K2Zr3OF12 crystallizes in the trigonal R-3m space group. There are three inequivalent K sites. In the first K site, K(1) is bonded to six equivalent F(2) and six equivalent F(3) atoms to form face-sharing KF12 cuboctahedra. In the second K site, K(2) is bonded to six equivalent F(1) and six equivalent F(4) atoms to form distorted corner-sharing KF12 cuboctahedra. The corner-sharing octahedral tilt angles are 66°. In the third K site, K(3) is bonded to three equivalent F(2) and three equivalent F(4) atoms to form a mixture of corner and face-sharing KF6 octahedra. Zr(1) is bonded in a 8-coordinate geometry to one O(1), one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. O(1) is bonded in a trigonal planar geometry to three equivalent Zr(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one K(2) and two equivalent Zr(1) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one K(1), one K(3), and two equivalent Zr(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one K(1) and two equivalent Zr(1) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one K(2), one K(3), and one Zr(1) atom.
K2Zr3OF12 crystallizes in the trigonal R-3m space group. There are three inequivalent K sites. In the first K site, K(1) is bonded to six equivalent F(2) and six equivalent F(3) atoms to form face-sharing KF12 cuboctahedra. All K(1)-F(2) bond lengths are 3.15 Å. All K(1)-F(3) bond lengths are 2.74 Å. In the second K site, K(2) is bonded to six equivalent F(1) and six equivalent F(4) atoms to form distorted corner-sharing KF12 cuboctahedra. The corner-sharing octahedral tilt angles are 66°. All K(2)-F(1) bond lengths are 3.10 Å. All K(2)-F(4) bond lengths are 2.75 Å. In the third K site, K(3) is bonded to three equivalent F(2) and three equivalent F(4) atoms to form a mixture of corner and face-sharing KF6 octahedra. All K(3)-F(2) bond lengths are 2.84 Å. All K(3)-F(4) bond lengths are 2.72 Å. Zr(1) is bonded in a 8-coordinate geometry to one O(1), one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. The Zr(1)-O(1) bond length is 2.09 Å. The Zr(1)-F(4) bond length is 2.02 Å. Both Zr(1)-F(1) bond lengths are 2.18 Å. Both Zr(1)-F(2) bond lengths are 2.24 Å. Both Zr(1)-F(3) bond lengths are 2.18 Å. O(1) is bonded in a trigonal planar geometry to three equivalent Zr(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one K(2) and two equivalent Zr(1) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one K(1), one K(3), and two equivalent Zr(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one K(1) and two equivalent Zr(1) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one K(2), one K(3), and one Zr(1) atom.