Li4Mn7O9F7 is beta indium sulfide-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(5), and two equivalent F(4) atoms to form LiO2F2 tetrahedra that share corners with two equivalent Mn(2)O3F3 octahedra, corners with two equivalent Mn(4)O4F2 octahedra, corners with three equivalent Mn(1)O2F4 octahedra, and corners with four equivalent Mn(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 48-74°. In the second Li site, Li(2) is bonded to one O(3), one O(8), and two equivalent F(2) atoms to form LiO2F2 tetrahedra that share  a cornercorner with one Mn(4)O4F2 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with three equivalent Mn(1)O2F4 octahedra, and corners with four equivalent Mn(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-63°. In the third Li site, Li(3) is bonded to one O(7), two equivalent O(6), and one F(3) atom to form LiO3F tetrahedra that share corners with two equivalent Mn(2)O3F3 octahedra, corners with two equivalent Mn(4)O4F2 octahedra, corners with three equivalent Mn(5)O4F2 octahedra, and corners with four equivalent Mn(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 53-60°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share  a cornercorner with one Mn(4)O4F2 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with three equivalent Mn(5)O4F2 octahedra, and corners with four equivalent Mn(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-64°. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), two equivalent F(2), and two equivalent F(4) atoms to form MnO2F4 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O2F2 tetrahedra,  an edgeedge with one Mn(4)O4F2 octahedra, edges with two equivalent Mn(2)O3F3 octahedra, and edges with two equivalent Mn(3)O5F octahedra. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), one O(5), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share  a cornercorner with one Li(1)O2F2 tetrahedra,  a cornercorner with one Li(3)O3F tetrahedra, corners with two equivalent Li(2)O2F2 tetrahedra, corners with two equivalent Li(4)O2F2 tetrahedra,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Mn(5)O4F2 octahedra, and edges with two equivalent Mn(2)O3F3 octahedra. In the third Mn site, Mn(3) is bonded to one O(1), one O(4), one O(6), one O(7), one O(8), and one F(4) atom to form MnO5F octahedra that share  a cornercorner with one Li(2)O2F2 tetrahedra,  a cornercorner with one Li(4)O2F2 tetrahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Mn(5)O4F2 octahedra, edges with two equivalent Mn(4)O4F2 octahedra, and edges with two equivalent Mn(3)O5F octahedra. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(8), two equivalent O(6), and two equivalent F(4) atoms to form MnO4F2 octahedra that share  a cornercorner with one Li(2)O2F2 tetrahedra,  a cornercorner with one Li(4)O2F2 tetrahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Mn(5)O4F2 octahedra, and edges with four equivalent Mn(3)O5F octahedra. In the fifth Mn site, Mn(5) is bonded to one O(2), one O(7), two equivalent O(6), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with three equivalent Li(4)O2F2 tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(4)O4F2 octahedra, edges with two equivalent Mn(2)O3F3 octahedra, and edges with two equivalent Mn(3)O5F octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(4), one Mn(4), and two equivalent Mn(3) atoms to form a mixture of edge and corner-sharing OLiMn3 tetrahedra. In the second O site, O(2) is bonded to one Li(4), one Mn(5), and two equivalent Mn(2) atoms to form corner-sharing OLiMn3 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Mn(1), and two equivalent Mn(2) atoms to form distorted corner-sharing OLiMn3 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Mn(1), and two equivalent Mn(3) atoms to form a mixture of edge and corner-sharing OLiMn3 tetrahedra. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(2) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(3), one Mn(3), one Mn(4), and one Mn(5) atom. In the seventh O site, O(7) is bonded to one Li(3), one Mn(5), and two equivalent Mn(3) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. In the eighth O site, O(8) is bonded to one Li(2), one Mn(4), and two equivalent Mn(3) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(2), and one Mn(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(3) and two equivalent Mn(2) atoms. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom.
