Li2FeF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to two equivalent F(2) and three equivalent F(1) atoms to form distorted LiF5 square pyramids that share corners with four equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F5 square pyramids, edges with three equivalent Li(1)F5 square pyramids, and  a faceface with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-50°. Fe(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)F6 octahedra, corners with eight equivalent Li(1)F5 square pyramids, and faces with two equivalent Li(1)F5 square pyramids. The corner-sharing octahedral tilt angles are 50°. There are two inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Li(1) and one Fe(1) atom to form a mixture of distorted edge and corner-sharing FLi3Fe trigonal pyramids. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to two equivalent Li(1) and two equivalent Fe(1) atoms.
Li2FeF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to two equivalent F(2) and three equivalent F(1) atoms to form distorted LiF5 square pyramids that share corners with four equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F5 square pyramids, edges with three equivalent Li(1)F5 square pyramids, and  a faceface with one Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-50°. There is one shorter (2.03 Å) and one longer (2.22 Å) Li(1)-F(2) bond length. There are a spread of Li(1)-F(1) bond distances ranging from 1.88-2.05 Å. Fe(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)F6 octahedra, corners with eight equivalent Li(1)F5 square pyramids, and faces with two equivalent Li(1)F5 square pyramids. The corner-sharing octahedral tilt angles are 50°. Both Fe(1)-F(1) bond lengths are 2.16 Å. There are two shorter (2.05 Å) and two longer (2.13 Å) Fe(1)-F(2) bond lengths. There are two inequivalent F sites. In the first F site, F(1) is bonded to three equivalent Li(1) and one Fe(1) atom to form a mixture of distorted edge and corner-sharing FLi3Fe trigonal pyramids. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to two equivalent Li(1) and two equivalent Fe(1) atoms.