LiMnF3 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(5), and two equivalent F(1) atoms to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra, and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-65°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(6), and two equivalent F(5) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form MnF6 octahedra that share corners with four equivalent Mn(2)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-54°. In the second Mn site, Mn(2) is bonded to one F(2), one F(6), two equivalent F(3), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with four equivalent Mn(1)F6 octahedra,  a cornercorner with one Li(1)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra, and edges with two equivalent Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-54°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Mn(1), and one Mn(2) atom to form a mixture of distorted edge and corner-sharing FLi2Mn2 tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), and two equivalent Mn(2) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent Mn(2) atoms. In the fifth F site, F(5) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form FLi3Mn tetrahedra that share corners with two equivalent F(2)Li2Mn2 tetrahedra, corners with two equivalent F(5)Li3Mn tetrahedra, and  an edgeedge with one F(2)Li2Mn2 tetrahedra. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom.
LiMnF3 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(5), and two equivalent F(1) atoms to form LiF4 tetrahedra that share  a cornercorner with one Mn(2)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra, and corners with two equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-65°. The Li(1)-F(2) bond length is 1.97 Å. The Li(1)-F(5) bond length is 1.96 Å. There is one shorter (1.88 Å) and one longer (1.89 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(6), and two equivalent F(5) atoms. The Li(2)-F(2) bond length is 2.36 Å. The Li(2)-F(3) bond length is 2.09 Å. The Li(2)-F(6) bond length is 1.94 Å. There is one shorter (1.96 Å) and one longer (2.00 Å) Li(2)-F(5) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form MnF6 octahedra that share corners with four equivalent Mn(2)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-54°. The Mn(1)-F(1) bond length is 2.05 Å. The Mn(1)-F(2) bond length is 2.20 Å. The Mn(1)-F(3) bond length is 2.32 Å. The Mn(1)-F(4) bond length is 2.14 Å. The Mn(1)-F(5) bond length is 2.16 Å. The Mn(1)-F(6) bond length is 2.12 Å. In the second Mn site, Mn(2) is bonded to one F(2), one F(6), two equivalent F(3), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with four equivalent Mn(1)F6 octahedra,  a cornercorner with one Li(1)F4 tetrahedra,  an edgeedge with one Mn(1)F6 octahedra, and edges with two equivalent Mn(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-54°. The Mn(2)-F(2) bond length is 2.09 Å. The Mn(2)-F(6) bond length is 2.09 Å. There is one shorter (2.18 Å) and one longer (2.39 Å) Mn(2)-F(3) bond length. Both Mn(2)-F(4) bond lengths are 2.12 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Mn(1), and one Mn(2) atom to form a mixture of distorted edge and corner-sharing FLi2Mn2 tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(2), one Mn(1), and two equivalent Mn(2) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent Mn(2) atoms. In the fifth F site, F(5) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form FLi3Mn tetrahedra that share corners with two equivalent F(2)Li2Mn2 tetrahedra, corners with two equivalent F(5)Li3Mn tetrahedra, and  an edgeedge with one F(2)Li2Mn2 tetrahedra. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom.