Li2MnO2F crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(4), one F(1), and one F(2) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(1)O4F2 octahedra,  an edgeedge with one Li(3)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, edges with three equivalent Li(4)O4F2 octahedra, and edges with three equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(3), one F(1), and one F(2) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(2)O4F2 octahedra,  an edgeedge with one Li(4)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with three equivalent Li(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 3-10°. In the third Li site, Li(3) is bonded to one O(3), three equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one Li(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(3)O4F2 octahedra,  an edgeedge with one Li(1)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, edges with three equivalent Li(3)O4F2 octahedra, and edges with five equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the fourth Li site, Li(4) is bonded to one O(4), three equivalent O(1), and two equivalent F(2) atoms to form LiO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one Li(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra,  an edgeedge with one Li(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(4)O4F2 octahedra, and edges with five equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent F(2) atoms to form MnO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one Li(2)O4F2 octahedra,  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with five equivalent Li(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one Li(2)O4F2 octahedra,  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, and edges with five equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), three equivalent Li(4), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(3)Li4Mn2 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn2 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one O(3)Li4Mn2 octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with five equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second O site, O(2) is bonded to one Li(2), three equivalent Li(3), and two equivalent Mn(2) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(3)Li4Mn2 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn2 octahedra, corners with two equivalent O(2)Li4Mn2 octahedra,  an edgeedge with one O(4)Li4Mn2 octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, edges with three equivalent O(3)Li4Mn2 octahedra, and edges with five equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the third O site, O(3) is bonded to one Li(1), one Li(3), two equivalent Li(2), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra,  an edgeedge with one O(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with three equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), two equivalent Li(1), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra,  an edgeedge with one O(2)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li4Mn2 octahedra, and edges with three equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Mn(2) atoms to form FLi4Mn2 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra,  an edgeedge with one F(1)Li4Mn2 octahedra,  an edgeedge with one F(2)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with three equivalent O(3)Li4Mn2 octahedra, and edges with five equivalent O(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second F site, F(2) is bonded to one Li(1), one Li(2), two equivalent Li(4), and two equivalent Mn(1) atoms to form FLi4Mn2 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn2 octahedra,  an edgeedge with one F(1)Li4Mn2 octahedra,  an edgeedge with one F(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with five equivalent O(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.
Li2MnO2F crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(4), one F(1), and one F(2) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(1)O4F2 octahedra,  an edgeedge with one Li(3)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, edges with three equivalent Li(4)O4F2 octahedra, and edges with three equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. The Li(1)-O(1) bond length is 2.05 Å. The Li(1)-O(3) bond length is 2.06 Å. There is one shorter (2.20 Å) and one longer (2.44 Å) Li(1)-O(4) bond length. The Li(1)-F(1) bond length is 2.09 Å. The Li(1)-F(2) bond length is 2.09 Å. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(3), one F(1), and one F(2) atom to form LiO4F2 octahedra that share  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(2)O4F2 octahedra,  an edgeedge with one Li(4)O4F2 octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with three equivalent Li(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 3-10°. The Li(2)-O(2) bond length is 2.05 Å. The Li(2)-O(4) bond length is 2.06 Å. There is one shorter (2.20 Å) and one longer (2.45 Å) Li(2)-O(3) bond length. The Li(2)-F(1) bond length is 2.09 Å. The Li(2)-F(2) bond length is 2.09 Å. In the third Li site, Li(3) is bonded to one O(3), three equivalent O(2), and two equivalent F(1) atoms to form LiO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one Li(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(3)O4F2 octahedra,  an edgeedge with one Li(1)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, edges with three equivalent Li(3)O4F2 octahedra, and edges with five equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. The Li(3)-O(3) bond length is 2.05 Å. There are a spread of Li(3)-O(2) bond distances ranging from 2.06-2.45 Å. Both Li(3)-F(1) bond lengths are 2.09 Å. In the fourth Li site, Li(4) is bonded to one O(4), three equivalent O(1), and two equivalent F(2) atoms to form LiO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one Li(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(4)O4F2 octahedra,  an edgeedge with one Li(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(4)O4F2 octahedra, and edges with five equivalent Mn(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. The Li(4)-O(4) bond length is 2.05 Å. There are a spread of Li(4)-O(1) bond distances ranging from 2.06-2.45 Å. Both Li(4)-F(2) bond lengths are 2.09 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent F(2) atoms to form MnO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one Li(2)O4F2 octahedra,  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with three equivalent Li(1)O4F2 octahedra, and edges with five equivalent Li(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. The Mn(1)-O(3) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 1.94 Å. Both Mn(1)-O(1) bond lengths are 1.94 Å. There is one shorter (2.31 Å) and one longer (2.32 Å) Mn(1)-F(2) bond length. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share  a cornercorner with one Li(1)O4F2 octahedra,  a cornercorner with one Li(2)O4F2 octahedra,  a cornercorner with one Li(3)O4F2 octahedra,  a cornercorner with one Li(4)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra,  an edgeedge with one Mn(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra, edges with two equivalent Li(1)O4F2 octahedra, edges with three equivalent Li(2)O4F2 octahedra, and edges with five equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. The Mn(2)-O(3) bond length is 1.94 Å. The Mn(2)-O(4) bond length is 1.94 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Mn(2)-O(2) bond length. There is one shorter (2.30 Å) and one longer (2.32 Å) Mn(2)-F(1) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), three equivalent Li(4), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(3)Li4Mn2 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn2 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one O(3)Li4Mn2 octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with five equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second O site, O(2) is bonded to one Li(2), three equivalent Li(3), and two equivalent Mn(2) atoms to form OLi4Mn2 octahedra that share  a cornercorner with one O(3)Li4Mn2 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn2 octahedra, corners with two equivalent O(2)Li4Mn2 octahedra,  an edgeedge with one O(4)Li4Mn2 octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, edges with three equivalent O(3)Li4Mn2 octahedra, and edges with five equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the third O site, O(3) is bonded to one Li(1), one Li(3), two equivalent Li(2), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn2 octahedra, corners with two equivalent O(3)Li4Mn2 octahedra,  an edgeedge with one O(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn2 octahedra, edges with three equivalent O(2)Li4Mn2 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with three equivalent F(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), two equivalent Li(1), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn2 octahedra, corners with two equivalent O(4)Li4Mn2 octahedra,  an edgeedge with one O(2)Li4Mn2 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li4Mn2 octahedra, and edges with three equivalent F(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Mn(2) atoms to form FLi4Mn2 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra,  an edgeedge with one F(1)Li4Mn2 octahedra,  an edgeedge with one F(2)Li4Mn2 octahedra, edges with two equivalent O(4)Li4Mn2 octahedra, edges with three equivalent O(3)Li4Mn2 octahedra, and edges with five equivalent O(2)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the second F site, F(2) is bonded to one Li(1), one Li(2), two equivalent Li(4), and two equivalent Mn(1) atoms to form FLi4Mn2 octahedra that share  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one O(2)Li4Mn2 octahedra,  a cornercorner with one O(3)Li4Mn2 octahedra,  a cornercorner with one O(4)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn2 octahedra,  an edgeedge with one F(1)Li4Mn2 octahedra,  an edgeedge with one F(2)Li4Mn2 octahedra, edges with two equivalent O(3)Li4Mn2 octahedra, edges with three equivalent O(4)Li4Mn2 octahedra, and edges with five equivalent O(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.