Li3FeF6 is pyrite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(2), one F(3), and two equivalent F(1) atoms. In the second Li site, Li(2) 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 six equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-50°. 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 six equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-50°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form distorted corner-sharing FLi3Fe tetrahedra. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Fe(1) atom.
Li3FeF6 is pyrite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(2), one F(3), and two equivalent F(1) atoms. The Li(1)-F(2) bond length is 1.99 Å. The Li(1)-F(3) bond length is 1.99 Å. There is one shorter (1.99 Å) and one longer (2.09 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) 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 six equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-50°. Both Li(2)-F(1) bond lengths are 2.21 Å. Both Li(2)-F(2) bond lengths are 2.10 Å. Both Li(2)-F(3) bond lengths are 1.98 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 six equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-50°. Both Fe(1)-F(1) bond lengths are 1.98 Å. Both Fe(1)-F(2) bond lengths are 1.95 Å. Both Fe(1)-F(3) bond lengths are 1.95 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form distorted corner-sharing FLi3Fe tetrahedra. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Fe(1) atom.