LiFeF6 crystallizes in the tetragonal P4_2nm space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra 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 39-44°. Fe(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form FeF6 octahedra that share corners with four equivalent Li(1)F6 octahedra and  an edgeedge with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 39-44°. 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 water-like geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one Fe(1) atom.
LiFeF6 crystallizes in the tetragonal P4_2nm space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra 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 39-44°. Both Li(1)-F(1) bond lengths are 1.95 Å. Both Li(1)-F(2) bond lengths are 2.05 Å. Both Li(1)-F(3) bond lengths are 2.01 Å. Fe(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form FeF6 octahedra that share corners with four equivalent Li(1)F6 octahedra and  an edgeedge with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 39-44°. Both Fe(1)-F(1) bond lengths are 1.76 Å. Both Fe(1)-F(2) bond lengths are 1.76 Å. Both Fe(1)-F(3) bond lengths are 1.75 Å. 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 water-like geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one Fe(1) atom.