Li5FeOF5 is Caswellsilverite-derived structured and crystallizes in the monoclinic Cc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(4)OF5 octahedra, corners with two equivalent Li(5)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(5)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, and edges with three equivalent Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(4)OF5 octahedra, corners with two equivalent Li(5)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(5)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(4)OF5 octahedra, corners with two equivalent Li(5)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(5)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with three equivalent Li(5)OF5 octahedra, and edges with three equivalent Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the fifth Li site, Li(5) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with three equivalent Li(4)OF5 octahedra, and edges with three equivalent Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. Fe(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form FeOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with three equivalent Li(4)OF5 octahedra, and edges with three equivalent Li(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. O(1) 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 OLi5Fe octahedra that share corners with two equivalent F(1)Li5Fe octahedra, corners with two equivalent F(3)Li5Fe octahedra, corners with two equivalent F(4)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(3)Li5Fe octahedra, edges with two equivalent F(4)Li5Fe octahedra, edges with three equivalent F(2)Li5Fe octahedra, and edges with three equivalent F(5)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are five inequivalent F sites. In the first F site, F(3) 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 two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, corners with two equivalent F(5)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(5)Li5Fe octahedra, edges with three equivalent F(1)Li5Fe octahedra, and edges with three equivalent F(4)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the second F site, F(4) 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 two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, corners with two equivalent F(5)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(5)Li5Fe octahedra, edges with three equivalent F(1)Li5Fe octahedra, and edges with three equivalent F(3)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third F site, F(5) 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 two equivalent F(1)Li5Fe octahedra, corners with two equivalent F(3)Li5Fe octahedra, corners with two equivalent F(4)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(3)Li5Fe octahedra, edges with two equivalent F(4)Li5Fe octahedra, edges with three equivalent O(1)Li5Fe octahedra, and edges with three equivalent F(2)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the fourth F site, F(1) 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 two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, corners with two equivalent F(5)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(5)Li5Fe octahedra, edges with three equivalent F(3)Li5Fe octahedra, and edges with three equivalent F(4)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the fifth 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 two equivalent F(1)Li5Fe octahedra, corners with two equivalent F(3)Li5Fe octahedra, corners with two equivalent F(4)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(3)Li5Fe octahedra, edges with two equivalent F(4)Li5Fe octahedra, edges with three equivalent O(1)Li5Fe octahedra, and edges with three equivalent F(5)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 5-9°.
Li5FeOF5 is Caswellsilverite-derived structured and crystallizes in the monoclinic Cc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(4)OF5 octahedra, corners with two equivalent Li(5)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(5)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, and edges with three equivalent Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. The Li(1)-O(1) bond length is 1.95 Å. The Li(1)-F(1) bond length is 2.28 Å. The Li(1)-F(2) bond length is 2.11 Å. The Li(1)-F(3) bond length is 2.14 Å. The Li(1)-F(4) bond length is 2.20 Å. The Li(1)-F(5) bond length is 2.10 Å. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(4)OF5 octahedra, corners with two equivalent Li(5)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(5)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Li(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-F(1) bond length is 2.06 Å. The Li(2)-F(2) bond length is 2.16 Å. The Li(2)-F(3) bond length is 2.16 Å. The Li(2)-F(4) bond length is 2.08 Å. The Li(2)-F(5) bond length is 2.10 Å. