Li3FeOF3 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form LiF6 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with three equivalent Li(4)OF5 octahedra, edges with two equivalent Fe(1)O3F3 octahedra, edges with three equivalent Li(2)F6 octahedra, edges with three equivalent Li(4)OF5 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. In the second Li site, Li(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Fe(1)O3F3 octahedra, corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with four equivalent Li(4)OF5 octahedra, and edges with six equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. In the third Li site, Li(3) is bonded to four equivalent O(1) and two equivalent F(3) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Fe(1)O3F3 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with four equivalent Li(4)OF5 octahedra, and edges with six equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Fe(1)O3F3 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with three equivalent Li(1)F6 octahedra, and edges with three equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. Fe(1) is bonded to three equivalent O(1), one F(2), and two equivalent F(3) atoms to form FeO3F3 octahedra that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(3)O4F2 octahedra, corners with three equivalent Li(4)OF5 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with three equivalent Li(3)O4F2 octahedra, edges with three equivalent Li(4)OF5 octahedra, and edges with four equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. O(1) is bonded to one Li(4), two equivalent Li(3), and three equivalent Fe(1) atoms to form OLi3Fe3 octahedra that share  a cornercorner with one F(2)Li5Fe octahedra,  a cornercorner with one F(1)Li6 octahedra, corners with two equivalent O(1)Li3Fe3 octahedra, corners with two equivalent F(3)Li4Fe2 octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with five equivalent O(1)Li3Fe3 octahedra, and edges with five equivalent F(3)Li4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(4), two equivalent Li(2), and three equivalent Li(1) atoms to form FLi6 octahedra that share  a cornercorner with one O(1)Li3Fe3 octahedra,  a cornercorner with one F(3)Li4Fe2 octahedra, corners with two equivalent F(2)Li5Fe octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent F(3)Li4Fe2 octahedra, edges with five equivalent F(2)Li5Fe octahedra, and edges with five equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(4), and one Fe(1) atom to form FLi5Fe octahedra that share  a cornercorner with one O(1)Li3Fe3 octahedra,  a cornercorner with one F(2)Li5Fe octahedra, corners with two equivalent F(3)Li4Fe2 octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent O(1)Li3Fe3 octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with three equivalent F(3)Li4Fe2 octahedra, and edges with five equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third F site, F(3) is bonded to one Li(1), one Li(3), two equivalent Li(4), and two equivalent Fe(1) atoms to form FLi4Fe2 octahedra that share  a cornercorner with one F(3)Li4Fe2 octahedra,  a cornercorner with one F(1)Li6 octahedra, corners with two equivalent O(1)Li3Fe3 octahedra, corners with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(3)Li4Fe2 octahedra, edges with two equivalent F(1)Li6 octahedra, edges with three equivalent F(2)Li5Fe octahedra, and edges with five equivalent O(1)Li3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.
Li3FeOF3 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form LiF6 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra, corners with two equivalent Li(2)F6 octahedra, corners with three equivalent Li(4)OF5 octahedra, edges with two equivalent Fe(1)O3F3 octahedra, edges with three equivalent Li(2)F6 octahedra, edges with three equivalent Li(4)OF5 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. The Li(1)-F(3) bond length is 2.03 Å. Both Li(1)-F(2) bond lengths are 2.15 Å. There is one shorter (2.01 Å) and two longer (2.03 Å) Li(1)-F(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Fe(1)O3F3 octahedra, corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with four equivalent Li(4)OF5 octahedra, and edges with six equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. Both Li(2)-F(2) bond lengths are 2.00 Å. All Li(2)-F(1) bond lengths are 2.13 Å. In the third Li site, Li(3) is bonded to four equivalent O(1) and two equivalent F(3) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Fe(1)O3F3 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with four equivalent Li(4)OF5 octahedra, and edges with six equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. All Li(3)-O(1) bond lengths are 2.12 Å. Both Li(3)-F(3) bond lengths are 2.27 Å. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiOF5 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with three equivalent Fe(1)O3F3 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with three equivalent Li(1)F6 octahedra, and edges with three equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. The Li(4)-O(1) bond length is 2.06 Å. The Li(4)-F(1) bond length is 2.14 Å. Both Li(4)-F(2) bond lengths are 2.15 Å. Both Li(4)-F(3) bond lengths are 2.04 Å. Fe(1) is bonded to three equivalent O(1), one F(2), and two equivalent F(3) atoms to form FeO3F3 octahedra that share  a cornercorner with one Li(2)F6 octahedra, corners with two equivalent Li(3)O4F2 octahedra, corners with three equivalent Li(4)OF5 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with three equivalent Li(3)O4F2 octahedra, edges with three equivalent Li(4)OF5 octahedra, and edges with four equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. There are two shorter (2.00 Å) and one longer (2.15 Å) Fe(1)-O(1) bond length. The Fe(1)-F(2) bond length is 2.25 Å. Both Fe(1)-F(3) bond lengths are 2.28 Å. O(1) is bonded to one Li(4), two equivalent Li(3), and three equivalent Fe(1) atoms to form OLi3Fe3 octahedra that share  a cornercorner with one F(2)Li5Fe octahedra,  a cornercorner with one F(1)Li6 octahedra, corners with two equivalent O(1)Li3Fe3 octahedra, corners with two equivalent F(3)Li4Fe2 octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with five equivalent O(1)Li3Fe3 octahedra, and edges with five equivalent F(3)Li4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(4), two equivalent Li(2), and three equivalent Li(1) atoms to form FLi6 octahedra that share  a cornercorner with one O(1)Li3Fe3 octahedra,  a cornercorner with one F(3)Li4Fe2 octahedra, corners with two equivalent F(2)Li5Fe octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent F(3)Li4Fe2 octahedra, edges with five equivalent F(2)Li5Fe octahedra, and edges with five equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second F site, F(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(4), and one Fe(1) atom to form FLi5Fe octahedra that share  a cornercorner with one O(1)Li3Fe3 octahedra,  a cornercorner with one F(2)Li5Fe octahedra, corners with two equivalent F(3)Li4Fe2 octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent O(1)Li3Fe3 octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with three equivalent F(3)Li4Fe2 octahedra, and edges with five equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third F site, F(3) is bonded to one Li(1), one Li(3), two equivalent Li(4), and two equivalent Fe(1) atoms to form FLi4Fe2 octahedra that share  a cornercorner with one F(3)Li4Fe2 octahedra,  a cornercorner with one F(1)Li6 octahedra, corners with two equivalent O(1)Li3Fe3 octahedra, corners with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(3)Li4Fe2 octahedra, edges with two equivalent F(1)Li6 octahedra, edges with three equivalent F(2)Li5Fe octahedra, and edges with five equivalent O(1)Li3Fe3 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.