Ba6Zn7F26 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 12-coordinate geometry to one F(5), two equivalent F(6), two equivalent F(9), three equivalent F(3), and four equivalent F(8) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one F(1), one F(5), two equivalent F(4), two equivalent F(9), and four equivalent F(7) atoms. In the third Ba site, Ba(3) is bonded to one F(3), one F(4), two equivalent F(1), two equivalent F(7), two equivalent F(8), and four equivalent F(6) atoms to form distorted BaF12 cuboctahedra that share corners with two equivalent Ba(3)F12 cuboctahedra,  a faceface with one Ba(3)F12 cuboctahedra, faces with two equivalent Zn(2)F6 octahedra, faces with two equivalent Zn(3)F6 octahedra, and faces with two equivalent Zn(4)F6 octahedra. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent F(2), two equivalent F(5), and two equivalent F(9) atoms to form a mixture of corner and edge-sharing ZnF6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the second Zn site, Zn(2) is bonded to one F(3), one F(4), two equivalent F(6), and two equivalent F(9) atoms to form ZnF6 octahedra that share corners with two equivalent Zn(1)F6 octahedra, corners with two equivalent Zn(4)F6 octahedra, and faces with two equivalent Ba(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-54°. In the third Zn site, Zn(3) is bonded to one F(1), one F(2), two equivalent F(7), and two equivalent F(8) atoms to form distorted ZnF6 octahedra that share  a cornercorner with one Zn(4)F6 octahedra, corners with two equivalent Zn(1)F6 octahedra, and faces with two equivalent Ba(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 17-48°. In the fourth Zn site, Zn(4) is bonded to two equivalent F(1) and four equivalent F(6) atoms to form ZnF6 octahedra that share corners with two equivalent Zn(3)F6 octahedra, corners with four equivalent Zn(2)F6 octahedra, and faces with four equivalent Ba(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-17°. There are nine inequivalent F sites. In the first F site, F(4) is bonded in a 1-coordinate geometry to one Ba(3), two equivalent Ba(2), and one Zn(2) atom. In the second F site, F(5) is bonded in a distorted L-shaped geometry to one Ba(1), one Ba(2), and two equivalent Zn(1) atoms. In the third F site, F(6) is bonded in a 2-coordinate geometry to one Ba(1), two equivalent Ba(3), one Zn(2), and one Zn(4) atom. In the fourth F site, F(7) is bonded in a 4-coordinate geometry to one Ba(3), two equivalent Ba(2), and one Zn(3) atom. In the fifth F site, F(8) is bonded to one Ba(3), two equivalent Ba(1), and one Zn(3) atom to form distorted FBa3Zn tetrahedra that share corners with two equivalent F(8)Ba3Zn tetrahedra, corners with four equivalent F(9)Ba2Zn2 tetrahedra, and edges with three equivalent F(8)Ba3Zn tetrahedra. In the sixth F site, F(9) is bonded to one Ba(1), one Ba(2), one Zn(1), and one Zn(2) atom to form distorted FBa2Zn2 tetrahedra that share corners with two equivalent F(9)Ba2Zn2 tetrahedra, corners with four equivalent F(8)Ba3Zn tetrahedra, and  an edgeedge with one F(9)Ba2Zn2 tetrahedra. In the seventh F site, F(1) is bonded in a 5-coordinate geometry to one Ba(2), two equivalent Ba(3), one Zn(3), and one Zn(4) atom. In the eighth F site, F(2) is bonded in a distorted trigonal planar geometry to one Zn(3) and two equivalent Zn(1) atoms. In the ninth F site, F(3) is bonded in a distorted single-bond geometry to one Ba(3), three equivalent Ba(1), and one Zn(2) atom.
