Li3FeOF3 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form LiO2F4 octahedra that share corners with six equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with four equivalent Li(5)O2F4 octahedra, and edges with four equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form LiO2F4 octahedra that share corners with six equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with four equivalent Li(5)O2F4 octahedra, and edges with four equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. In the third Li site, Li(3) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with six equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(5)O2F4 octahedra, and edges with four equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. In the fourth Li site, Li(4) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with six equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(5)O2F4 octahedra, and edges with four equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. In the fifth Li site, Li(5) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with six equivalent Fe(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(5)O2F4 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. Fe(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with six equivalent Li(5)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(5)O2F4 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. O(1) is bonded to one Li(1), one Li(2), two equivalent Li(5), and two equivalent Fe(1) atoms to form OLi4Fe2 octahedra that share corners with six equivalent O(1)Li4Fe2 octahedra, edges with four equivalent F(1)Li4Fe2 octahedra, and edges with eight equivalent F(2)Li5Fe octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), one Li(4), two equivalent Li(5), and two equivalent Fe(1) atoms to form FLi4Fe2 octahedra that share corners with six equivalent F(1)Li4Fe2 octahedra, edges with four equivalent O(1)Li4Fe2 octahedra, and edges with eight equivalent F(2)Li5Fe octahedra. The corner-sharing octahedra are not tilted. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Fe(1) atom to form FLi5Fe octahedra that share corners with six equivalent F(2)Li5Fe octahedra, edges with four equivalent O(1)Li4Fe2 octahedra, edges with four equivalent F(1)Li4Fe2 octahedra, and edges with four equivalent F(2)Li5Fe octahedra. The corner-sharing octahedra are not tilted.
Li3FeOF3 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form LiO2F4 octahedra that share corners with six equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with four equivalent Li(5)O2F4 octahedra, and edges with four equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Li(1)-O(1) bond lengths are 2.18 Å. All Li(1)-F(2) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form LiO2F4 octahedra that share corners with six equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with four equivalent Li(5)O2F4 octahedra, and edges with four equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Li(2)-O(1) bond lengths are 2.16 Å. All Li(2)-F(2) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with six equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(5)O2F4 octahedra, and edges with four equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. Both Li(3)-F(1) bond lengths are 2.21 Å. All Li(3)-F(2) bond lengths are 2.09 Å. In the fourth Li site, Li(4) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with six equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with four equivalent Li(5)O2F4 octahedra, and edges with four equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-9°. Both Li(4)-F(1) bond lengths are 2.12 Å. All Li(4)-F(2) bond lengths are 2.12 Å. In the fifth Li site, Li(5) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with six equivalent Fe(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(5)O2F4 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. Both Li(5)-O(1) bond lengths are 2.24 Å. Both Li(5)-F(1) bond lengths are 1.99 Å. Both Li(5)-F(2) bond lengths are 2.08 Å. Fe(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with six equivalent Li(5)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Li(5)O2F4 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. Both Fe(1)-O(1) bond lengths are 1.98 Å. Both Fe(1)-F(1) bond lengths are 2.22 Å. Both Fe(1)-F(2) bond lengths are 2.24 Å. O(1) is bonded to one Li(1), one Li(2), two equivalent Li(5), and two equivalent Fe(1) atoms to form OLi4Fe2 octahedra that share corners with six equivalent O(1)Li4Fe2 octahedra, edges with four equivalent F(1)Li4Fe2 octahedra, and edges with eight equivalent F(2)Li5Fe octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(3), one Li(4), two equivalent Li(5), and two equivalent Fe(1) atoms to form FLi4Fe2 octahedra that share corners with six equivalent F(1)Li4Fe2 octahedra, edges with four equivalent O(1)Li4Fe2 octahedra, and edges with eight equivalent F(2)Li5Fe octahedra. The corner-sharing octahedra are not tilted. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Fe(1) atom to form FLi5Fe octahedra that share corners with six equivalent F(2)Li5Fe octahedra, edges with four equivalent O(1)Li4Fe2 octahedra, edges with four equivalent F(1)Li4Fe2 octahedra, and edges with four equivalent F(2)Li5Fe octahedra. The corner-sharing octahedra are not tilted.