Ba7Fe6(OF16)2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a distorted q6 geometry to two equivalent F(9), four equivalent F(4), and four equivalent F(6) atoms. In the second Ba site, Ba(2) is bonded in a 12-coordinate geometry to one F(8), one F(9), two equivalent F(1), two equivalent F(2), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to one O(1), one F(1), one F(2), one F(3), one F(4), one F(6), one F(7), one F(8), and two equivalent F(5) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(8), one F(9), two equivalent F(5), and two equivalent F(7) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 38°. In the second Fe site, Fe(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(7) atom to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 38°. O(1) is bonded in a water-like geometry to two equivalent Ba(3) atoms. There are nine inequivalent F sites. In the first F site, F(2) is bonded in a 1-coordinate geometry to one Ba(2), one Ba(3), and one Fe(2) atom. In the second F site, F(8) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(3), and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to one Ba(2), one Ba(3), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(3), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(3), and one Fe(1) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Ba(1), one Ba(3), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Ba(3), one Fe(1), and one Fe(2) atom. In the eighth F site, F(9) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one Fe(1) atom. In the ninth F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one Ba(3), and one Fe(2) atom.
Ba7Fe6(OF16)2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a distorted q6 geometry to two equivalent F(9), four equivalent F(4), and four equivalent F(6) atoms. Both Ba(1)-F(9) bond lengths are 2.74 Å. All Ba(1)-F(4) bond lengths are 2.76 Å. All Ba(1)-F(6) bond lengths are 2.88 Å. In the second Ba site, Ba(2) is bonded in a 12-coordinate geometry to one F(8), one F(9), two equivalent F(1), two equivalent F(2), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. The Ba(2)-F(8) bond length is 2.79 Å. The Ba(2)-F(9) bond length is 3.19 Å. Both Ba(2)-F(1) bond lengths are 2.77 Å. Both Ba(2)-F(2) bond lengths are 3.27 Å. Both Ba(2)-F(3) bond lengths are 2.85 Å. Both Ba(2)-F(4) bond lengths are 2.78 Å. Both Ba(2)-F(5) bond lengths are 2.95 Å. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to one O(1), one F(1), one F(2), one F(3), one F(4), one F(6), one F(7), one F(8), and two equivalent F(5) atoms. The Ba(3)-O(1) bond length is 2.98 Å. The Ba(3)-F(1) bond length is 2.65 Å. The Ba(3)-F(2) bond length is 2.72 Å. The Ba(3)-F(3) bond length is 2.72 Å. The Ba(3)-F(4) bond length is 2.97 Å. The Ba(3)-F(6) bond length is 2.61 Å. The Ba(3)-F(7) bond length is 3.27 Å. The Ba(3)-F(8) bond length is 3.07 Å. There is one shorter (2.71 Å) and one longer (2.76 Å) Ba(3)-F(5) bond length. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(8), one F(9), two equivalent F(5), and two equivalent F(7) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 38°. The Fe(1)-F(8) bond length is 1.96 Å. The Fe(1)-F(9) bond length is 1.93 Å. Both Fe(1)-F(5) bond lengths are 1.96 Å. Both Fe(1)-F(7) bond lengths are 1.95 Å. In the second Fe site, Fe(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(6), and one F(7) atom to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 38°. The Fe(2)-F(1) bond length is 1.94 Å. The Fe(2)-F(2) bond length is 1.92 Å. The Fe(2)-F(3) bond length is 1.94 Å. The Fe(2)-F(4) bond length is 1.99 Å. The Fe(2)-F(6) bond length is 1.92 Å. The Fe(2)-F(7) bond length is 2.01 Å. O(1) is bonded in a water-like geometry to two equivalent Ba(3) atoms. There are nine inequivalent F sites. In the first F site, F(2) is bonded in a 1-coordinate geometry to one Ba(2), one Ba(3), and one Fe(2) atom. In the second F site, F(8) is bonded in a distorted single-bond geometry to one Ba(2), two equivalent Ba(3), and one Fe(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to one Ba(2), one Ba(3), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), one Ba(3), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Ba(2), two equivalent Ba(3), and one Fe(1) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Ba(1), one Ba(3), and one Fe(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Ba(3), one Fe(1), and one Fe(2) atom. In the eighth F site, F(9) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one Fe(1) atom. In the ninth F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Ba(2), one Ba(3), and one Fe(2) atom.