K3Zr2S(O2F3)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one O(1), one F(1), two equivalent F(3), and four equivalent F(5) atoms. In the second K site, K(2) is bonded in a 8-coordinate geometry to one O(1), two equivalent O(2), one F(1), two equivalent F(5), and two equivalent F(6) atoms. In the third K site, K(3) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), two equivalent O(4), and two equivalent F(3) atoms. Zr(1) is bonded in a 8-coordinate geometry to one O(4), one F(1), one F(2), one F(3), one F(4), one F(5), and two equivalent F(6) atoms. S(1) is bonded in a tetrahedral geometry to one O(1), one O(3), and two equivalent O(2) atoms. There are four inequivalent O sites. In the first O site, O(4) is bonded in a distorted water-like geometry to one K(3) and one Zr(1) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one S(1) atom. In the third O site, O(2) is bonded in a distorted single-bond geometry to one K(2), one K(3), and one S(1) atom. In the fourth O site, O(3) is bonded in a distorted single-bond geometry to two equivalent K(3) and one S(1) atom. There are six inequivalent F sites. In the first F site, F(4) is bonded in a bent 120 degrees geometry to two equivalent Zr(1) atoms. In the second F site, F(5) is bonded in a 4-coordinate geometry to one K(2), two equivalent K(1), and one Zr(1) atom. In the third F site, F(1) is bonded in a tetrahedral geometry to one K(1), one K(2), and two equivalent Zr(1) atoms. In the fourth F site, F(2) is bonded in a linear geometry to two equivalent Zr(1) atoms. In the fifth F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one K(3), and one Zr(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to one K(2) and two equivalent Zr(1) atoms.
K3Zr2S(O2F3)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one O(1), one F(1), two equivalent F(3), and four equivalent F(5) atoms. The K(1)-O(1) bond length is 3.13 Å. The K(1)-F(1) bond length is 2.84 Å. Both K(1)-F(3) bond lengths are 2.77 Å. There are two shorter (2.64 Å) and two longer (3.21 Å) K(1)-F(5) bond lengths. In the second K site, K(2) is bonded in a 8-coordinate geometry to one O(1), two equivalent O(2), one F(1), two equivalent F(5), and two equivalent F(6) atoms. The K(2)-O(1) bond length is 2.85 Å. Both K(2)-O(2) bond lengths are 2.88 Å. The K(2)-F(1) bond length is 2.73 Å. Both K(2)-F(5) bond lengths are 3.02 Å. Both K(2)-F(6) bond lengths are 2.89 Å. In the third K site, K(3) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), two equivalent O(4), and two equivalent F(3) atoms. Both K(3)-O(2) bond lengths are 2.91 Å. Both K(3)-O(3) bond lengths are 2.94 Å. Both K(3)-O(4) bond lengths are 3.01 Å. Both K(3)-F(3) bond lengths are 2.77 Å. Zr(1) is bonded in a 8-coordinate geometry to one O(4), one F(1), one F(2), one F(3), one F(4), one F(5), and two equivalent F(6) atoms. The Zr(1)-O(4) bond length is 2.24 Å. The Zr(1)-F(1) bond length is 2.24 Å. The Zr(1)-F(2) bond length is 2.15 Å. The Zr(1)-F(3) bond length is 2.04 Å. The Zr(1)-F(4) bond length is 2.17 Å. The Zr(1)-F(5) bond length is 2.02 Å. There is one shorter (2.18 Å) and one longer (2.20 Å) Zr(1)-F(6) bond length. S(1) is bonded in a tetrahedral geometry to one O(1), one O(3), and two equivalent O(2) atoms. The S(1)-O(1) bond length is 1.49 Å. The S(1)-O(3) bond length is 1.48 Å. Both S(1)-O(2) bond lengths are 1.51 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded in a distorted water-like geometry to one K(3) and one Zr(1) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one S(1) atom. In the third O site, O(2) is bonded in a distorted single-bond geometry to one K(2), one K(3), and one S(1) atom. In the fourth O site, O(3) is bonded in a distorted single-bond geometry to two equivalent K(3) and one S(1) atom. There are six inequivalent F sites. In the first F site, F(4) is bonded in a bent 120 degrees geometry to two equivalent Zr(1) atoms. In the second F site, F(5) is bonded in a 4-coordinate geometry to one K(2), two equivalent K(1), and one Zr(1) atom. In the third F site, F(1) is bonded in a tetrahedral geometry to one K(1), one K(2), and two equivalent Zr(1) atoms. In the fourth F site, F(2) is bonded in a linear geometry to two equivalent Zr(1) atoms. In the fifth F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one K(3), and one Zr(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to one K(2) and two equivalent Zr(1) atoms.