LiMnF4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(3), one F(4), one F(7), one F(9), and two equivalent F(5) atoms. In the second Li site, Li(2) is bonded to one F(1), one F(5), one F(6), and two equivalent F(7) atoms to form distorted LiF5 square pyramids that share corners with two equivalent Li(2)F5 square pyramids,  an edgeedge with one Mn(2)F6 octahedra, and edges with two equivalent Mn(1)F6 octahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(2), one F(3), one F(7), one F(9), and two equivalent F(1) atoms to form MnF6 octahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with three equivalent Mn(1)F6 octahedra, and edges with two equivalent Li(2)F5 square pyramids. The corner-sharing octahedral tilt angles range from 0-13°. In the second Mn site, Mn(2) is bonded to one F(2), one F(5), one F(6), one F(8), and two equivalent F(4) atoms to form MnF6 octahedra that share  a cornercorner with one Mn(1)F6 octahedra, corners with three equivalent Mn(2)F6 octahedra, and  an edgeedge with one Li(2)F5 square pyramid. The corner-sharing octahedral tilt angles range from 0-15°. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Mn(1) and one Mn(2) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1) and two equivalent Mn(2) atoms. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(1), and one Mn(2) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the sixth F site, F(6) is bonded in a water-like geometry to one Li(2) and one Mn(2) atom. In the seventh F site, F(7) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent Mn(2) atoms. In the ninth F site, F(9) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Mn(1) atoms.
LiMnF4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one F(3), one F(4), one F(7), one F(9), and two equivalent F(5) atoms. The Li(1)-F(3) bond length is 1.92 Å. The Li(1)-F(4) bond length is 2.10 Å. The Li(1)-F(7) bond length is 2.23 Å. The Li(1)-F(9) bond length is 2.44 Å. Both Li(1)-F(5) bond lengths are 2.04 Å. In the second Li site, Li(2) is bonded to one F(1), one F(5), one F(6), and two equivalent F(7) atoms to form distorted LiF5 square pyramids that share corners with two equivalent Li(2)F5 square pyramids,  an edgeedge with one Mn(2)F6 octahedra, and edges with two equivalent Mn(1)F6 octahedra. The Li(2)-F(1) bond length is 2.42 Å. The Li(2)-F(5) bond length is 2.01 Å. The Li(2)-F(6) bond length is 1.98 Å. Both Li(2)-F(7) bond lengths are 2.12 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(2), one F(3), one F(7), one F(9), and two equivalent F(1) atoms to form MnF6 octahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with three equivalent Mn(1)F6 octahedra, and edges with two equivalent Li(2)F5 square pyramids. The corner-sharing octahedral tilt angles range from 0-13°. The Mn(1)-F(2) bond length is 2.05 Å. The Mn(1)-F(3) bond length is 1.81 Å. The Mn(1)-F(7) bond length is 1.91 Å. The Mn(1)-F(9) bond length is 2.05 Å. Both Mn(1)-F(1) bond lengths are 2.00 Å. In the second Mn site, Mn(2) is bonded to one F(2), one F(5), one F(6), one F(8), and two equivalent F(4) atoms to form MnF6 octahedra that share  a cornercorner with one Mn(1)F6 octahedra, corners with three equivalent Mn(2)F6 octahedra, and  an edgeedge with one Li(2)F5 square pyramid. The corner-sharing octahedral tilt angles range from 0-15°. The Mn(2)-F(2) bond length is 1.88 Å. The Mn(2)-F(5) bond length is 2.03 Å. The Mn(2)-F(6) bond length is 1.85 Å. The Mn(2)-F(8) bond length is 1.96 Å. Both Mn(2)-F(4) bond lengths are 2.01 Å. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Mn(1) and one Mn(2) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1) and two equivalent Mn(2) atoms. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(1), and one Mn(2) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the sixth F site, F(6) is bonded in a water-like geometry to one Li(2) and one Mn(2) atom. In the seventh F site, F(7) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of corner and edge-sharing FLi3Mn trigonal pyramids. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent Mn(2) atoms. In the ninth F site, F(9) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Mn(1) atoms.