Mn7O7F crystallizes in the trigonal P3m1 space group. There are seven inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent O(4) and one F(1) atom to form MnO3F tetrahedra that share corners with three equivalent Mn(5)O4 tetrahedra and corners with six equivalent Mn(1)O3F tetrahedra. In the second Mn site, Mn(2) is bonded to one O(1) and three equivalent O(5) atoms to form corner-sharing MnO4 tetrahedra. In the third Mn site, Mn(3) is bonded to one O(2), one O(3), and three equivalent O(6) atoms to form distorted MnO5 trigonal bipyramids that share corners with three equivalent Mn(6)O4 tetrahedra, corners with six equivalent Mn(3)O5 trigonal bipyramids, and edges with three equivalent Mn(7)O5 trigonal bipyramids. In the fourth Mn site, Mn(4) is bonded in a 5-coordinate geometry to one O(3), three equivalent O(7), and one F(1) atom. In the fifth Mn site, Mn(5) is bonded to one O(4) and three equivalent O(1) atoms to form MnO4 tetrahedra that share corners with three equivalent Mn(1)O3F tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra, and corners with six equivalent Mn(5)O4 tetrahedra. In the sixth Mn site, Mn(6) is bonded to one O(5) and three equivalent O(2) atoms to form MnO4 tetrahedra that share corners with three equivalent Mn(2)O4 tetrahedra, corners with six equivalent Mn(6)O4 tetrahedra, and corners with three equivalent Mn(3)O5 trigonal bipyramids. In the seventh Mn site, Mn(7) is bonded to one O(6), one O(7), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing MnO5 trigonal bipyramids. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Mn(2) and three equivalent Mn(5) atoms to form corner-sharing OMn4 tetrahedra. In the second O site, O(2) is bonded to one Mn(3) and three equivalent Mn(6) atoms to form OMn4 tetrahedra that share corners with three equivalent O(5)Mn4 tetrahedra, corners with three equivalent O(6)Mn4 tetrahedra, corners with six equivalent O(2)Mn4 tetrahedra, and  a cornercorner with one O(3)Mn5 trigonal bipyramid. In the third O site, O(3) is bonded to one Mn(3), one Mn(4), and three equivalent Mn(7) atoms to form OMn5 trigonal bipyramids that share  a cornercorner with one O(2)Mn4 tetrahedra, corners with six equivalent O(3)Mn5 trigonal bipyramids, edges with three equivalent O(6)Mn4 tetrahedra, and edges with three equivalent O(7)Mn4 tetrahedra. In the fourth O site, O(4) is bonded to one Mn(5) and three equivalent Mn(1) atoms to form corner-sharing OMn4 tetrahedra. In the fifth O site, O(5) is bonded to one Mn(6) and three equivalent Mn(2) atoms to form corner-sharing OMn4 tetrahedra. In the sixth O site, O(6) is bonded to one Mn(7) and three equivalent Mn(3) atoms to form OMn4 tetrahedra that share  a cornercorner with one O(7)Mn4 tetrahedra, corners with three equivalent O(2)Mn4 tetrahedra, corners with six equivalent O(6)Mn4 tetrahedra, and edges with three equivalent O(3)Mn5 trigonal bipyramids. In the seventh O site, O(7) is bonded to one Mn(7) and three equivalent Mn(4) atoms to form OMn4 tetrahedra that share  a cornercorner with one O(6)Mn4 tetrahedra, corners with six equivalent O(7)Mn4 tetrahedra, and edges with three equivalent O(3)Mn5 trigonal bipyramids. F(1) is bonded in a linear geometry to one Mn(1) and one Mn(4) atom.
