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(1), one F(2), one F(4), and one F(6) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with two equivalent Mn(1)F7 pentagonal bipyramids,  a cornercorner with one Li(2)F4 tetrahedra,  a cornercorner with one Li(3)F4 tetrahedra, and  an edgeedge with one Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles are 69°. In the second Li site, Li(2) is bonded to one F(3), one F(4), one F(5), and one F(9) atom to form distorted LiF4 tetrahedra that share corners with three equivalent Mn(2)F6 octahedra,  a cornercorner with one Mn(1)F7 pentagonal bipyramid,  a cornercorner with one Li(1)F4 tetrahedra,  a cornercorner with one Li(3)F4 tetrahedra, and  an edgeedge with one Mn(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 39-60°. In the third Li site, Li(3) is bonded to one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra,  a cornercorner with one Mn(1)F7 pentagonal bipyramid,  a cornercorner with one Li(1)F4 tetrahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  an edgeedge with one Mn(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 52°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(2), one F(5), two equivalent F(3), and two equivalent F(7) atoms to form distorted MnF7 pentagonal bipyramids that share  a cornercorner with one Li(2)F4 tetrahedra,  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, edges with two equivalent Mn(2)F6 octahedra, edges with two equivalent Mn(1)F7 pentagonal bipyramids,  an edgeedge with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(3)F4 tetrahedra. In the second Mn site, Mn(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(8), and one F(9) atom to form distorted MnF6 octahedra that share  a cornercorner with one Li(1)F4 tetrahedra,  a cornercorner with one Li(3)F4 tetrahedra, corners with three equivalent Li(2)F4 tetrahedra, edges with two equivalent Mn(1)F7 pentagonal bipyramids, and  an edgeedge with one Li(1)F4 tetrahedra. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(6), one F(7), one F(8), and one F(9) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), 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 second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the third F site, F(3) is bonded to one Li(2), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Mn(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(3), and one Mn(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(3), and one Mn(3) atom. In the seventh F site, F(7) is bonded to one Li(3), one Mn(3), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 trigonal pyramids. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(3), one Mn(2), and one Mn(3) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) 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(1), one F(2), one F(4), and one F(6) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with two equivalent Mn(1)F7 pentagonal bipyramids,  a cornercorner with one Li(2)F4 tetrahedra,  a cornercorner with one Li(3)F4 tetrahedra, and  an edgeedge with one Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles are 69°. The Li(1)-F(1) bond length is 1.89 Å. The Li(1)-F(2) bond length is 1.87 Å. The Li(1)-F(4) bond length is 1.88 Å. The Li(1)-F(6) bond length is 1.89 Å. In the second Li site, Li(2) is bonded to one F(3), one F(4), one F(5), and one F(9) atom to form distorted LiF4 tetrahedra that share corners with three equivalent Mn(2)F6 octahedra,  a cornercorner with one Mn(1)F7 pentagonal bipyramid,  a cornercorner with one Li(1)F4 tetrahedra,  a cornercorner with one Li(3)F4 tetrahedra, and  an edgeedge with one Mn(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 39-60°. The Li(2)-F(3) bond length is 2.00 Å. The Li(2)-F(4) bond length is 1.85 Å. The Li(2)-F(5) bond length is 1.80 Å. The Li(2)-F(9) bond length is 1.88 Å. In the third Li site, Li(3) is bonded to one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra,  a cornercorner with one Mn(1)F7 pentagonal bipyramid,  a cornercorner with one Li(1)F4 tetrahedra,  a cornercorner with one Li(2)F4 tetrahedra, and  an edgeedge with one Mn(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 52°. The Li(3)-F(5) bond length is 1.79 Å. The Li(3)-F(6) bond length is 1.85 Å. The Li(3)-F(7) bond length is 2.03 Å. The Li(3)-F(8) bond length is 1.88 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(2), one F(5), two equivalent F(3), and two equivalent F(7) atoms to form distorted MnF7 pentagonal bipyramids that share  a cornercorner with one Li(2)F4 tetrahedra,  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, edges with two equivalent Mn(2)F6 octahedra, edges with two equivalent Mn(1)F7 pentagonal bipyramids,  an edgeedge with one Li(2)F4 tetrahedra, and  an edgeedge with one Li(3)F4 tetrahedra. The Mn(1)-F(1) bond length is 2.19 Å. The Mn(1)-F(2) bond length is 2.12 Å. The Mn(1)-F(5) bond length is 2.08 Å. There is one shorter (2.22 Å) and one longer (2.36 Å) Mn(1)-F(3) bond length. There is one shorter (2.24 Å) and one longer (2.37 Å) Mn(1)-F(7) bond length. In the second Mn site, Mn(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(8), and one F(9) atom to form distorted MnF6 octahedra that share  a cornercorner with one Li(1)F4 tetrahedra,  a cornercorner with one Li(3)F4 tetrahedra, corners with three equivalent Li(2)F4 tetrahedra, edges with two equivalent Mn(1)F7 pentagonal bipyramids, and  an edgeedge with one Li(1)F4 tetrahedra. The Mn(2)-F(1) bond length is 2.31 Å. The Mn(2)-F(2) bond length is 2.30 Å. The Mn(2)-F(3) bond length is 2.18 Å. The Mn(2)-F(4) bond length is 2.07 Å. The Mn(2)-F(8) bond length is 2.14 Å. The Mn(2)-F(9) bond length is 2.13 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(6), one F(7), one F(8), and one F(9) atom. The Mn(3)-F(1) bond length is 2.37 Å. The Mn(3)-F(2) bond length is 2.38 Å. The Mn(3)-F(6) bond length is 2.06 Å. The Mn(3)-F(7) bond length is 2.18 Å. The Mn(3)-F(8) bond length is 2.17 Å. The Mn(3)-F(9) bond length is 2.16 Å. There are nine inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), 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 second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the third F site, F(3) is bonded to one Li(2), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Mn(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(3), and one Mn(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(3), and one Mn(3) atom. In the seventh F site, F(7) is bonded to one Li(3), one Mn(3), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing FLiMn3 trigonal pyramids. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(3), one Mn(2), and one Mn(3) atom. In the ninth F site, F(9) is bonded in a trigonal planar geometry to one Li(2), one Mn(2), and one Mn(3) atom.