LiFeF4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(2), one F(4), and one F(5) atom. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(3), one F(4), two equivalent F(2), and two equivalent F(5) atoms to form a mixture of corner and face-sharing FeF6 octahedra. In the second Fe site, Fe(2) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(5) atoms to form a mixture of distorted corner and face-sharing FeF6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 46°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to one Li(1) and one Fe(2) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one Fe(2) atom. In the fourth F site, F(4) is bonded in a trigonal pyramidal geometry to two equivalent Li(1), one Fe(1), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one Fe(2) atom.
LiFeF4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(2), one F(4), and one F(5) atom. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(2) bond length is 1.85 Å. The Li(1)-F(4) bond length is 2.15 Å. The Li(1)-F(5) bond length is 1.95 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(3), one F(4), two equivalent F(2), and two equivalent F(5) atoms to form a mixture of corner and face-sharing FeF6 octahedra. The Fe(1)-F(3) bond length is 2.02 Å. The Fe(1)-F(4) bond length is 2.07 Å. Both Fe(1)-F(2) bond lengths are 1.84 Å. Both Fe(1)-F(5) bond lengths are 2.06 Å. In the second Fe site, Fe(2) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(5) atoms to form a mixture of distorted corner and face-sharing FeF6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 46°. The Fe(2)-F(3) bond length is 1.92 Å. The Fe(2)-F(4) bond length is 2.17 Å. Both Fe(2)-F(1) bond lengths are 1.87 Å. Both Fe(2)-F(5) bond lengths are 2.06 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to one Li(1) and one Fe(2) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one Fe(2) atom. In the fourth F site, F(4) is bonded in a trigonal pyramidal geometry to two equivalent Li(1), one Fe(1), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one Fe(2) atom.