LiFe2F6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with eight equivalent Fe(1)F6 octahedra and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. Fe(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form FeF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Fe(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Fe(1) atoms.
LiFe2F6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with eight equivalent Fe(1)F6 octahedra and edges with two equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. Both Li(1)-F(1) bond lengths are 1.93 Å. All Li(1)-F(2) bond lengths are 2.02 Å. Fe(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form FeF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Fe(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. Both Fe(1)-F(1) bond lengths are 2.00 Å. There are two shorter (1.96 Å) and two longer (2.03 Å) Fe(1)-F(2) bond lengths. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Fe(1) atoms.