Ba6Zn7F26 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 12-coordinate geometry to one F(5), two equivalent F(6), two equivalent F(9), three equivalent F(3), and four equivalent F(8) atoms. The Ba(1)-F(5) bond length is 3.26 Å. Both Ba(1)-F(6) bond lengths are 3.14 Å. Both Ba(1)-F(9) bond lengths are 2.79 Å. There are two shorter (3.00 Å) and one longer (3.02 Å) Ba(1)-F(3) bond length. There are two shorter (2.66 Å) and two longer (2.78 Å) Ba(1)-F(8) bond lengths. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to one F(1), one F(5), two equivalent F(4), two equivalent F(9), and four equivalent F(7) atoms. The Ba(2)-F(1) bond length is 2.85 Å. The Ba(2)-F(5) bond length is 2.89 Å. Both Ba(2)-F(4) bond lengths are 3.04 Å. Both Ba(2)-F(9) bond lengths are 2.84 Å. There are two shorter (2.62 Å) and two longer (2.79 Å) Ba(2)-F(7) bond lengths. In the third Ba site, Ba(3) is bonded to one F(3), one F(4), two equivalent F(1), two equivalent F(7), two equivalent F(8), and four equivalent F(6) atoms to form distorted BaF12 cuboctahedra that share corners with two equivalent Ba(3)F12 cuboctahedra,  a faceface with one Ba(3)F12 cuboctahedra, faces with two equivalent Zn(2)F6 octahedra, faces with two equivalent Zn(3)F6 octahedra, and faces with two equivalent Zn(4)F6 octahedra. The Ba(3)-F(3) bond length is 2.87 Å. The Ba(3)-F(4) bond length is 2.64 Å. Both Ba(3)-F(1) bond lengths are 2.99 Å. Both Ba(3)-F(7) bond lengths are 2.73 Å. Both Ba(3)-F(8) bond lengths are 2.66 Å. There are two shorter (2.84 Å) and two longer (3.15 Å) Ba(3)-F(6) bond lengths. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent F(2), two equivalent F(5), and two equivalent F(9) atoms to form a mixture of corner and edge-sharing ZnF6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. Both Zn(1)-F(2) bond lengths are 2.04 Å. Both Zn(1)-F(5) bond lengths are 2.02 Å. Both Zn(1)-F(9) bond lengths are 2.02 Å. In the second Zn site, Zn(2) is bonded to one F(3), one F(4), two equivalent F(6), and two equivalent F(9) atoms to form ZnF6 octahedra that share corners with two equivalent Zn(1)F6 octahedra, corners with two equivalent Zn(4)F6 octahedra, and faces with two equivalent Ba(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-54°. The Zn(2)-F(3) bond length is 1.96 Å. The Zn(2)-F(4) bond length is 1.95 Å. Both Zn(2)-F(6) bond lengths are 2.13 Å. Both Zn(2)-F(9) bond lengths are 2.01 Å. In the third Zn site, Zn(3) is bonded to one F(1), one F(2), two equivalent F(7), and two equivalent F(8) atoms to form distorted ZnF6 octahedra that share  a cornercorner with one Zn(4)F6 octahedra, corners with two equivalent Zn(1)F6 octahedra, and faces with two equivalent Ba(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 17-48°. The Zn(3)-F(1) bond length is 2.28 Å. The Zn(3)-F(2) bond length is 2.01 Å. Both Zn(3)-F(7) bond lengths are 2.00 Å. Both Zn(3)-F(8) bond lengths are 2.01 Å. In the fourth Zn site, Zn(4) is bonded to two equivalent F(1) and four equivalent F(6) atoms to form ZnF6 octahedra that share corners with two equivalent Zn(3)F6 octahedra, corners with four equivalent Zn(2)F6 octahedra, and faces with four equivalent Ba(3)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-17°. Both Zn(4)-F(1) bond lengths are 1.98 Å. All Zn(4)-F(6) bond lengths are 2.04 Å. There are nine inequivalent F sites. In the first F site, F(4) is bonded in a 1-coordinate geometry to one Ba(3), two equivalent Ba(2), and one Zn(2) atom. In the second F site, F(5) is bonded in a distorted L-shaped geometry to one Ba(1), one Ba(2), and two equivalent Zn(1) atoms. In the third F site, F(6) is bonded in a 2-coordinate geometry to one Ba(1), two equivalent Ba(3), one Zn(2), and one Zn(4) atom. In the fourth F site, F(7) is bonded in a 4-coordinate geometry to one Ba(3), two equivalent Ba(2), and one Zn(3) atom. In the fifth F site, F(8) is bonded to one Ba(3), two equivalent Ba(1), and one Zn(3) atom to form distorted FBa3Zn tetrahedra that share corners with two equivalent F(8)Ba3Zn tetrahedra, corners with four equivalent F(9)Ba2Zn2 tetrahedra, and edges with three equivalent F(8)Ba3Zn tetrahedra. In the sixth F site, F(9) is bonded to one Ba(1), one Ba(2), one Zn(1), and one Zn(2) atom to form distorted FBa2Zn2 tetrahedra that share corners with two equivalent F(9)Ba2Zn2 tetrahedra, corners with four equivalent F(8)Ba3Zn tetrahedra, and  an edgeedge with one F(9)Ba2Zn2 tetrahedra. In the seventh F site, F(1) is bonded in a 5-coordinate geometry to one Ba(2), two equivalent Ba(3), one Zn(3), and one Zn(4) atom. In the eighth F site, F(2) is bonded in a distorted trigonal planar geometry to one Zn(3) and two equivalent Zn(1) atoms. In the ninth F site, F(3) is bonded in a distorted single-bond geometry to one Ba(3), three equivalent Ba(1), and one Zn(2) atom.