LiMnF3 crystallizes in the trigonal R-3c space group. Li(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiF5 trigonal bipyramids that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F7 pentagonal bipyramids, corners with six equivalent Li(1)F5 trigonal bipyramids, and edges with two equivalent Mn(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 64°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent F(1) atoms to form distorted MnF6 octahedra that share corners with six equivalent Li(1)F5 trigonal bipyramids and edges with six equivalent Mn(2)F7 pentagonal bipyramids. In the second Mn site, Mn(2) is bonded to one F(2) and six equivalent F(1) atoms to form distorted MnF7 pentagonal bipyramids that share corners with three equivalent Li(1)F5 trigonal bipyramids, edges with three equivalent Mn(1)F6 octahedra, edges with three equivalent Mn(2)F7 pentagonal bipyramids, and edges with three equivalent Li(1)F5 trigonal bipyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Mn(1), and two equivalent Mn(2) atoms to form FLiMn3 tetrahedra that share corners with ten equivalent F(1)LiMn3 tetrahedra, corners with two equivalent F(2)Li3Mn trigonal pyramids, edges with three equivalent F(1)LiMn3 tetrahedra, and  an edgeedge with one F(2)Li3Mn trigonal pyramid. In the second F site, F(2) is bonded to three equivalent Li(1) and one Mn(2) atom to form FLi3Mn trigonal pyramids that share corners with six equivalent F(1)LiMn3 tetrahedra, corners with three equivalent F(2)Li3Mn trigonal pyramids, and edges with three equivalent F(1)LiMn3 tetrahedra. In the third F site, F(3) is bonded in a trigonal planar geometry to three equivalent Li(1) atoms.
LiMnF3 crystallizes in the trigonal R-3c space group. Li(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiF5 trigonal bipyramids that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F7 pentagonal bipyramids, corners with six equivalent Li(1)F5 trigonal bipyramids, and edges with two equivalent Mn(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 64°. The Li(1)-F(3) bond length is 1.88 Å. Both Li(1)-F(1) bond lengths are 2.04 Å. Both Li(1)-F(2) bond lengths are 2.07 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent F(1) atoms to form distorted MnF6 octahedra that share corners with six equivalent Li(1)F5 trigonal bipyramids and edges with six equivalent Mn(2)F7 pentagonal bipyramids. All Mn(1)-F(1) bond lengths are 2.15 Å. In the second Mn site, Mn(2) is bonded to one F(2) and six equivalent F(1) atoms to form distorted MnF7 pentagonal bipyramids that share corners with three equivalent Li(1)F5 trigonal bipyramids, edges with three equivalent Mn(1)F6 octahedra, edges with three equivalent Mn(2)F7 pentagonal bipyramids, and edges with three equivalent Li(1)F5 trigonal bipyramids. The Mn(2)-F(2) bond length is 2.24 Å. There are three shorter (2.17 Å) and three longer (2.28 Å) Mn(2)-F(1) bond lengths. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Mn(1), and two equivalent Mn(2) atoms to form FLiMn3 tetrahedra that share corners with ten equivalent F(1)LiMn3 tetrahedra, corners with two equivalent F(2)Li3Mn trigonal pyramids, edges with three equivalent F(1)LiMn3 tetrahedra, and  an edgeedge with one F(2)Li3Mn trigonal pyramid. In the second F site, F(2) is bonded to three equivalent Li(1) and one Mn(2) atom to form FLi3Mn trigonal pyramids that share corners with six equivalent F(1)LiMn3 tetrahedra, corners with three equivalent F(2)Li3Mn trigonal pyramids, and edges with three equivalent F(1)LiMn3 tetrahedra. In the third F site, F(3) is bonded in a trigonal planar geometry to three equivalent Li(1) atoms.