LiMnF3 crystallizes in the trigonal P-3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form LiF6 octahedra that share corners with three equivalent Mn(1)F6 octahedra, edges with three equivalent Mn(2)F6 octahedra,  a faceface with one Li(3)F6 octahedra, and  a faceface with one Mn(4)F6 octahedra. The corner-sharing octahedral tilt angles are 52°. In the second Li site, Li(2) is bonded in a trigonal planar geometry to three equivalent F(1) atoms. In the third Li site, Li(3) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted LiF6 octahedra that share corners with three equivalent Mn(2)F6 octahedra, edges with three equivalent Mn(1)F6 octahedra,  a faceface with one Li(1)F6 octahedra, and  a faceface with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles are 44°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted MnF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Mn(2)F6 octahedra, corners with three equivalent Mn(3)F6 octahedra, and edges with three equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. In the second Mn site, Mn(2) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form distorted MnF6 octahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Mn(1)F6 octahedra, corners with three equivalent Mn(4)F6 octahedra, and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-56°. In the third Mn site, Mn(3) is bonded to six equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra and faces with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles are 42°. In the fourth Mn site, Mn(4) is bonded to six equivalent F(3) atoms to form distorted MnF6 octahedra that share corners with six equivalent Mn(2)F6 octahedra and faces with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 40°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Mn(1), and one Mn(3) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one Mn(4) atom.
LiMnF3 crystallizes in the trigonal P-3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form LiF6 octahedra that share corners with three equivalent Mn(1)F6 octahedra, edges with three equivalent Mn(2)F6 octahedra,  a faceface with one Li(3)F6 octahedra, and  a faceface with one Mn(4)F6 octahedra. The corner-sharing octahedral tilt angles are 52°. All Li(1)-F(2) bond lengths are 2.18 Å. All Li(1)-F(3) bond lengths are 1.92 Å. In the second Li site, Li(2) is bonded in a trigonal planar geometry to three equivalent F(1) atoms. All Li(2)-F(1) bond lengths are 1.91 Å. In the third Li site, Li(3) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted LiF6 octahedra that share corners with three equivalent Mn(2)F6 octahedra, edges with three equivalent Mn(1)F6 octahedra,  a faceface with one Li(1)F6 octahedra, and  a faceface with one Mn(3)F6 octahedra. The corner-sharing octahedral tilt angles are 44°. All Li(3)-F(1) bond lengths are 2.28 Å. All Li(3)-F(2) bond lengths are 1.93 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted MnF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Mn(2)F6 octahedra, corners with three equivalent Mn(3)F6 octahedra, and edges with three equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. All Mn(1)-F(1) bond lengths are 2.34 Å. All Mn(1)-F(2) bond lengths are 2.07 Å. In the second Mn site, Mn(2) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form distorted MnF6 octahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Mn(1)F6 octahedra, corners with three equivalent Mn(4)F6 octahedra, and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-56°. All Mn(2)-F(2) bond lengths are 2.37 Å. All Mn(2)-F(3) bond lengths are 2.02 Å. In the third Mn site, Mn(3) is bonded to six equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra and faces with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles are 42°. All Mn(3)-F(1) bond lengths are 2.13 Å. In the fourth Mn site, Mn(4) is bonded to six equivalent F(3) atoms to form distorted MnF6 octahedra that share corners with six equivalent Mn(2)F6 octahedra and faces with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 40°. All Mn(4)-F(3) bond lengths are 2.17 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Mn(1), and one Mn(3) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one Mn(4) atom.