Li2FeF5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form distorted LiF6 octahedra that share corners with three equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, edges with two equivalent Fe(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. 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 two equivalent Fe(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. There are three inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Li(1) and one Fe(1) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one F(3)Li2Fe2 trigonal pyramid, corners with three equivalent F(1)Li3Fe trigonal pyramids, edges with two equivalent F(3)Li2Fe2 trigonal pyramids, and edges with two equivalent F(1)Li3Fe trigonal pyramids. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent F(3)Li2Fe2 trigonal pyramids, corners with two equivalent F(1)Li3Fe trigonal pyramids, and edges with four equivalent F(1)Li3Fe trigonal pyramids.
Li2FeF5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form distorted LiF6 octahedra that share corners with three equivalent Fe(1)F6 octahedra, corners with four equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, edges with two equivalent Fe(1)F6 octahedra, and  a faceface with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. The Li(1)-F(3) bond length is 2.17 Å. There is one shorter (1.86 Å) and one longer (1.91 Å) Li(1)-F(2) bond length. There are a spread of Li(1)-F(1) bond distances ranging from 1.98-2.23 Å. 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 two equivalent Fe(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. Both Fe(1)-F(1) bond lengths are 1.92 Å. Both Fe(1)-F(2) bond lengths are 1.90 Å. Both Fe(1)-F(3) bond lengths are 2.00 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Li(1) and one Fe(1) atom to form distorted FLi3Fe trigonal pyramids that share  a cornercorner with one F(3)Li2Fe2 trigonal pyramid, corners with three equivalent F(1)Li3Fe trigonal pyramids, edges with two equivalent F(3)Li2Fe2 trigonal pyramids, and edges with two equivalent F(1)Li3Fe trigonal pyramids. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent F(3)Li2Fe2 trigonal pyramids, corners with two equivalent F(1)Li3Fe trigonal pyramids, and edges with four equivalent F(1)Li3Fe trigonal pyramids.