Li2Fe3F8 crystallizes in the orthorhombic Cmce space group. Li(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with three equivalent Fe(2)F6 octahedra and corners with six equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-57°. There are two inequivalent Fe sites. In the first Fe site, 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(1)F4 tetrahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. In the second Fe site, Fe(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form FeF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra and edges with four equivalent Fe(1)F6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms.
Li2Fe3F8 crystallizes in the orthorhombic Cmce space group. Li(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with three equivalent Fe(2)F6 octahedra and corners with six equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-57°. The Li(1)-F(2) bond length is 1.99 Å. The Li(1)-F(3) bond length is 1.89 Å. Both Li(1)-F(1) bond lengths are 1.95 Å. There are two inequivalent Fe sites. In the first Fe site, 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(1)F4 tetrahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Fe(2)F6 octahedra. Both Fe(1)-F(1) bond lengths are 2.04 Å. Both Fe(1)-F(2) bond lengths are 2.23 Å. Both Fe(1)-F(3) bond lengths are 2.07 Å. In the second Fe site, Fe(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form FeF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra and edges with four equivalent Fe(1)F6 octahedra. Both Fe(2)-F(2) bond lengths are 2.12 Å. All Fe(2)-F(1) bond lengths are 2.10 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one Fe(2) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms.