LiFeF4 crystallizes in the orthorhombic Pmn2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), two equivalent F(5), and two equivalent F(8) atoms to form distorted LiF5 trigonal bipyramids that share corners with two equivalent Fe(2)F6 octahedra and corners with four equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-69°. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(2) and two equivalent F(8) atoms. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(3), two equivalent F(6), and two equivalent F(7) atoms. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one F(4) and two equivalent F(7) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(3), one F(4), one F(5), one F(8), and two equivalent F(10) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)F6 octahedra and corners with two equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 32-51°. In the second Fe site, Fe(2) is bonded to one F(1), one F(2), one F(6), one F(7), and two equivalent F(9) atoms to form FeF6 octahedra that share corners with four equivalent Fe(2)F6 octahedra and  a cornercorner with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 30-49°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(3) and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(4) and two equivalent Fe(1) atoms. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one Fe(1) atom. In the sixth F site, F(6) is bonded in a bent 120 degrees geometry to one Li(3) and one Fe(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Li(4), and one Fe(2) atom. In the eighth F site, F(8) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to two equivalent Fe(2) atoms. In the tenth F site, F(10) is bonded in a distorted bent 150 degrees geometry to two equivalent Fe(1) atoms.
LiFeF4 crystallizes in the orthorhombic Pmn2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), two equivalent F(5), and two equivalent F(8) atoms to form distorted LiF5 trigonal bipyramids that share corners with two equivalent Fe(2)F6 octahedra and corners with four equivalent Fe(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-69°. The Li(1)-F(1) bond length is 2.10 Å. Both Li(1)-F(5) bond lengths are 2.02 Å. Both Li(1)-F(8) bond lengths are 2.21 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one F(2) and two equivalent F(8) atoms. The Li(2)-F(2) bond length is 2.03 Å. Both Li(2)-F(8) bond lengths are 2.05 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one F(3), two equivalent F(6), and two equivalent F(7) atoms. The Li(3)-F(3) bond length is 2.05 Å. Both Li(3)-F(6) bond lengths are 1.98 Å. Both Li(3)-F(7) bond lengths are 2.39 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one F(4) and two equivalent F(7) atoms. The Li(4)-F(4) bond length is 2.12 Å. Both Li(4)-F(7) bond lengths are 2.07 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(3), one F(4), one F(5), one F(8), and two equivalent F(10) atoms to form FeF6 octahedra that share corners with four equivalent Fe(1)F6 octahedra and corners with two equivalent Li(1)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 32-51°. The Fe(1)-F(3) bond length is 2.06 Å. The Fe(1)-F(4) bond length is 2.05 Å. The Fe(1)-F(5) bond length is 1.85 Å. The Fe(1)-F(8) bond length is 1.92 Å. There is one shorter (1.97 Å) and one longer (1.99 Å) Fe(1)-F(10) bond length. In the second Fe site, Fe(2) is bonded to one F(1), one F(2), one F(6), one F(7), and two equivalent F(9) atoms to form FeF6 octahedra that share corners with four equivalent Fe(2)F6 octahedra and  a cornercorner with one Li(1)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 30-49°. The Fe(2)-F(1) bond length is 2.05 Å. The Fe(2)-F(2) bond length is 2.06 Å. The Fe(2)-F(6) bond length is 1.88 Å. The Fe(2)-F(7) bond length is 1.88 Å. There is one shorter (1.96 Å) and one longer (1.99 Å) Fe(2)-F(9) bond length. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(3) and two equivalent Fe(1) atoms. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(4) and two equivalent Fe(1) atoms. In the fifth F site, F(5) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one Fe(1) atom. In the sixth F site, F(6) is bonded in a bent 120 degrees geometry to one Li(3) and one Fe(2) atom. In the seventh F site, F(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Li(4), and one Fe(2) atom. In the eighth F site, F(8) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one Fe(1) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to two equivalent Fe(2) atoms. In the tenth F site, F(10) is bonded in a distorted bent 150 degrees geometry to two equivalent Fe(1) atoms.