K3Zr2NF12 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 6-coordinate geometry to one F(6), one F(7), two equivalent F(1), and two equivalent F(2) atoms. In the second K site, K(2) is bonded in a 8-coordinate geometry to one F(3), one F(7), two equivalent F(2), two equivalent F(4), and two equivalent F(8) atoms. In the third K site, K(3) is bonded in a 11-coordinate geometry to one N(1), one F(5), one F(7), two equivalent F(2), two equivalent F(8), and four equivalent F(1) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(5), and two equivalent F(7) atoms. In the second Zr site, Zr(2) is bonded to two equivalent F(4), two equivalent F(6), and two equivalent F(8) atoms to form distorted edge-sharing ZrF6 pentagonal pyramids. N(1) is bonded in a single-bond geometry to one K(3) and one F(3) atom. There are eight inequivalent F sites. In the first F site, F(3) is bonded in a single-bond geometry to one K(2) and one N(1) atom. In the second F site, F(4) is bonded in a bent 150 degrees geometry to one K(2) and one Zr(2) atom. In the third F site, F(5) is bonded in a trigonal non-coplanar geometry to one K(3) and two equivalent Zr(1) atoms. In the fourth F site, F(6) is bonded in a trigonal planar geometry to one K(1) and two equivalent Zr(2) atoms. In the fifth F site, F(7) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), and two equivalent Zr(1) atoms. In the sixth F site, F(8) is bonded in a distorted single-bond geometry to one K(2), one K(3), and one Zr(2) atom. In the seventh F site, F(1) is bonded in a 2-coordinate geometry to one K(1), two equivalent K(3), and one Zr(1) atom. In the eighth F site, F(2) is bonded in a 3-coordinate geometry to one K(1), one K(2), one K(3), and one Zr(1) atom.
K3Zr2NF12 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 6-coordinate geometry to one F(6), one F(7), two equivalent F(1), and two equivalent F(2) atoms. The K(1)-F(6) bond length is 2.72 Å. The K(1)-F(7) bond length is 3.00 Å. Both K(1)-F(1) bond lengths are 2.58 Å. Both K(1)-F(2) bond lengths are 2.65 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to one F(3), one F(7), two equivalent F(2), two equivalent F(4), and two equivalent F(8) atoms. The K(2)-F(3) bond length is 2.89 Å. The K(2)-F(7) bond length is 3.14 Å. Both K(2)-F(2) bond lengths are 2.65 Å. Both K(2)-F(4) bond lengths are 2.66 Å. Both K(2)-F(8) bond lengths are 2.83 Å. In the third K site, K(3) is bonded in a 11-coordinate geometry to one N(1), one F(5), one F(7), two equivalent F(2), two equivalent F(8), and four equivalent F(1) atoms. The K(3)-N(1) bond length is 3.35 Å. The K(3)-F(5) bond length is 2.59 Å. The K(3)-F(7) bond length is 2.71 Å. Both K(3)-F(2) bond lengths are 3.29 Å. Both K(3)-F(8) bond lengths are 2.90 Å. There are two shorter (2.97 Å) and two longer (3.20 Å) K(3)-F(1) bond lengths. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(5), and two equivalent F(7) atoms. Both Zr(1)-F(1) bond lengths are 2.05 Å. Both Zr(1)-F(2) bond lengths are 2.05 Å. Both Zr(1)-F(5) bond lengths are 2.32 Å. Both Zr(1)-F(7) bond lengths are 2.43 Å. In the second Zr site, Zr(2) is bonded to two equivalent F(4), two equivalent F(6), and two equivalent F(8) atoms to form distorted edge-sharing ZrF6 pentagonal pyramids. Both Zr(2)-F(4) bond lengths are 2.00 Å. Both Zr(2)-F(6) bond lengths are 2.16 Å. Both Zr(2)-F(8) bond lengths are 2.00 Å. N(1) is bonded in a single-bond geometry to one K(3) and one F(3) atom. The N(1)-F(3) bond length is 1.36 Å. There are eight inequivalent F sites. In the first F site, F(3) is bonded in a single-bond geometry to one K(2) and one N(1) atom. In the second F site, F(4) is bonded in a bent 150 degrees geometry to one K(2) and one Zr(2) atom. In the third F site, F(5) is bonded in a trigonal non-coplanar geometry to one K(3) and two equivalent Zr(1) atoms. In the fourth F site, F(6) is bonded in a trigonal planar geometry to one K(1) and two equivalent Zr(2) atoms. In the fifth F site, F(7) is bonded in a 5-coordinate geometry to one K(1), one K(2), one K(3), and two equivalent Zr(1) atoms. In the sixth F site, F(8) is bonded in a distorted single-bond geometry to one K(2), one K(3), and one Zr(2) atom. In the seventh F site, F(1) is bonded in a 2-coordinate geometry to one K(1), two equivalent K(3), and one Zr(1) atom. In the eighth F site, F(2) is bonded in a 3-coordinate geometry to one K(1), one K(2), one K(3), and one Zr(1) atom.