Mn7O7F crystallizes in the trigonal P3m1 space group. There are seven inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent O(4) and one F(1) atom to form MnO3F tetrahedra that share corners with three equivalent Mn(5)O4 tetrahedra and corners with six equivalent Mn(1)O3F tetrahedra. All Mn(1)-O(4) bond lengths are 2.12 Å. The Mn(1)-F(1) bond length is 2.04 Å. In the second Mn site, Mn(2) is bonded to one O(1) and three equivalent O(5) atoms to form corner-sharing MnO4 tetrahedra. The Mn(2)-O(1) bond length is 2.11 Å. All Mn(2)-O(5) bond lengths are 2.10 Å. In the third Mn site, Mn(3) is bonded to one O(2), one O(3), and three equivalent O(6) atoms to form distorted MnO5 trigonal bipyramids that share corners with three equivalent Mn(6)O4 tetrahedra, corners with six equivalent Mn(3)O5 trigonal bipyramids, and edges with three equivalent Mn(7)O5 trigonal bipyramids. The Mn(3)-O(2) bond length is 2.13 Å. The Mn(3)-O(3) bond length is 2.40 Å. All Mn(3)-O(6) bond lengths are 2.09 Å. In the fourth Mn site, Mn(4) is bonded in a 5-coordinate geometry to one O(3), three equivalent O(7), and one F(1) atom. The Mn(4)-O(3) bond length is 2.58 Å. All Mn(4)-O(7) bond lengths are 2.12 Å. The Mn(4)-F(1) bond length is 2.02 Å. In the fifth Mn site, Mn(5) is bonded to one O(4) and three equivalent O(1) atoms to form MnO4 tetrahedra that share corners with three equivalent Mn(1)O3F tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra, and corners with six equivalent Mn(5)O4 tetrahedra. The Mn(5)-O(4) bond length is 2.10 Å. All Mn(5)-O(1) bond lengths are 2.11 Å. In the sixth Mn site, Mn(6) is bonded to one O(5) and three equivalent O(2) atoms to form MnO4 tetrahedra that share corners with three equivalent Mn(2)O4 tetrahedra, corners with six equivalent Mn(6)O4 tetrahedra, and corners with three equivalent Mn(3)O5 trigonal bipyramids. The Mn(6)-O(5) bond length is 2.11 Å. All Mn(6)-O(2) bond lengths are 2.10 Å. In the seventh Mn site, Mn(7) is bonded to one O(6), one O(7), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing MnO5 trigonal bipyramids. The Mn(7)-O(6) bond length is 2.00 Å. The Mn(7)-O(7) bond length is 1.96 Å. All Mn(7)-O(3) bond lengths are 2.04 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Mn(2) and three equivalent Mn(5) atoms to form corner-sharing OMn4 tetrahedra. In the second O site, O(2) is bonded to one Mn(3) and three equivalent Mn(6) atoms to form OMn4 tetrahedra that share corners with three equivalent O(5)Mn4 tetrahedra, corners with three equivalent O(6)Mn4 tetrahedra, corners with six equivalent O(2)Mn4 tetrahedra, and  a cornercorner with one O(3)Mn5 trigonal bipyramid. In the third O site, O(3) is bonded to one Mn(3), one Mn(4), and three equivalent Mn(7) atoms to form OMn5 trigonal bipyramids that share  a cornercorner with one O(2)Mn4 tetrahedra, corners with six equivalent O(3)Mn5 trigonal bipyramids, edges with three equivalent O(6)Mn4 tetrahedra, and edges with three equivalent O(7)Mn4 tetrahedra. In the fourth O site, O(4) is bonded to one Mn(5) and three equivalent Mn(1) atoms to form corner-sharing OMn4 tetrahedra. In the fifth O site, O(5) is bonded to one Mn(6) and three equivalent Mn(2) atoms to form corner-sharing OMn4 tetrahedra. In the sixth O site, O(6) is bonded to one Mn(7) and three equivalent Mn(3) atoms to form OMn4 tetrahedra that share  a cornercorner with one O(7)Mn4 tetrahedra, corners with three equivalent O(2)Mn4 tetrahedra, corners with six equivalent O(6)Mn4 tetrahedra, and edges with three equivalent O(3)Mn5 trigonal bipyramids. In the seventh O site, O(7) is bonded to one Mn(7) and three equivalent Mn(4) atoms to form OMn4 tetrahedra that share  a cornercorner with one O(6)Mn4 tetrahedra, corners with six equivalent O(7)Mn4 tetrahedra, and edges with three equivalent O(3)Mn5 trigonal bipyramids. F(1) is bonded in a linear geometry to one Mn(1) and one Mn(4) atom.