LiMnF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 6-coordinate geometry to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing MnF6 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing MnF6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(2) atom. In the third F site, F(3) is bonded in a trigonal non-coplanar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom.
LiMnF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 6-coordinate geometry to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms. The Li(1)-F(3) bond length is 2.07 Å. The Li(1)-F(4) bond length is 1.98 Å. There is one shorter (1.98 Å) and one longer (2.49 Å) Li(1)-F(1) bond length. There is one shorter (1.98 Å) and one longer (2.36 Å) Li(1)-F(2) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing MnF6 octahedra. Both Mn(1)-F(1) bond lengths are 1.85 Å. Both Mn(1)-F(3) bond lengths are 2.19 Å. Both Mn(1)-F(4) bond lengths are 1.94 Å. In the second Mn site, Mn(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form edge-sharing MnF6 octahedra. Both Mn(2)-F(2) bond lengths are 1.86 Å. Both Mn(2)-F(3) bond lengths are 1.91 Å. Both Mn(2)-F(4) bond lengths are 2.24 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(2) atom. In the third F site, F(3) is bonded in a trigonal non-coplanar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom.