LiFeF3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form distorted LiF6 pentagonal pyramids that share corners with two equivalent Fe(1)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, edges with four equivalent Fe(1)F6 octahedra, edges with two equivalent Li(1)F6 pentagonal pyramids, and  an edgeedge with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. In the second Li site, Li(2) is bonded to two equivalent F(1) and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with six equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F6 pentagonal pyramids, and  an edgeedge with one Li(1)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 50-54°. Fe(1) is bonded to one F(1), two equivalent F(3), and three equivalent F(2) atoms to form distorted FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra,  a cornercorner with one Li(1)F6 pentagonal pyramid, corners with three equivalent Li(2)F4 tetrahedra, edges with three equivalent Fe(1)F6 octahedra, and edges with two equivalent Li(1)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form a mixture of edge and corner-sharing FLi3Fe trigonal pyramids. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(1) atoms.
LiFeF3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form distorted LiF6 pentagonal pyramids that share corners with two equivalent Fe(1)F6 octahedra, corners with two equivalent Li(2)F4 tetrahedra, edges with four equivalent Fe(1)F6 octahedra, edges with two equivalent Li(1)F6 pentagonal pyramids, and  an edgeedge with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. Both Li(1)-F(2) bond lengths are 2.23 Å. There are two shorter (2.04 Å) and two longer (2.10 Å) Li(1)-F(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent F(1) and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with six equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F6 pentagonal pyramids, and  an edgeedge with one Li(1)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 50-54°. Both Li(2)-F(1) bond lengths are 1.92 Å. Both Li(2)-F(3) bond lengths are 1.90 Å. Fe(1) is bonded to one F(1), two equivalent F(3), and three equivalent F(2) atoms to form distorted FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra,  a cornercorner with one Li(1)F6 pentagonal pyramid, corners with three equivalent Li(2)F4 tetrahedra, edges with three equivalent Fe(1)F6 octahedra, and edges with two equivalent Li(1)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. The Fe(1)-F(1) bond length is 2.02 Å. There is one shorter (2.04 Å) and one longer (2.10 Å) Fe(1)-F(3) bond length. There are a spread of Fe(1)-F(2) bond distances ranging from 2.10-2.25 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form a mixture of edge and corner-sharing FLi3Fe trigonal pyramids. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(1) atoms.