Li2MnO2F is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, and edges with three equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-18°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with three equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-18°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form distorted LiO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with three equivalent Li(4)O4F2 octahedra, and edges with three equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with three equivalent Li(3)O4F2 octahedra, and edges with three equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-18°. There are two 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 F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with three equivalent Li(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with three equivalent Li(3)O4F2 octahedra, and edges with three equivalent Li(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 5-18°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 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, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with three equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, edges with three equivalent O(3)Li4Mn2 octahedra, and edges with three equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, and edges with three equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 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, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with three equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-12°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form FLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, and edges with three equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form FLi4Mn2 octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 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, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with three equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 3-10°.
Li2MnO2F is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, and edges with three equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-18°. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-O(2) bond length is 2.05 Å. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(4) bond length is 2.14 Å. The Li(1)-F(1) bond length is 2.15 Å. The Li(1)-F(2) bond length is 2.11 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with three equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-18°. The Li(2)-O(1) bond length is 2.11 Å. The Li(2)-O(2) bond length is 2.11 Å. The Li(2)-O(3) bond length is 2.06 Å. The Li(2)-O(4) bond length is 2.15 Å. The Li(2)-F(1) bond length is 2.33 Å. The Li(2)-F(2) bond length is 2.20 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form distorted LiO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with three equivalent Li(4)O4F2 octahedra, and edges with three equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. The Li(3)-O(1) bond length is 2.44 Å. The Li(3)-O(2) bond length is 1.96 Å. The Li(3)-O(3) bond length is 2.50 Å. The Li(3)-O(4) bond length is 1.99 Å. The Li(3)-F(1) bond length is 2.07 Å. The Li(3)-F(2) bond length is 2.02 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form LiO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with three equivalent Li(3)O4F2 octahedra, and edges with three equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-18°. The Li(4)-O(1) bond length is 2.00 Å. The Li(4)-O(2) bond length is 2.23 Å. The Li(4)-O(3) bond length is 2.04 Å. The Li(4)-O(4) bond length is 2.30 Å. The Li(4)-F(1) bond length is 2.12 Å. The Li(4)-F(2) bond length is 2.05 Å. There are two 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 F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(4)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with three equivalent Li(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. The Mn(1)-O(1) bond length is 1.94 Å. The Mn(1)-O(2) bond length is 2.09 Å. The Mn(1)-O(3) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 1.95 Å. The Mn(1)-F(1) bond length is 2.10 Å. The Mn(1)-F(2) bond length is 2.29 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with three equivalent Li(3)O4F2 octahedra, and edges with three equivalent Li(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 5-18°. The Mn(2)-O(1) bond length is 1.99 Å. The Mn(2)-O(2) bond length is 1.94 Å. The Mn(2)-O(3) bond length is 1.98 Å. The Mn(2)-O(4) bond length is 1.97 Å. The Mn(2)-F(1) bond length is 2.28 Å. The Mn(2)-F(2) bond length is 2.24 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 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, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with three equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, edges with three equivalent O(3)Li4Mn2 octahedra, and edges with three equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, and edges with three equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 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, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with three equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-12°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form FLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, and edges with three equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Mn(1), and one Mn(2) atom to form FLi4Mn2 octahedra that share corners with two equivalent O(2)Li4Mn2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 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, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with three equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 3-10°.