Cs6Hf5(O2F13)2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one O(1), one F(3), two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(4), two equivalent F(5), and two equivalent F(7) atoms. In the third Cs site, Cs(3) is bonded in a 9-coordinate geometry to one F(8), two equivalent F(1), two equivalent F(3), two equivalent F(6), and two equivalent F(7) atoms. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 8-coordinate geometry to one O(1), one F(3), two equivalent F(1), two equivalent F(2), and two equivalent F(7) atoms. In the second Hf site, Hf(2) is bonded in a 7-coordinate geometry to one O(2), two equivalent F(1), two equivalent F(5), and two equivalent F(6) atoms. In the third Hf site, Hf(3) is bonded in an octahedral geometry to two equivalent F(8) and four equivalent F(4) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Cs(1) and one Hf(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Hf(2) atom. There are eight inequivalent F sites. In the first F site, F(2) is bonded in a water-like geometry to two equivalent Hf(1) atoms. In the second F site, F(3) is bonded in a single-bond geometry to one Cs(1), two equivalent Cs(3), and one Hf(1) atom. In the third F site, F(4) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), and one Hf(3) atom. In the fourth F site, F(5) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), and one Hf(2) atom. In the fifth F site, F(6) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(3), and one Hf(2) atom. In the sixth F site, F(7) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(3), and one Hf(1) atom. In the seventh F site, F(8) is bonded in a distorted linear geometry to one Cs(3) and one Hf(3) atom. In the eighth F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Cs(2), one Cs(3), one Hf(1), and one Hf(2) atom.
Cs6Hf5(O2F13)2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one O(1), one F(3), two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms. The Cs(1)-O(1) bond length is 3.35 Å. The Cs(1)-F(3) bond length is 3.43 Å. Both Cs(1)-F(4) bond lengths are 3.09 Å. Both Cs(1)-F(5) bond lengths are 3.25 Å. Both Cs(1)-F(6) bond lengths are 3.24 Å. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(4), two equivalent F(5), and two equivalent F(7) atoms. Both Cs(2)-F(1) bond lengths are 3.22 Å. Both Cs(2)-F(4) bond lengths are 2.98 Å. Both Cs(2)-F(5) bond lengths are 3.28 Å. Both Cs(2)-F(7) bond lengths are 3.07 Å. In the third Cs site, Cs(3) is bonded in a 9-coordinate geometry to one F(8), two equivalent F(1), two equivalent F(3), two equivalent F(6), and two equivalent F(7) atoms. The Cs(3)-F(8) bond length is 2.87 Å. Both Cs(3)-F(1) bond lengths are 3.36 Å. Both Cs(3)-F(3) bond lengths are 3.51 Å. Both Cs(3)-F(6) bond lengths are 3.19 Å. Both Cs(3)-F(7) bond lengths are 3.12 Å. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 8-coordinate geometry to one O(1), one F(3), two equivalent F(1), two equivalent F(2), and two equivalent F(7) atoms. The Hf(1)-O(1) bond length is 2.26 Å. The Hf(1)-F(3) bond length is 2.05 Å. Both Hf(1)-F(1) bond lengths are 2.20 Å. There is one shorter (2.10 Å) and one longer (2.19 Å) Hf(1)-F(2) bond length. Both Hf(1)-F(7) bond lengths are 1.99 Å. In the second Hf site, Hf(2) is bonded in a 7-coordinate geometry to one O(2), two equivalent F(1), two equivalent F(5), and two equivalent F(6) atoms. The Hf(2)-O(2) bond length is 2.25 Å. Both Hf(2)-F(1) bond lengths are 2.12 Å. Both Hf(2)-F(5) bond lengths are 2.00 Å. Both Hf(2)-F(6) bond lengths are 2.02 Å. In the third Hf site, Hf(3) is bonded in an octahedral geometry to two equivalent F(8) and four equivalent F(4) atoms. Both Hf(3)-F(8) bond lengths are 2.01 Å. All Hf(3)-F(4) bond lengths are 2.02 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Cs(1) and one Hf(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Hf(2) atom. There are eight inequivalent F sites. In the first F site, F(2) is bonded in a water-like geometry to two equivalent Hf(1) atoms. In the second F site, F(3) is bonded in a single-bond geometry to one Cs(1), two equivalent Cs(3), and one Hf(1) atom. In the third F site, F(4) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), and one Hf(3) atom. In the fourth F site, F(5) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), and one Hf(2) atom. In the fifth F site, F(6) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(3), and one Hf(2) atom. In the sixth F site, F(7) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(3), and one Hf(1) atom. In the seventh F site, F(8) is bonded in a distorted linear geometry to one Cs(3) and one Hf(3) atom. In the eighth F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Cs(2), one Cs(3), one Hf(1), and one Hf(2) atom.