Li4Mn3O6F is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), two equivalent O(3), and one F(1) atom to form LiO5F octahedra that share  a cornercorner with one Li(2)O5F octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with three equivalent Li(1)O5F octahedra,  an edgeedge with one Li(1)O5F octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with four equivalent Li(2)O5F octahedra, and edges with five equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Li site, Li(2) is bonded to one O(2), one O(3), three equivalent O(1), and one F(1) atom to form LiO5F octahedra that share  a cornercorner with one Li(1)O5F octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Li(2)O5F octahedra, edges with two equivalent Li(2)O5F octahedra, edges with three equivalent Mn(1)O4F2 octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-9°. 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)O5F octahedra, corners with two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O5F octahedra, and edges with six equivalent Li(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second Mn site, Mn(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O5F octahedra,  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent Li(2)O5F octahedra, corners with two equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(1)O4F2 octahedra, edges with three equivalent Li(2)O5F octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with five equivalent Li(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-7°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), three equivalent Li(2), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with three equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li3Mn3 octahedra, edges with three equivalent F(1)Li4Mn2 octahedra, and edges with four equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra, corners with three equivalent O(2)Li3Mn3 octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), and three equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one F(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li3Mn3 octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Mn(1) atoms to form FLi4Mn2 octahedra that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with six equivalent O(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
Li4Mn3O6F is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), two equivalent O(3), and one F(1) atom to form LiO5F octahedra that share  a cornercorner with one Li(2)O5F octahedra,  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with three equivalent Li(1)O5F octahedra,  an edgeedge with one Li(1)O5F octahedra, edges with two equivalent Mn(1)O4F2 octahedra, edges with four equivalent Li(2)O5F octahedra, and edges with five equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Li(1)-O(1) bond length is 2.17 Å. Both Li(1)-O(2) bond lengths are 2.23 Å. There is one shorter (2.00 Å) and one longer (2.23 Å) Li(1)-O(3) bond length. The Li(1)-F(1) bond length is 2.08 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), three equivalent O(1), and one F(1) atom to form LiO5F octahedra that share  a cornercorner with one Li(1)O5F octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Li(2)O5F octahedra, edges with two equivalent Li(2)O5F octahedra, edges with three equivalent Mn(1)O4F2 octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Li(2)-O(2) bond length is 2.15 Å. The Li(2)-O(3) bond length is 2.11 Å. There is one shorter (2.04 Å) and two longer (2.23 Å) Li(2)-O(1) bond lengths. The Li(2)-F(1) bond length is 2.10 Å. 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)O5F octahedra, corners with two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O5F octahedra, and edges with six equivalent Li(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Mn(1)-O(1) bond lengths are 1.93 Å. Both Mn(1)-O(2) bond lengths are 2.01 Å. Both Mn(1)-F(1) bond lengths are 2.22 Å. In the second Mn site, Mn(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O5F octahedra,  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent Li(2)O5F octahedra, corners with two equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(1)O4F2 octahedra, edges with three equivalent Li(2)O5F octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with five equivalent Li(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 0-7°. The Mn(2)-O(1) bond length is 1.99 Å. There is one shorter (1.95 Å) and one longer (2.12 Å) Mn(2)-O(2) bond length. There is one shorter (1.91 Å) and two longer (2.23 Å) Mn(2)-O(3) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), three equivalent Li(2), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with three equivalent O(1)Li4Mn2 octahedra, edges with two equivalent O(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li3Mn3 octahedra, edges with three equivalent F(1)Li4Mn2 octahedra, and edges with four equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(1)Li4Mn2 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra, corners with three equivalent O(2)Li3Mn3 octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with two equivalent F(1)Li4Mn2 octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), and three equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one F(1)Li4Mn2 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one F(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li3Mn3 octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Mn(1) atoms to form FLi4Mn2 octahedra that share corners with two equivalent O(2)Li3Mn3 octahedra, corners with two equivalent O(3)Li3Mn3 octahedra, corners with two equivalent F(1)Li4Mn2 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, and edges with six equivalent O(1)Li4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.