LiFe2F5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Fe(1) is bonded to one F(3), two equivalent F(1), and three equivalent F(2) atoms to form a mixture of distorted edge and corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 27-56°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded to one Li(1) and three equivalent Fe(1) atoms to form distorted FLiFe3 trigonal pyramids that share  a cornercorner with one F(3)Li2Fe2 tetrahedra, corners with three equivalent F(2)LiFe3 trigonal pyramids, edges with two equivalent F(3)Li2Fe2 tetrahedra, and edges with two equivalent F(2)LiFe3 trigonal pyramids. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form distorted FLi2Fe2 tetrahedra that share corners with two equivalent F(3)Li2Fe2 tetrahedra, corners with two equivalent F(2)LiFe3 trigonal pyramids, and edges with four equivalent F(2)LiFe3 trigonal pyramids.
LiFe2F5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Li(1)-F(1) bond lengths are 1.91 Å. Both Li(1)-F(2) bond lengths are 2.40 Å. Both Li(1)-F(3) bond lengths are 2.18 Å. Fe(1) is bonded to one F(3), two equivalent F(1), and three equivalent F(2) atoms to form a mixture of distorted edge and corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 27-56°. The Fe(1)-F(3) bond length is 2.13 Å. There is one shorter (2.05 Å) and one longer (2.09 Å) Fe(1)-F(1) bond length. There are two shorter (2.04 Å) and one longer (2.36 Å) Fe(1)-F(2) bond length. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded to one Li(1) and three equivalent Fe(1) atoms to form distorted FLiFe3 trigonal pyramids that share  a cornercorner with one F(3)Li2Fe2 tetrahedra, corners with three equivalent F(2)LiFe3 trigonal pyramids, edges with two equivalent F(3)Li2Fe2 tetrahedra, and edges with two equivalent F(2)LiFe3 trigonal pyramids. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form distorted FLi2Fe2 tetrahedra that share corners with two equivalent F(3)Li2Fe2 tetrahedra, corners with two equivalent F(2)LiFe3 trigonal pyramids, and edges with four equivalent F(2)LiFe3 trigonal pyramids.