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(4)OF5 octahedra, corners with two equivalent Li(5)OF5 octahedra, corners with two equivalent Fe(1)OF5 octahedra, edges with two equivalent Li(4)OF5 octahedra, edges with two equivalent Li(5)OF5 octahedra, edges with two equivalent Fe(1)OF5 octahedra, edges with three equivalent Li(1)OF5 octahedra, and edges with three equivalent Li(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. The Li(3)-O(1) bond length is 2.00 Å. The Li(3)-F(1) bond length is 2.09 Å. The Li(3)-F(2) bond length is 2.05 Å. The Li(3)-F(3) bond length is 2.00 Å. The Li(3)-F(4) bond length is 2.25 Å. The Li(3)-F(5) bond length is 2.18 Å. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with three equivalent Li(5)OF5 octahedra, and edges with three equivalent Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. The Li(4)-O(1) bond length is 1.99 Å. The Li(4)-F(1) bond length is 2.10 Å. The Li(4)-F(2) bond length is 2.05 Å. The Li(4)-F(3) bond length is 2.24 Å. The Li(4)-F(4) bond length is 2.14 Å. The Li(4)-F(5) bond length is 2.10 Å. In the fifth Li site, Li(5) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with three equivalent Li(4)OF5 octahedra, and edges with three equivalent Fe(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. The Li(5)-O(1) bond length is 1.99 Å. The Li(5)-F(1) bond length is 2.22 Å. The Li(5)-F(2) bond length is 2.11 Å. The Li(5)-F(3) bond length is 2.15 Å. The Li(5)-F(4) bond length is 2.18 Å. The Li(5)-F(5) bond length is 2.04 Å. Fe(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form FeOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(3)OF5 octahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Li(2)OF5 octahedra, edges with two equivalent Li(3)OF5 octahedra, edges with three equivalent Li(4)OF5 octahedra, and edges with three equivalent Li(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Fe(1)-O(1) bond length is 1.93 Å. The Fe(1)-F(1) bond length is 2.17 Å. The Fe(1)-F(2) bond length is 2.17 Å. The Fe(1)-F(3) bond length is 2.16 Å. The Fe(1)-F(4) bond length is 2.11 Å. The Fe(1)-F(5) bond length is 2.18 Å. O(1) 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 OLi5Fe octahedra that share corners with two equivalent F(1)Li5Fe octahedra, corners with two equivalent F(3)Li5Fe octahedra, corners with two equivalent F(4)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(3)Li5Fe octahedra, edges with two equivalent F(4)Li5Fe octahedra, edges with three equivalent F(2)Li5Fe octahedra, and edges with three equivalent F(5)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are five inequivalent F sites. In the first F site, F(3) 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 two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, corners with two equivalent F(5)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(5)Li5Fe octahedra, edges with three equivalent F(1)Li5Fe octahedra, and edges with three equivalent F(4)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the second F site, F(4) 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 two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, corners with two equivalent F(5)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(5)Li5Fe octahedra, edges with three equivalent F(1)Li5Fe octahedra, and edges with three equivalent F(3)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third F site, F(5) 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 two equivalent F(1)Li5Fe octahedra, corners with two equivalent F(3)Li5Fe octahedra, corners with two equivalent F(4)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(3)Li5Fe octahedra, edges with two equivalent F(4)Li5Fe octahedra, edges with three equivalent O(1)Li5Fe octahedra, and edges with three equivalent F(2)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the fourth F site, F(1) 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 two equivalent O(1)Li5Fe octahedra, corners with two equivalent F(2)Li5Fe octahedra, corners with two equivalent F(5)Li5Fe octahedra, edges with two equivalent O(1)Li5Fe octahedra, edges with two equivalent F(2)Li5Fe octahedra, edges with two equivalent F(5)Li5Fe octahedra, edges with three equivalent F(3)Li5Fe octahedra, and edges with three equivalent F(4)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the fifth 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 two equivalent F(1)Li5Fe octahedra, corners with two equivalent F(3)Li5Fe octahedra, corners with two equivalent F(4)Li5Fe octahedra, edges with two equivalent F(1)Li5Fe octahedra, edges with two equivalent F(3)Li5Fe octahedra, edges with two equivalent F(4)Li5Fe octahedra, edges with three equivalent O(1)Li5Fe octahedra, and edges with three equivalent F(5)Li5Fe octahedra. The corner-sharing octahedral tilt angles range from 5-9°.