LiFeF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(3), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with four equivalent Fe(1)F6 octahedra and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-57°. Fe(1) is bonded to one F(1), one F(3), one F(4), and three equivalent F(2) atoms to form distorted FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles are 29°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to three equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom.
LiFeF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(3), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with four equivalent Fe(1)F6 octahedra and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-57°. The Li(1)-F(1) bond length is 1.86 Å. The Li(1)-F(3) bond length is 1.88 Å. There is one shorter (1.96 Å) and one longer (1.97 Å) Li(1)-F(4) bond length. Fe(1) is bonded to one F(1), one F(3), one F(4), and three equivalent F(2) atoms to form distorted FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles are 29°. The Fe(1)-F(1) bond length is 1.86 Å. The Fe(1)-F(3) bond length is 1.85 Å. The Fe(1)-F(4) bond length is 1.93 Å. There are a spread of Fe(1)-F(2) bond distances ranging from 2.03-2.32 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to three equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom.