LiMnF3 crystallizes in the tetragonal P4_2/n space group. Li(1) is bonded to one F(1), one F(3), and three equivalent F(2) atoms to form LiF5 trigonal bipyramids that share corners with four equivalent Mn(1)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with three equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 40-71°. Mn(1) is bonded to one F(2), two equivalent F(1), and three equivalent F(3) atoms to form distorted MnF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra, corners with four equivalent Li(1)F5 trigonal bipyramids,  an edgeedge with one Mn(1)F6 octahedra, and edges with two equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 27-68°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to three equivalent Li(1) and one Mn(1) atom. In the third F site, F(3) is bonded to one Li(1) and three equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra.
LiMnF3 crystallizes in the tetragonal P4_2/n space group. Li(1) is bonded to one F(1), one F(3), and three equivalent F(2) atoms to form LiF5 trigonal bipyramids that share corners with four equivalent Mn(1)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with three equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 40-71°. The Li(1)-F(1) bond length is 2.06 Å. The Li(1)-F(3) bond length is 1.95 Å. There are a spread of Li(1)-F(2) bond distances ranging from 1.92-2.03 Å. Mn(1) is bonded to one F(2), two equivalent F(1), and three equivalent F(3) atoms to form distorted MnF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra, corners with four equivalent Li(1)F5 trigonal bipyramids,  an edgeedge with one Mn(1)F6 octahedra, and edges with two equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 27-68°. The Mn(1)-F(2) bond length is 2.09 Å. Both Mn(1)-F(1) bond lengths are 2.09 Å. There are a spread of Mn(1)-F(3) bond distances ranging from 2.14-2.41 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to three equivalent Li(1) and one Mn(1) atom. In the third F site, F(3) is bonded to one Li(1) and three equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra.