LiFeF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form distorted LiF5 square pyramids that share corners with four equivalent Fe(1)F5 tetrahedra,  an edgeedge with one Li(1)F5 square pyramid, and  an edgeedge with one Fe(1)F5 tetrahedra. Fe(1) is bonded to one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form distorted FeF5 tetrahedra that share corners with four equivalent Li(1)F5 square pyramids,  an edgeedge with one Li(1)F5 square pyramid, and  an edgeedge with one Fe(1)F5 tetrahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 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 one Li(1) and two 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 T-shaped 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(2), one F(3), and two equivalent F(4) atoms to form distorted LiF5 square pyramids that share corners with four equivalent Fe(1)F5 tetrahedra,  an edgeedge with one Li(1)F5 square pyramid, and  an edgeedge with one Fe(1)F5 tetrahedra. The Li(1)-F(1) bond length is 1.91 Å. The Li(1)-F(2) bond length is 2.16 Å. The Li(1)-F(3) bond length is 1.97 Å. There is one shorter (2.00 Å) and one longer (2.05 Å) Li(1)-F(4) bond length. Fe(1) is bonded to one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form distorted FeF5 tetrahedra that share corners with four equivalent Li(1)F5 square pyramids,  an edgeedge with one Li(1)F5 square pyramid, and  an edgeedge with one Fe(1)F5 tetrahedra. The Fe(1)-F(1) bond length is 1.84 Å. The Fe(1)-F(3) bond length is 1.84 Å. The Fe(1)-F(4) bond length is 1.88 Å. There is one shorter (1.87 Å) and one longer (2.47 Å) Fe(1)-F(2) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 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 one Li(1) and two 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 T-shaped geometry to two equivalent Li(1) and one Fe(1) atom.