LiMnF4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one F(1), one F(2), one F(4), and three equivalent F(3) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 11-34°. Mn(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra, and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 7-26°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Li(1) and one Mn(1) atom. In the third F site, F(3) is bonded to three equivalent Li(1) and one Mn(1) atom to form a mixture of edge and corner-sharing FLi3Mn trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Mn(1) atoms.
LiMnF4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one F(1), one F(2), one F(4), and three equivalent F(3) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 11-34°. The Li(1)-F(1) bond length is 2.06 Å. The Li(1)-F(2) bond length is 1.94 Å. The Li(1)-F(4) bond length is 2.46 Å. There are two shorter (2.06 Å) and one longer (2.14 Å) Li(1)-F(3) bond length. Mn(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Mn(1)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra, and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 7-26°. The Mn(1)-F(2) bond length is 1.81 Å. The Mn(1)-F(3) bond length is 2.03 Å. There is one shorter (1.92 Å) and one longer (2.16 Å) Mn(1)-F(1) bond length. Both Mn(1)-F(4) bond lengths are 1.97 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Li(1) and one Mn(1) atom. In the third F site, F(3) is bonded to three equivalent Li(1) and one Mn(1) atom to form a mixture of edge and corner-sharing FLi3Mn trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Mn(1) atoms.