Li2MnO2F is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with six equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with three equivalent Mn(1)O4F2 octahedra, edges with three equivalent Mn(2)O4F2 octahedra, and edges with four equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with three equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, edges with three equivalent Mn(2)O4F2 octahedra, and edges with four equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, edges with three equivalent Mn(1)O4F2 octahedra, and edges with four equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), 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(2)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with five equivalent O(2)Li4Mn2 octahedra, and edges with five equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the second O site, O(2) is bonded to one Li(1), one Li(2), two equivalent Li(3), 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(2)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with five equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. F(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), 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(2)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with five equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent O(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°.
Li2MnO2F is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with six equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(1)-O(1) bond lengths are 2.26 Å. Both Li(1)-O(2) bond lengths are 2.09 Å. Both Li(1)-F(1) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with three equivalent Mn(1)O4F2 octahedra, edges with three equivalent Mn(2)O4F2 octahedra, and edges with four equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. Both Li(2)-O(1) bond lengths are 2.04 Å. Both Li(2)-O(2) bond lengths are 2.17 Å. Both Li(2)-F(1) bond lengths are 2.21 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share corners with two equivalent Li(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with three equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. There is one shorter (2.13 Å) and one longer (2.29 Å) Li(3)-O(1) bond length. There is one shorter (1.99 Å) and one longer (2.22 Å) Li(3)-O(2) bond length. There is one shorter (2.06 Å) and one longer (2.24 Å) Li(3)-F(1) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, edges with three equivalent Mn(2)O4F2 octahedra, and edges with four equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. Both Mn(1)-O(1) bond lengths are 1.98 Å. Both Mn(1)-O(2) bond lengths are 1.96 Å. Both Mn(1)-F(1) bond lengths are 2.23 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Li(1)O4F2 octahedra, corners with four equivalent Li(3)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, edges with three equivalent Mn(1)O4F2 octahedra, and edges with four equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. Both Mn(2)-O(1) bond lengths are 1.94 Å. Both Mn(2)-O(2) bond lengths are 2.03 Å. Both Mn(2)-F(1) bond lengths are 2.18 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), 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(2)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with five equivalent O(2)Li4Mn2 octahedra, and edges with five equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the second O site, O(2) is bonded to one Li(1), one Li(2), two equivalent Li(3), 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(2)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent O(2)Li4Mn2 octahedra, edges with five equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. F(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), 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(2)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with five equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent O(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°.