LiMnF3 crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with three equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(1)F6 pentagonal pyramids, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Mn(1)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 27-68°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted MnF6 pentagonal pyramids that share corners with four equivalent Li(1)F4 tetrahedra, edges with three equivalent Mn(2)F6 octahedra, and edges with two equivalent Li(1)F4 tetrahedra. In the second Mn site, Mn(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, edges with two equivalent Mn(2)F6 octahedra, and edges with three equivalent Mn(1)F6 pentagonal pyramids. 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 a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom.
LiMnF3 crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with three equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(1)F6 pentagonal pyramids, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Mn(1)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 27-68°. The Li(1)-F(1) bond length is 1.96 Å. The Li(1)-F(2) bond length is 1.90 Å. There is one shorter (1.84 Å) and one longer (1.92 Å) Li(1)-F(3) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted MnF6 pentagonal pyramids that share corners with four equivalent Li(1)F4 tetrahedra, edges with three equivalent Mn(2)F6 octahedra, and edges with two equivalent Li(1)F4 tetrahedra. Both Mn(1)-F(1) bond lengths are 2.31 Å. Both Mn(1)-F(2) bond lengths are 2.15 Å. Both Mn(1)-F(3) bond lengths are 2.08 Å. In the second Mn site, Mn(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, edges with two equivalent Mn(2)F6 octahedra, and edges with three equivalent Mn(1)F6 pentagonal pyramids. Both Mn(2)-F(2) bond lengths are 2.07 Å. There are two shorter (2.21 Å) and two longer (2.24 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 a mixture of distorted corner and edge-sharing FLiMn3 tetrahedra. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom.