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 one F(4) atom to form LiF4 tetrahedra that share corners with five equivalent Fe(1)F5 trigonal bipyramids. Fe(1) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form FeF5 trigonal bipyramids that share corners with five equivalent Li(1)F4 tetrahedra and  an edgeedge with one Fe(1)F5 trigonal bipyramid. 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 linear geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms.
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 one F(4) atom to form LiF4 tetrahedra that share corners with five equivalent Fe(1)F5 trigonal bipyramids. The Li(1)-F(1) bond length is 1.88 Å. The Li(1)-F(2) bond length is 1.86 Å. The Li(1)-F(3) bond length is 1.87 Å. The Li(1)-F(4) bond length is 1.98 Å. Fe(1) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form FeF5 trigonal bipyramids that share corners with five equivalent Li(1)F4 tetrahedra and  an edgeedge with one Fe(1)F5 trigonal bipyramid. The Fe(1)-F(1) bond length is 1.87 Å. The Fe(1)-F(2) bond length is 1.84 Å. The Fe(1)-F(3) bond length is 1.85 Å. There is one shorter (2.00 Å) and one longer (2.09 Å) Fe(1)-F(4) 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 linear geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms.