Li3Fe(OF)2 is beta Polonium-derived structured and crystallizes in the monoclinic P2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with four equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(3)O2F4 octahedra, corners with four equivalent Fe(1)O4F2 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Fe(1)O4F2 octahedra, edges with four equivalent Li(3)O2F4 octahedra, and edges with four equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. In the third Li site, Li(3) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with four equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. Fe(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Fe(1)O4F2 octahedra, edges with four equivalent Li(3)O2F4 octahedra, and edges with four equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. O(1) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Fe(1) atoms to form OLi4Fe2 octahedra that share corners with two equivalent O(1)Li4Fe2 octahedra, corners with four equivalent F(1)Li5Fe octahedra, edges with six equivalent O(1)Li4Fe2 octahedra, and edges with six equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 2-9°. F(1) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Fe(1) atom to form FLi5Fe octahedra that share corners with two equivalent F(1)Li5Fe octahedra, corners with four equivalent O(1)Li4Fe2 octahedra, edges with six equivalent O(1)Li4Fe2 octahedra, and edges with six equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-8°.
Li3Fe(OF)2 is beta Polonium-derived structured and crystallizes in the monoclinic P2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with four equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. There are two shorter (2.09 Å) and two longer (2.18 Å) Li(1)-O(1) bond lengths. Both Li(1)-F(1) bond lengths are 2.17 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(3)O2F4 octahedra, corners with four equivalent Fe(1)O4F2 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Fe(1)O4F2 octahedra, edges with four equivalent Li(3)O2F4 octahedra, and edges with four equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. Both Li(2)-O(1) bond lengths are 2.07 Å. There are two shorter (2.06 Å) and two longer (2.18 Å) Li(2)-F(1) bond lengths. In the third Li site, Li(3) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with four equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. Both Li(3)-O(1) bond lengths are 2.08 Å. There are two shorter (2.08 Å) and two longer (2.10 Å) Li(3)-F(1) bond lengths. Fe(1) is bonded to four equivalent O(1) and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Fe(1)O4F2 octahedra, edges with four equivalent Li(3)O2F4 octahedra, and edges with four equivalent Li(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. There are two shorter (1.96 Å) and two longer (1.98 Å) Fe(1)-O(1) bond lengths. Both Fe(1)-F(1) bond lengths are 2.20 Å. O(1) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Fe(1) atoms to form OLi4Fe2 octahedra that share corners with two equivalent O(1)Li4Fe2 octahedra, corners with four equivalent F(1)Li5Fe octahedra, edges with six equivalent O(1)Li4Fe2 octahedra, and edges with six equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 2-9°. F(1) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Fe(1) atom to form FLi5Fe octahedra that share corners with two equivalent F(1)Li5Fe octahedra, corners with four equivalent O(1)Li4Fe2 octahedra, edges with six equivalent O(1)Li4Fe2 octahedra, and edges with six equivalent F(1)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-8°.