Li2FeF5 crystallizes in the orthorhombic P2_12_12_1 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(1), one F(5), and two equivalent F(2) atoms. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiF5 square pyramids that share corners with three equivalent Fe(1)F5 square pyramids and  an edgeedge with one Fe(1)F5 square pyramid. Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form FeF5 square pyramids that share corners with three equivalent Li(2)F5 square pyramids and  an edgeedge with one Li(2)F5 square pyramid. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Fe(1) atom. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form corner-sharing FLi3Fe tetrahedra. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(2) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to one Li(2) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom.
Li2FeF5 crystallizes in the orthorhombic P2_12_12_1 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(1), one F(5), and two equivalent F(2) atoms. The Li(1)-F(1) bond length is 1.89 Å. The Li(1)-F(5) bond length is 1.88 Å. Both Li(1)-F(2) bond lengths are 2.19 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form distorted LiF5 square pyramids that share corners with three equivalent Fe(1)F5 square pyramids and  an edgeedge with one Fe(1)F5 square pyramid. The Li(2)-F(1) bond length is 2.18 Å. The Li(2)-F(2) bond length is 2.18 Å. The Li(2)-F(3) bond length is 1.94 Å. The Li(2)-F(4) bond length is 1.98 Å. The Li(2)-F(5) bond length is 1.96 Å. Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form FeF5 square pyramids that share corners with three equivalent Li(2)F5 square pyramids and  an edgeedge with one Li(2)F5 square pyramid. The Fe(1)-F(1) bond length is 1.92 Å. The Fe(1)-F(2) bond length is 1.90 Å. The Fe(1)-F(3) bond length is 1.90 Å. The Fe(1)-F(4) bond length is 1.89 Å. The Fe(1)-F(5) bond length is 1.92 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one Fe(1) atom. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form corner-sharing FLi3Fe tetrahedra. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(2) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a 2-coordinate geometry to one Li(2) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom.