LiMnF3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal pyramidal geometry to one F(1), one F(2), one F(3), and one F(5) atom. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(3), one F(4), one F(5), and two equivalent F(6) atoms. There are two 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(4), one F(5), and two equivalent F(2) atoms. In the second Mn site, Mn(2) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), and two equivalent F(6) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the second F site, F(2) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form FLiMn3 tetrahedra that share corners with two equivalent F(5)Li2Mn2 tetrahedra, corners with two equivalent F(2)LiMn3 tetrahedra, and  an edgeedge with one F(5)Li2Mn2 tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(2), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi2Mn2 tetrahedra. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to two equivalent Li(2) and two equivalent Mn(2) atoms.
LiMnF3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal pyramidal geometry to one F(1), one F(2), one F(3), and one F(5) atom. The Li(1)-F(1) bond length is 1.93 Å. The Li(1)-F(2) bond length is 2.04 Å. The Li(1)-F(3) bond length is 1.93 Å. The Li(1)-F(5) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(3), one F(4), one F(5), and two equivalent F(6) atoms. The Li(2)-F(3) bond length is 2.57 Å. The Li(2)-F(4) bond length is 1.91 Å. The Li(2)-F(5) bond length is 1.90 Å. There is one shorter (1.92 Å) and one longer (2.52 Å) Li(2)-F(6) bond length. There are two 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(4), one F(5), and two equivalent F(2) atoms. The Mn(1)-F(1) bond length is 2.09 Å. The Mn(1)-F(3) bond length is 2.09 Å. The Mn(1)-F(4) bond length is 2.12 Å. The Mn(1)-F(5) bond length is 2.41 Å. There is one shorter (2.14 Å) and one longer (2.17 Å) Mn(1)-F(2) bond length. In the second Mn site, Mn(2) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(3), one F(4), one F(5), and two equivalent F(6) atoms. The Mn(2)-F(1) bond length is 2.13 Å. The Mn(2)-F(2) bond length is 2.31 Å. The Mn(2)-F(3) bond length is 2.40 Å. The Mn(2)-F(4) bond length is 2.14 Å. The Mn(2)-F(5) bond length is 2.29 Å. There is one shorter (2.09 Å) and one longer (2.29 Å) Mn(2)-F(6) bond length. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the second F site, F(2) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form FLiMn3 tetrahedra that share corners with two equivalent F(5)Li2Mn2 tetrahedra, corners with two equivalent F(2)LiMn3 tetrahedra, and  an edgeedge with one F(5)Li2Mn2 tetrahedra. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(2), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing FLi2Mn2 tetrahedra. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to two equivalent Li(2) and two equivalent Mn(2) atoms.