Li5Mn3O5F3 is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(5), one F(1), and one F(3) atom to form LiO4F2 octahedra that share corners with six equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(3)O3F3 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the third Li site, Li(3) is bonded to one O(1), one O(4), one O(5), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Mn(3)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(2) atom to form LiO5F octahedra that share corners with six equivalent Mn(1)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth Li site, Li(5) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(3)O3F3 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-11°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(2) atom to form distorted MnO5F octahedra that share corners with six equivalent Li(4)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(5), one F(1), and one F(3) atom to form MnO4F2 octahedra that share corners with six equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the third Mn site, Mn(3) is bonded to one O(1), one O(4), one O(5), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share corners with six equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-10°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi3Mn3 octahedra that share corners with six equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(4), one Li(5), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), one Li(5), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Mn(1), and one Mn(3) atom to form OLi4Mn2 octahedra that share corners with six equivalent F(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi3Mn3 octahedra that share corners with six equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Mn(2), and one Mn(3) atom to form FLi4Mn2 octahedra that share corners with six equivalent F(3)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, and edges with two equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second F site, F(2) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Mn(1), and one Mn(3) atom to form distorted FLi4Mn2 octahedra that share corners with six equivalent O(4)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Mn(2), and one Mn(3) atom to form FLi4Mn2 octahedra that share corners with six equivalent F(1)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, and edges with two equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.
Li5Mn3O5F3 is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(5), one F(1), and one F(3) atom to form LiO4F2 octahedra that share corners with six equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 5-8°. The Li(1)-O(1) bond length is 2.22 Å. The Li(1)-O(2) bond length is 2.18 Å. The Li(1)-O(3) bond length is 2.18 Å. The Li(1)-O(5) bond length is 2.23 Å. The Li(1)-F(1) bond length is 2.11 Å. The Li(1)-F(3) bond length is 2.14 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(3)O3F3 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-11°. The Li(2)-O(2) bond length is 2.31 Å. The Li(2)-O(3) bond length is 2.23 Å. The Li(2)-O(4) bond length is 2.02 Å. The Li(2)-F(1) bond length is 2.10 Å. The Li(2)-F(2) bond length is 2.18 Å. The Li(2)-F(3) bond length is 2.05 Å. In the third Li site, Li(3) is bonded to one O(1), one O(4), one O(5), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Mn(3)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Li(3)-O(1) bond length is 2.29 Å. The Li(3)-O(4) bond length is 1.98 Å. The Li(3)-O(5) bond length is 2.42 Å. The Li(3)-F(1) bond length is 2.01 Å. The Li(3)-F(2) bond length is 2.09 Å. The Li(3)-F(3) bond length is 1.99 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(2) atom to form LiO5F octahedra that share corners with six equivalent Mn(1)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Li(4)-O(1) bond length is 2.12 Å. The Li(4)-O(2) bond length is 2.23 Å. The Li(4)-O(3) bond length is 2.23 Å. The Li(4)-O(4) bond length is 2.11 Å. The Li(4)-O(5) bond length is 2.18 Å. The Li(4)-F(2) bond length is 2.27 Å. In the fifth Li site, Li(5) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form LiO3F3 octahedra that share corners with six equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(3)O3F3 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-11°. The Li(5)-O(2) bond length is 2.24 Å. The Li(5)-O(3) bond length is 2.33 Å. The Li(5)-O(4) bond length is 2.01 Å. The Li(5)-F(1) bond length is 2.05 Å. The Li(5)-F(2) bond length is 2.17 Å. The Li(5)-F(3) bond length is 2.07 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(2) atom to form distorted MnO5F octahedra that share corners with six equivalent Li(4)O5F octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Mn(1)-O(1) bond length is 2.00 Å. The Mn(1)-O(2) bond length is 1.97 Å. The Mn(1)-O(3) bond length is 1.97 Å. The Mn(1)-O(4) bond length is 2.13 Å. The Mn(1)-O(5) bond length is 1.98 Å. The Mn(1)-F(2) bond length is 2.56 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(5), one F(1), and one F(3) atom to form MnO4F2 octahedra that share corners with six equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 5-8°. The Mn(2)-O(1) bond length is 1.96 Å. The Mn(2)-O(2) bond length is 1.94 Å. The Mn(2)-O(3) bond length is 1.94 Å. The Mn(2)-O(5) bond length is 1.97 Å. The Mn(2)-F(1) bond length is 2.41 Å. The Mn(2)-F(3) bond length is 2.41 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(4), one O(5), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share corners with six equivalent Li(3)O3F3 octahedra, edges with two equivalent Li(2)O3F3 octahedra, edges with two equivalent Li(5)O3F3 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(4)O5F octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Mn(3)-O(1) bond length is 2.23 Å. The Mn(3)-O(4) bond length is 2.02 Å. The Mn(3)-O(5) bond length is 2.16 Å. The Mn(3)-F(1) bond length is 2.20 Å. The Mn(3)-F(2) bond length is 2.15 Å. The Mn(3)-F(3) bond length is 2.19 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi3Mn3 octahedra that share corners with six equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(4), one Li(5), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), one Li(5), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Mn(1), and one Mn(3) atom to form OLi4Mn2 octahedra that share corners with six equivalent F(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi3Mn3 octahedra that share corners with six equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Mn(2), and one Mn(3) atom to form FLi4Mn2 octahedra that share corners with six equivalent F(3)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, and edges with two equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second F site, F(2) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Mn(1), and one Mn(3) atom to form distorted FLi4Mn2 octahedra that share corners with six equivalent O(4)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, and edges with two equivalent F(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Mn(2), and one Mn(3) atom to form FLi4Mn2 octahedra that share corners with six equivalent F(1)Li4Mn2 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Mn3 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, and edges with two equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.