two equivalent F(2)Li4Mn square pyramids, and edges with two equivalent F(1)Li5 square pyramids. In the second F site, F(2) is bonded to four equivalent Li(1) and one Mn(1) atom to form FLi4Mn square pyramids that share  a cornercorner with one F(2)Li4Mn square pyramid, corners with four equivalent F(1)Li5 square pyramids, edges with two equivalent F(2)Li4Mn square pyramids, and edges with two equivalent F(1)Li5 square pyramids. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Mn(1) atom.