LiMnF3 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), one F(6), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(3)F6 pentagonal pyramids,  a cornercorner with one Li(2)F4 tetrahedra, and  a cornercorner with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-72°. In the second Li site, Li(2) is bonded to one F(1), one F(5), one F(6), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with four equivalent Mn(3)F6 pentagonal pyramids,  a cornercorner with one Li(1)F4 tetrahedra, and  a cornercorner with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the third Li site, Li(3) is bonded to one F(3), one F(7), one F(8), and one F(9) atom to form LiF4 tetrahedra that share corners with three equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(3)F6 pentagonal pyramids,  a cornercorner with one Li(1)F4 tetrahedra, and  a cornercorner with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 62-66°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one F(1), one F(3), one F(8), one F(9), and two equivalent F(4) atoms. In the second Mn site, Mn(2) is bonded to one F(2), one F(4), one F(5), one F(8), and two equivalent F(3) atoms to form MnF6 octahedra that share  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)F4 tetrahedra,  an edgeedge with one Mn(2)F6 octahedra, and edges with two equivalent Mn(3)F6 pentagonal pyramids. In the third Mn site, Mn(3) is bonded to one F(2), one F(6), one F(7), one F(8), and two equivalent F(5) atoms to form distorted MnF6 pentagonal pyramids that share corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra, corners with four equivalent Li(2)F4 tetrahedra, edges with two equivalent Mn(2)F6 octahedra, and  an edgeedge with one Mn(3)F6 pentagonal pyramid. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one Mn(3) atom. In the third F site, F(3) is bonded to one Li(3), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the fourth F site, F(4) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the fifth F site, F(5) is bonded to one Li(2), one Mn(2), and two equivalent Mn(3) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Mn(3) atom. In the seventh F site, F(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(3), and one Mn(3) atom. In the eighth F site, F(8) is bonded to one Li(3), one Mn(1), one Mn(2), and one Mn(3) atom to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the ninth F site, F(9) is bonded in a T-shaped geometry to one Li(1), one Li(3), and one Mn(1) atom.
LiMnF3 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), one F(6), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(3)F6 pentagonal pyramids,  a cornercorner with one Li(2)F4 tetrahedra, and  a cornercorner with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-72°. The Li(1)-F(2) bond length is 1.87 Å. The Li(1)-F(4) bond length is 1.95 Å. The Li(1)-F(6) bond length is 1.80 Å. The Li(1)-F(9) bond length is 1.95 Å. In the second Li site, Li(2) is bonded to one F(1), one F(5), one F(6), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with four equivalent Mn(3)F6 pentagonal pyramids,  a cornercorner with one Li(1)F4 tetrahedra, and  a cornercorner with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. The Li(2)-F(1) bond length is 1.82 Å. The Li(2)-F(5) bond length is 1.92 Å. The Li(2)-F(6) bond length is 1.86 Å. The Li(2)-F(7) bond length is 1.86 Å. In the third Li site, Li(3) is bonded to one F(3), one F(7), one F(8), and one F(9) atom to form LiF4 tetrahedra that share corners with three equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(3)F6 pentagonal pyramids,  a cornercorner with one Li(1)F4 tetrahedra, and  a cornercorner with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 62-66°. The Li(3)-F(3) bond length is 1.93 Å. The Li(3)-F(7) bond length is 1.83 Å. The Li(3)-F(8) bond length is 1.95 Å. The Li(3)-F(9) bond length is 1.90 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one F(1), one F(3), one F(8), one F(9), and two equivalent F(4) atoms. The Mn(1)-F(1) bond length is 1.95 Å. The Mn(1)-F(3) bond length is 2.27 Å. The Mn(1)-F(8) bond length is 2.58 Å. The Mn(1)-F(9) bond length is 2.05 Å. There is one shorter (2.29 Å) and one longer (2.42 Å) Mn(1)-F(4) bond length. In the second Mn site, Mn(2) is bonded to one F(2), one F(4), one F(5), one F(8), and two equivalent F(3) atoms to form MnF6 octahedra that share  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)F4 tetrahedra,  an edgeedge with one Mn(2)F6 octahedra, and edges with two equivalent Mn(3)F6 pentagonal pyramids. The Mn(2)-F(2) bond length is 2.10 Å. The Mn(2)-F(4) bond length is 2.19 Å. The Mn(2)-F(5) bond length is 2.19 Å. The Mn(2)-F(8) bond length is 2.12 Å. There is one shorter (2.22 Å) and one longer (2.25 Å) Mn(2)-F(3) bond length. In the third Mn site, Mn(3) is bonded to one F(2), one F(6), one F(7), one F(8), and two equivalent F(5) atoms to form distorted MnF6 pentagonal pyramids that share corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra, corners with four equivalent Li(2)F4 tetrahedra, edges with two equivalent Mn(2)F6 octahedra, and  an edgeedge with one Mn(3)F6 pentagonal pyramid. The Mn(3)-F(2) bond length is 2.21 Å. The Mn(3)-F(6) bond length is 2.04 Å. The Mn(3)-F(7) bond length is 2.06 Å. The Mn(3)-F(8) bond length is 2.32 Å. There is one shorter (2.26 Å) and one longer (2.36 Å) Mn(3)-F(5) bond length. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(2) and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one Mn(3) atom. In the third F site, F(3) is bonded to one Li(3), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the fourth F site, F(4) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the fifth F site, F(5) is bonded to one Li(2), one Mn(2), and two equivalent Mn(3) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Mn(3) atom. In the seventh F site, F(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(3), and one Mn(3) atom. In the eighth F site, F(8) is bonded to one Li(3), one Mn(1), one Mn(2), and one Mn(3) atom to form a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the ninth F site, F(9) is bonded in a T-shaped geometry to one Li(1), one Li(3), and one Mn(1) atom.