Li4Mn7O9F7 is beta indium sulfide-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(5), and two equivalent F(4) atoms to form LiO2F2 tetrahedra that share corners with two equivalent Mn(2)O3F3 octahedra, corners with two equivalent Mn(4)O4F2 octahedra, corners with three equivalent Mn(1)O2F4 octahedra, and corners with four equivalent Mn(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 48-74°. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(5) bond length is 1.96 Å. Both Li(1)-F(4) bond lengths are 1.94 Å. In the second Li site, Li(2) is bonded to one O(3), one O(8), and two equivalent F(2) atoms to form LiO2F2 tetrahedra that share  a cornercorner with one Mn(4)O4F2 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with three equivalent Mn(1)O2F4 octahedra, and corners with four equivalent Mn(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-63°. The Li(2)-O(3) bond length is 1.99 Å. The Li(2)-O(8) bond length is 2.25 Å. Both Li(2)-F(2) bond lengths are 1.87 Å. In the third Li site, Li(3) is bonded to one O(7), two equivalent O(6), and one F(3) atom to form LiO3F tetrahedra that share corners with two equivalent Mn(2)O3F3 octahedra, corners with two equivalent Mn(4)O4F2 octahedra, corners with three equivalent Mn(5)O4F2 octahedra, and corners with four equivalent Mn(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 53-60°. The Li(3)-O(7) bond length is 2.13 Å. Both Li(3)-O(6) bond lengths are 2.01 Å. The Li(3)-F(3) bond length is 1.94 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share  a cornercorner with one Mn(4)O4F2 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with three equivalent Mn(5)O4F2 octahedra, and corners with four equivalent Mn(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-64°. The Li(4)-O(1) bond length is 2.11 Å. The Li(4)-O(2) bond length is 2.10 Å. Both Li(4)-F(1) bond lengths are 1.96 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), two equivalent F(2), and two equivalent F(4) atoms to form MnO2F4 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O2F2 tetrahedra,  an edgeedge with one Mn(4)O4F2 octahedra, edges with two equivalent Mn(2)O3F3 octahedra, and edges with two equivalent Mn(3)O5F octahedra. The Mn(1)-O(3) bond length is 2.13 Å. The Mn(1)-O(4) bond length is 2.10 Å. Both Mn(1)-F(2) bond lengths are 2.05 Å. Both Mn(1)-F(4) bond lengths are 2.28 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), one O(5), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share  a cornercorner with one Li(1)O2F2 tetrahedra,  a cornercorner with one Li(3)O3F tetrahedra, corners with two equivalent Li(2)O2F2 tetrahedra, corners with two equivalent Li(4)O2F2 tetrahedra,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Mn(5)O4F2 octahedra, and edges with two equivalent Mn(2)O3F3 octahedra. The Mn(2)-O(2) bond length is 1.98 Å. The Mn(2)-O(3) bond length is 1.96 Å. The Mn(2)-O(5) bond length is 1.86 Å. The Mn(2)-F(1) bond length is 2.33 Å. The Mn(2)-F(2) bond length is 2.24 Å. The Mn(2)-F(3) bond length is 2.04 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(4), one O(6), one O(7), one O(8), and one F(4) atom to form MnO5F octahedra that share  a cornercorner with one Li(2)O2F2 tetrahedra,  a cornercorner with one Li(4)O2F2 tetrahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Mn(5)O4F2 octahedra, edges with two equivalent Mn(4)O4F2 octahedra, and edges with two equivalent Mn(3)O5F octahedra. The Mn(3)-O(1) bond length is 1.98 Å. The Mn(3)-O(4) bond length is 1.94 Å. The Mn(3)-O(6) bond length is 2.20 Å. The Mn(3)-O(7) bond length is 1.99 Å. The Mn(3)-O(8) bond length is 2.01 Å. The Mn(3)-F(4) bond length is 2.32 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(8), two equivalent O(6), and two equivalent F(4) atoms to form MnO4F2 octahedra that share  a cornercorner with one Li(2)O2F2 tetrahedra,  a cornercorner with one Li(4)O2F2 tetrahedra, corners with two equivalent Li(1)O2F2 tetrahedra, corners with two equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(1)O2F4 octahedra,  an edgeedge with one Mn(5)O4F2 octahedra, and edges with four equivalent Mn(3)O5F octahedra. The Mn(4)-O(1) bond length is 1.94 Å. The Mn(4)-O(8) bond length is 1.94 Å. Both Mn(4)-O(6) bond lengths are 2.04 Å. Both Mn(4)-F(4) bond lengths are 2.15 Å. In the fifth Mn site, Mn(5) is bonded to one O(2), one O(7), two equivalent O(6), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with three equivalent Li(4)O2F2 tetrahedra, corners with three equivalent Li(3)O3F tetrahedra,  an edgeedge with one Mn(4)O4F2 octahedra, edges with two equivalent Mn(2)O3F3 octahedra, and edges with two equivalent Mn(3)O5F octahedra. The Mn(5)-O(2) bond length is 1.95 Å. The Mn(5)-O(7) bond length is 1.99 Å. Both Mn(5)-O(6) bond lengths are 1.88 Å. Both Mn(5)-F(1) bond lengths are 1.95 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(4), one Mn(4), and two equivalent Mn(3) atoms to form a mixture of edge and corner-sharing OLiMn3 tetrahedra. In the second O site, O(2) is bonded to one Li(4), one Mn(5), and two equivalent Mn(2) atoms to form corner-sharing OLiMn3 tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Mn(1), and two equivalent Mn(2) atoms to form distorted corner-sharing OLiMn3 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Mn(1), and two equivalent Mn(3) atoms to form a mixture of edge and corner-sharing OLiMn3 tetrahedra. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(2) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(3), one Mn(3), one Mn(4), and one Mn(5) atom. In the seventh O site, O(7) is bonded to one Li(3), one Mn(5), and two equivalent Mn(3) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. In the eighth O site, O(8) is bonded to one Li(2), one Mn(4), and two equivalent Mn(3) atoms to form a mixture of distorted edge and corner-sharing OLiMn3 tetrahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(2), and one Mn(5) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(3) and two equivalent Mn(2) atoms. In the fourth F site, F(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom.