Li2FeO2F is Caswellsilverite-derived structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent Li(1)O4F2 octahedra, corners with two equivalent Fe(1)O5F octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with five equivalent Li(2)O3F3 octahedra, and edges with five equivalent Fe(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the second Li site, Li(2) is bonded to one O(1), two equivalent O(2), and three equivalent F(1) atoms to form LiO3F3 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with five equivalent Li(1)O4F2 octahedra, and edges with five equivalent Fe(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 3-5°. Fe(1) is bonded to two equivalent O(2), three equivalent O(1), and one F(1) atom to form FeO5F octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Fe(1)O5F octahedra, edges with two equivalent Fe(1)O5F octahedra, edges with five equivalent Li(2)O3F3 octahedra, and edges with five equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and three equivalent Fe(1) atoms to form OLi3Fe3 octahedra that share corners with two equivalent O(2)Li4Fe2 octahedra, corners with four equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(1)Li3Fe3 octahedra, edges with five equivalent O(2)Li4Fe2 octahedra, and edges with five equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms to form OLi4Fe2 octahedra that share corners with two equivalent O(1)Li3Fe3 octahedra, corners with two equivalent O(2)Li4Fe2 octahedra, corners with two equivalent F(1)Li5Fe octahedra, edges with two equivalent O(2)Li4Fe2 octahedra, edges with five equivalent O(1)Li3Fe3 octahedra, and edges with five equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 2-12°. F(1) is bonded to two equivalent Li(1), three equivalent Li(2), and one Fe(1) atom to form FLi5Fe octahedra that share corners with two equivalent O(2)Li4Fe2 octahedra, corners with four equivalent F(1)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with five equivalent O(1)Li3Fe3 octahedra, and edges with five equivalent O(2)Li4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°.
Li2FeO2F is Caswellsilverite-derived structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(2)O3F3 octahedra, corners with two equivalent Li(1)O4F2 octahedra, corners with two equivalent Fe(1)O5F octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with five equivalent Li(2)O3F3 octahedra, and edges with five equivalent Fe(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-6°. There is one shorter (2.10 Å) and one longer (2.14 Å) Li(1)-O(1) bond length. Both Li(1)-O(2) bond lengths are 2.05 Å. There is one shorter (2.09 Å) and one longer (2.20 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to one O(1), two equivalent O(2), and three equivalent F(1) atoms to form LiO3F3 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with five equivalent Li(1)O4F2 octahedra, and edges with five equivalent Fe(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 3-5°. The Li(2)-O(1) bond length is 2.15 Å. There is one shorter (2.09 Å) and one longer (2.11 Å) Li(2)-O(2) bond length. There is one shorter (1.99 Å) and two longer (2.05 Å) Li(2)-F(1) bond lengths. Fe(1) is bonded to two equivalent O(2), three equivalent O(1), and one F(1) atom to form FeO5F octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Fe(1)O5F octahedra, edges with two equivalent Fe(1)O5F octahedra, edges with five equivalent Li(2)O3F3 octahedra, and edges with five equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. Both Fe(1)-O(2) bond lengths are 1.96 Å. There is one shorter (2.05 Å) and two longer (2.06 Å) Fe(1)-O(1) bond lengths. The Fe(1)-F(1) bond length is 2.24 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and three equivalent Fe(1) atoms to form OLi3Fe3 octahedra that share corners with two equivalent O(2)Li4Fe2 octahedra, corners with four equivalent O(1)Li3Fe3 octahedra, edges with two equivalent O(1)Li3Fe3 octahedra, edges with five equivalent O(2)Li4Fe2 octahedra, and edges with five equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Fe(1) atoms to form OLi4Fe2 octahedra that share corners with two equivalent O(1)Li3Fe3 octahedra, corners with two equivalent O(2)Li4Fe2 octahedra, corners with two equivalent F(1)Li5Fe octahedra, edges with two equivalent O(2)Li4Fe2 octahedra, edges with five equivalent O(1)Li3Fe3 octahedra, and edges with five equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 2-12°. F(1) is bonded to two equivalent Li(1), three equivalent Li(2), and one Fe(1) atom to form FLi5Fe octahedra that share corners with two equivalent O(2)Li4Fe2 octahedra, corners with four equivalent F(1)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with five equivalent O(1)Li3Fe3 octahedra, and edges with five equivalent O(2)Li4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°.