Li4MnF6 crystallizes in the trigonal P-3m1 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 two equivalent Mn(2)F6 octahedra, corners with six equivalent Li(2)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. In the second Li site, Li(2) 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 four equivalent Mn(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra, edges with three equivalent Li(2)F6 octahedra, and faces with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form MnF6 octahedra that share corners with twelve equivalent Li(2)F6 octahedra and edges with six equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the second Mn site, Mn(2) is bonded to six equivalent F(1) atoms to form MnF6 octahedra that share corners with twelve equivalent Li(1)F6 octahedra and edges with six equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are three inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi4Mn trigonal bipyramids. In the second F site, F(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi4Mn trigonal bipyramids. In the third F site, F(3) is bonded to two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi4Mn square pyramids.
Li4MnF6 crystallizes in the trigonal P-3m1 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 two equivalent Mn(2)F6 octahedra, corners with six equivalent Li(2)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, edges with three equivalent Li(1)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. Both Li(1)-F(1) bond lengths are 2.01 Å. Both Li(1)-F(2) bond lengths are 1.98 Å. Both Li(1)-F(3) bond lengths are 2.15 Å. In the second Li site, Li(2) 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 four equivalent Mn(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra, edges with three equivalent Li(2)F6 octahedra, and faces with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-55°. Both Li(2)-F(1) bond lengths are 2.10 Å. Both Li(2)-F(2) bond lengths are 2.14 Å. Both Li(2)-F(3) bond lengths are 1.98 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form MnF6 octahedra that share corners with twelve equivalent Li(2)F6 octahedra and edges with six equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. All Mn(1)-F(2) bond lengths are 2.17 Å. All Mn(1)-F(3) bond lengths are 2.16 Å. In the second Mn site, Mn(2) is bonded to six equivalent F(1) atoms to form MnF6 octahedra that share corners with twelve equivalent Li(1)F6 octahedra and edges with six equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 54°. All Mn(2)-F(1) bond lengths are 2.15 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi4Mn trigonal bipyramids. In the second F site, F(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi4Mn trigonal bipyramids. In the third F site, F(3) is bonded to two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi4Mn square pyramids.