Li3FeF5 crystallizes in the tetragonal P4_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(4), and two equivalent F(1) 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 a mixture of distorted edge and corner-sharing LiF5 square pyramids. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(4), and two equivalent F(5) atoms to form a mixture of distorted edge and corner-sharing LiF5 square pyramids. Fe(1) is bonded in a 8-coordinate geometry to one F(1), one F(2), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Fe(1) atom to form distorted FLi4Fe trigonal bipyramids that share corners with two equivalent F(1)Li4Fe trigonal bipyramids, corners with three equivalent F(5)Li3Fe2 trigonal bipyramids, corners with four equivalent F(4)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid, and  an edgeedge with one F(5)Li3Fe2 trigonal bipyramid. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Fe(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Fe(1) atoms to form FLi3Fe2 trigonal bipyramids that share corners with two equivalent F(4)Li3Fe2 trigonal bipyramids, corners with two equivalent F(5)Li3Fe2 trigonal bipyramids, corners with four equivalent F(1)Li4Fe trigonal bipyramids,  an edgeedge with one F(5)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(1)Li4Fe trigonal bipyramid, and  a faceface with one F(5)Li3Fe2 trigonal bipyramid. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(3), and two equivalent Fe(1) atoms to form distorted FLi3Fe2 trigonal bipyramids that share corners with two equivalent F(4)Li3Fe2 trigonal bipyramids, corners with three equivalent F(1)Li4Fe trigonal bipyramids,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(1)Li4Fe trigonal bipyramid, edges with two equivalent F(5)Li3Fe2 trigonal bipyramids, and  a faceface with one F(4)Li3Fe2 trigonal bipyramid.
Li3FeF5 crystallizes in the tetragonal P4_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(2), one F(3), one F(4), and two equivalent F(1) atoms. The Li(1)-F(2) bond length is 1.91 Å. The Li(1)-F(3) bond length is 2.41 Å. The Li(1)-F(4) bond length is 2.11 Å. There is one shorter (2.04 Å) and one longer (2.08 Å) Li(1)-F(1) bond length. 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 a mixture of distorted edge and corner-sharing LiF5 square pyramids. The Li(2)-F(1) bond length is 2.04 Å. The Li(2)-F(2) bond length is 2.04 Å. The Li(2)-F(3) bond length is 2.03 Å. The Li(2)-F(4) bond length is 1.99 Å. The Li(2)-F(5) bond length is 1.98 Å. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(4), and two equivalent F(5) atoms to form a mixture of distorted edge and corner-sharing LiF5 square pyramids. The Li(3)-F(1) bond length is 2.07 Å. The Li(3)-F(2) bond length is 1.93 Å. The Li(3)-F(4) bond length is 2.27 Å. Both Li(3)-F(5) bond lengths are 1.98 Å. Fe(1) is bonded in a 8-coordinate geometry to one F(1), one F(2), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. The Fe(1)-F(1) bond length is 2.26 Å. The Fe(1)-F(2) bond length is 2.30 Å. There is one shorter (2.13 Å) and one longer (2.23 Å) Fe(1)-F(3) bond length. There is one shorter (2.12 Å) and one longer (2.22 Å) Fe(1)-F(4) bond length. There is one shorter (2.18 Å) and one longer (2.43 Å) Fe(1)-F(5) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Fe(1) atom to form distorted FLi4Fe trigonal bipyramids that share corners with two equivalent F(1)Li4Fe trigonal bipyramids, corners with three equivalent F(5)Li3Fe2 trigonal bipyramids, corners with four equivalent F(4)Li3Fe2 trigonal bipyramids,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid, and  an edgeedge with one F(5)Li3Fe2 trigonal bipyramid. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Fe(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Fe(1) atoms to form FLi3Fe2 trigonal bipyramids that share corners with two equivalent F(4)Li3Fe2 trigonal bipyramids, corners with two equivalent F(5)Li3Fe2 trigonal bipyramids, corners with four equivalent F(1)Li4Fe trigonal bipyramids,  an edgeedge with one F(5)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(1)Li4Fe trigonal bipyramid, and  a faceface with one F(5)Li3Fe2 trigonal bipyramid. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(3), and two equivalent Fe(1) atoms to form distorted FLi3Fe2 trigonal bipyramids that share corners with two equivalent F(4)Li3Fe2 trigonal bipyramids, corners with three equivalent F(1)Li4Fe trigonal bipyramids,  an edgeedge with one F(4)Li3Fe2 trigonal bipyramid,  an edgeedge with one F(1)Li4Fe trigonal bipyramid, edges with two equivalent F(5)Li3Fe2 trigonal bipyramids, and  a faceface with one F(4)Li3Fe2 trigonal bipyramid.