LiFeF4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with four equivalent Fe(1)F6 octahedra and  an edgeedge with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 32-62°. Fe(1) is bonded to one F(1), one F(2), and four equivalent F(3) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. There are three 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 distorted bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms.
LiFeF4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with four equivalent Fe(1)F6 octahedra and  an edgeedge with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 32-62°. The Li(1)-F(1) bond length is 1.83 Å. The Li(1)-F(2) bond length is 1.86 Å. Both Li(1)-F(3) bond lengths are 2.00 Å. Fe(1) is bonded to one F(1), one F(2), and four equivalent F(3) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The Fe(1)-F(1) bond length is 1.88 Å. The Fe(1)-F(2) bond length is 1.87 Å. There are two shorter (2.02 Å) and two longer (2.05 Å) Fe(1)-F(3) bond lengths. There are three 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 distorted bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms.