Li2FeF5 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), one F(5), and two equivalent F(1) atoms to form distorted LiF5 square pyramids that share corners with four equivalent Fe(1)F7 pentagonal bipyramids, corners with two equivalent Li(1)F5 square pyramids,  an edgeedge with one Fe(1)F7 pentagonal bipyramid, and edges with three equivalent Li(2)F5 square pyramids. In the second Li site, Li(2) is bonded to one F(2), one F(3), one F(5), and two equivalent F(1) atoms to form distorted LiF5 square pyramids that share corners with four equivalent Fe(1)F7 pentagonal bipyramids, corners with two equivalent Li(2)F5 square pyramids,  an edgeedge with one Fe(1)F7 pentagonal bipyramid, and edges with three equivalent Li(1)F5 square pyramids. Fe(1) is bonded to one F(1), one F(2), one F(5), two equivalent F(3), and two equivalent F(4) atoms to form distorted FeF7 pentagonal bipyramids that share corners with four equivalent Li(1)F5 square pyramids, corners with four equivalent Li(2)F5 square pyramids, edges with two equivalent Fe(1)F7 pentagonal bipyramids,  an edgeedge with one Li(1)F5 square pyramid, 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 to two equivalent Li(1), two equivalent Li(2), and one Fe(1) atom to form distorted edge-sharing FLi4Fe trigonal bipyramids. 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(2) and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Fe(1) atoms. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom.
Li2FeF5 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(4), one F(5), and two equivalent F(1) atoms to form distorted LiF5 square pyramids that share corners with four equivalent Fe(1)F7 pentagonal bipyramids, corners with two equivalent Li(1)F5 square pyramids,  an edgeedge with one Fe(1)F7 pentagonal bipyramid, and edges with three equivalent Li(2)F5 square pyramids. The Li(1)-F(2) bond length is 1.95 Å. The Li(1)-F(4) bond length is 1.94 Å. The Li(1)-F(5) bond length is 2.06 Å. There is one shorter (2.13 Å) and one longer (2.21 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to one F(2), one F(3), one F(5), and two equivalent F(1) atoms to form distorted LiF5 square pyramids that share corners with four equivalent Fe(1)F7 pentagonal bipyramids, corners with two equivalent Li(2)F5 square pyramids,  an edgeedge with one Fe(1)F7 pentagonal bipyramid, and edges with three equivalent Li(1)F5 square pyramids. The Li(2)-F(2) bond length is 1.94 Å. The Li(2)-F(3) bond length is 1.95 Å. The Li(2)-F(5) bond length is 2.00 Å. There is one shorter (2.20 Å) and one longer (2.24 Å) Li(2)-F(1) bond length. Fe(1) is bonded to one F(1), one F(2), one F(5), two equivalent F(3), and two equivalent F(4) atoms to form distorted FeF7 pentagonal bipyramids that share corners with four equivalent Li(1)F5 square pyramids, corners with four equivalent Li(2)F5 square pyramids, edges with two equivalent Fe(1)F7 pentagonal bipyramids,  an edgeedge with one Li(1)F5 square pyramid, and  an edgeedge with one Li(2)F5 square pyramid. The Fe(1)-F(1) bond length is 2.14 Å. The Fe(1)-F(2) bond length is 1.99 Å. The Fe(1)-F(5) bond length is 1.93 Å. There is one shorter (1.98 Å) and one longer (2.13 Å) Fe(1)-F(3) bond length. There is one shorter (1.98 Å) and one longer (2.13 Å) Fe(1)-F(4) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Fe(1) atom to form distorted edge-sharing FLi4Fe trigonal bipyramids. 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(2) and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Fe(1) atoms. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom.