Li2FeF4 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form LiF4 tetrahedra that share corners with six equivalent Li(2)F6 octahedra, corners with two equivalent Fe(1)F4 tetrahedra, and  an edgeedge with one Fe(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-60°. In the second Li site, Li(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, corners with six equivalent Fe(1)F4 tetrahedra, and edges with two equivalent Li(2)F6 octahedra. Fe(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form distorted FeF4 tetrahedra that share corners with six equivalent Li(2)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 64-66°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing FLi3Fe tetrahedra. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom.
Li2FeF4 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form LiF4 tetrahedra that share corners with six equivalent Li(2)F6 octahedra, corners with two equivalent Fe(1)F4 tetrahedra, and  an edgeedge with one Fe(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-60°. Both Li(1)-F(1) bond lengths are 1.91 Å. Both Li(1)-F(2) bond lengths are 1.85 Å. In the second Li site, Li(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, corners with six equivalent Fe(1)F4 tetrahedra, and edges with two equivalent Li(2)F6 octahedra. Both Li(2)-F(2) bond lengths are 1.99 Å. All Li(2)-F(1) bond lengths are 2.21 Å. Fe(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form distorted FeF4 tetrahedra that share corners with six equivalent Li(2)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 64-66°. Both Fe(1)-F(1) bond lengths are 2.07 Å. Both Fe(1)-F(2) bond lengths are 1.94 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing FLi3Fe tetrahedra. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Fe(1) atom.