Li2FeF4 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Fe(1)F5 trigonal bipyramids and corners with three equivalent Fe(2)F5 trigonal bipyramids. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(2), one F(4), one F(5), and one F(7) atom. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one F(1), one F(3), one F(5), and one F(7) atom. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one F(2), one F(4), one F(6), and one F(8) atom. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form distorted FeF5 trigonal bipyramids that share corners with three equivalent Li(1)F6 octahedra and  an edgeedge with one Fe(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 5-49°. In the second Fe site, Fe(2) is bonded to one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form distorted FeF5 trigonal bipyramids that share corners with three equivalent Li(1)F6 octahedra and  an edgeedge with one Fe(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 5-46°. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one Fe(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Fe(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(3), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(4), and one Fe(1) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Fe(2) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Li(4), one Fe(1), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Fe(2) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Li(1), one Li(4), and one Fe(2) atom.
Li2FeF4 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(8) atom to form LiF6 octahedra that share corners with three equivalent Fe(1)F5 trigonal bipyramids and corners with three equivalent Fe(2)F5 trigonal bipyramids. The Li(1)-F(1) bond length is 2.12 Å. The Li(1)-F(2) bond length is 2.02 Å. The Li(1)-F(4) bond length is 2.23 Å. The Li(1)-F(5) bond length is 2.02 Å. The Li(1)-F(7) bond length is 2.21 Å. The Li(1)-F(8) bond length is 2.12 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(2), one F(4), one F(5), and one F(7) atom. The Li(2)-F(2) bond length is 2.07 Å. The Li(2)-F(4) bond length is 2.02 Å. The Li(2)-F(5) bond length is 2.15 Å. The Li(2)-F(7) bond length is 2.00 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one F(1), one F(3), one F(5), and one F(7) atom. The Li(3)-F(1) bond length is 1.90 Å. The Li(3)-F(3) bond length is 1.80 Å. The Li(3)-F(5) bond length is 1.91 Å. The Li(3)-F(7) bond length is 1.90 Å. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one F(2), one F(4), one F(6), and one F(8) atom. The Li(4)-F(2) bond length is 1.92 Å. The Li(4)-F(4) bond length is 1.90 Å. The Li(4)-F(6) bond length is 1.80 Å. The Li(4)-F(8) bond length is 1.90 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form distorted FeF5 trigonal bipyramids that share corners with three equivalent Li(1)F6 octahedra and  an edgeedge with one Fe(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 5-49°. The Fe(1)-F(1) bond length is 2.04 Å. The Fe(1)-F(2) bond length is 2.02 Å. The Fe(1)-F(3) bond length is 2.08 Å. The Fe(1)-F(4) bond length is 2.02 Å. The Fe(1)-F(6) bond length is 2.13 Å. In the second Fe site, Fe(2) is bonded to one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form distorted FeF5 trigonal bipyramids that share corners with three equivalent Li(1)F6 octahedra and  an edgeedge with one Fe(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 5-46°. The Fe(2)-F(3) bond length is 2.12 Å. The Fe(2)-F(5) bond length is 2.02 Å. The Fe(2)-F(6) bond length is 2.08 Å. The Fe(2)-F(7) bond length is 2.02 Å. The Fe(2)-F(8) bond length is 2.05 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one Fe(1) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Fe(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(3), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(4), and one Fe(1) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Fe(2) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Li(4), one Fe(1), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Fe(2) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Li(1), one Li(4), and one Fe(2) atom.