LiFe2F5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form corner-sharing LiF6 octahedra. The corner-sharing octahedral tilt angles are 44°. Fe(1) is bonded in a 7-coordinate geometry to two equivalent F(2), two equivalent F(3), and three equivalent F(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1) and three equivalent Fe(1) atoms to form distorted FLiFe3 trigonal pyramids that share corners with four equivalent F(3)Fe4 tetrahedra, corners with three equivalent F(1)LiFe3 trigonal pyramids,  an edgeedge with one F(3)Fe4 tetrahedra, and edges with two equivalent F(1)LiFe3 trigonal pyramids. In the second F site, F(2) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded to four equivalent Fe(1) atoms to form distorted FFe4 tetrahedra that share corners with eight equivalent F(1)LiFe3 trigonal pyramids, edges with two equivalent F(3)Fe4 tetrahedra, and edges with two equivalent F(1)LiFe3 trigonal pyramids.
LiFe2F5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form corner-sharing LiF6 octahedra. The corner-sharing octahedral tilt angles are 44°. Both Li(1)-F(1) bond lengths are 2.08 Å. There are two shorter (2.04 Å) and two longer (2.08 Å) Li(1)-F(2) bond lengths. Fe(1) is bonded in a 7-coordinate geometry to two equivalent F(2), two equivalent F(3), and three equivalent F(1) atoms. There is one shorter (2.03 Å) and one longer (2.44 Å) Fe(1)-F(2) bond length. There is one shorter (2.19 Å) and one longer (2.25 Å) Fe(1)-F(3) bond length. There are a spread of Fe(1)-F(1) bond distances ranging from 2.12-2.29 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1) and three equivalent Fe(1) atoms to form distorted FLiFe3 trigonal pyramids that share corners with four equivalent F(3)Fe4 tetrahedra, corners with three equivalent F(1)LiFe3 trigonal pyramids,  an edgeedge with one F(3)Fe4 tetrahedra, and edges with two equivalent F(1)LiFe3 trigonal pyramids. In the second F site, F(2) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded to four equivalent Fe(1) atoms to form distorted FFe4 tetrahedra that share corners with eight equivalent F(1)LiFe3 trigonal pyramids, edges with two equivalent F(3)Fe4 tetrahedra, and edges with two equivalent F(1)LiFe3 trigonal pyramids.