Li2FeF4 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form LiF4 trigonal pyramids that share corners with five equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F4 trigonal pyramids, corners with two equivalent Li(2)F4 trigonal pyramids, and  an edgeedge with one Li(2)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 38-79°. In the second Li site, Li(2) is bonded to one F(1), one F(4), and two equivalent F(2) atoms to form distorted LiF4 trigonal pyramids that share corners with three equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F4 trigonal pyramids, corners with two equivalent Li(2)F4 trigonal pyramids,  an edgeedge with one Fe(1)F6 octahedra, and  an edgeedge with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 61-80°. Fe(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)F6 octahedra, corners with three equivalent Li(2)F4 trigonal pyramids, corners with five equivalent Li(1)F4 trigonal pyramids, and  an edgeedge with one Li(2)F4 trigonal pyramid. The corner-sharing octahedral tilt angles are 39°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Fe(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form distorted corner-sharing FLi3Fe tetrahedra.
Li2FeF4 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form LiF4 trigonal pyramids that share corners with five equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F4 trigonal pyramids, corners with two equivalent Li(2)F4 trigonal pyramids, and  an edgeedge with one Li(2)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 38-79°. The Li(1)-F(2) bond length is 1.95 Å. The Li(1)-F(3) bond length is 1.95 Å. There is one shorter (1.89 Å) and one longer (1.91 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded to one F(1), one F(4), and two equivalent F(2) atoms to form distorted LiF4 trigonal pyramids that share corners with three equivalent Fe(1)F6 octahedra, corners with two equivalent Li(1)F4 trigonal pyramids, corners with two equivalent Li(2)F4 trigonal pyramids,  an edgeedge with one Fe(1)F6 octahedra, and  an edgeedge with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 61-80°. The Li(2)-F(1) bond length is 1.92 Å. The Li(2)-F(4) bond length is 2.22 Å. There is one shorter (1.89 Å) and one longer (1.93 Å) Li(2)-F(2) bond length. Fe(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)F6 octahedra, corners with three equivalent Li(2)F4 trigonal pyramids, corners with five equivalent Li(1)F4 trigonal pyramids, and  an edgeedge with one Li(2)F4 trigonal pyramid. The corner-sharing octahedral tilt angles are 39°. The Fe(1)-F(2) bond length is 2.10 Å. The Fe(1)-F(4) bond length is 2.07 Å. There is one shorter (2.08 Å) and one longer (2.15 Å) Fe(1)-F(1) bond length. There is one shorter (2.13 Å) and one longer (2.14 Å) Fe(1)-F(3) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Fe(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and one Fe(1) atom to form distorted corner-sharing FLi3Fe tetrahedra.