Li2FeF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent F(3) and two equivalent F(4) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2) and four equivalent F(3) atoms. Fe(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedra are not tilted. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Li(2) and one Fe(1) atom. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form a mixture of distorted edge and corner-sharing FLi3Fe tetrahedra. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom.
Li2FeF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent F(3) and two equivalent F(4) atoms. Both Li(1)-F(3) bond lengths are 1.95 Å. There is one shorter (1.94 Å) and one longer (2.36 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2) and four equivalent F(3) atoms. The Li(2)-F(2) bond length is 1.86 Å. There are two shorter (2.03 Å) and two longer (2.15 Å) Li(2)-F(3) bond lengths. Fe(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedra are not tilted. The Fe(1)-F(2) bond length is 1.89 Å. The Fe(1)-F(4) bond length is 1.98 Å. Both Fe(1)-F(1) bond lengths are 1.98 Å. Both Fe(1)-F(3) bond lengths are 1.96 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Li(2) and one Fe(1) atom. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form a mixture of distorted edge and corner-sharing FLi3Fe tetrahedra. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom.