KNb3F9 crystallizes in the triclinic P1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to one F(12), one F(13), one F(15), one F(3), one F(5), and one F(8) atom. In the second K site, K(2) is bonded in a 6-coordinate geometry to one F(11), one F(14), one F(16), one F(4), one F(6), and one F(7) atom. There are six inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one F(11), one F(12), one F(15), one F(17), one F(2), and one F(6) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 21-45°. In the second Nb site, Nb(2) is bonded to one F(1), one F(11), one F(12), one F(16), one F(18), and one F(5) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 20-45°. In the third Nb site, Nb(3) is bonded to one F(10), one F(13), one F(14), one F(3), one F(4), and one F(9) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 15-45°. In the fourth Nb site, Nb(4) is bonded to one F(10), one F(15), one F(16), one F(5), one F(6), and one F(9) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 15-45°. In the fifth Nb site, Nb(5) is bonded to one F(1), one F(14), one F(18), one F(3), one F(7), and one F(8) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 20-44°. In the sixth Nb site, Nb(6) is bonded to one F(13), one F(17), one F(2), one F(4), one F(7), and one F(8) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 21-45°. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Nb(2) and one Nb(5) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Nb(1) and one Nb(6) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to one K(1), one Nb(3), and one Nb(5) atom. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one K(2), one Nb(3), and one Nb(6) atom. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to one K(1), one Nb(2), and one Nb(4) atom. In the sixth F site, F(6) is bonded in a 2-coordinate geometry to one K(2), one Nb(1), and one Nb(4) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one K(2), one Nb(5), and one Nb(6) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one K(1), one Nb(5), and one Nb(6) atom. In the ninth F site, F(9) is bonded in a linear geometry to one Nb(3) and one Nb(4) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Nb(3) and one Nb(4) atom. In the eleventh F site, F(11) is bonded in a 2-coordinate geometry to one K(2), one Nb(1), and one Nb(2) atom. In the twelfth F site, F(12) is bonded in a 3-coordinate geometry to one K(1), one Nb(1), and one Nb(2) atom. In the thirteenth F site, F(13) is bonded in a 2-coordinate geometry to one K(1), one Nb(3), and one Nb(6) atom. In the fourteenth F site, F(14) is bonded in a 3-coordinate geometry to one K(2), one Nb(3), and one Nb(5) atom. In the fifteenth F site, F(15) is bonded in a 3-coordinate geometry to one K(1), one Nb(1), and one Nb(4) atom. In the sixteenth F site, F(16) is bonded in a 2-coordinate geometry to one K(2), one Nb(2), and one Nb(4) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one Nb(1) and one Nb(6) atom. In the eighteenth F site, F(18) is bonded in a bent 150 degrees geometry to one Nb(2) and one Nb(5) atom.
KNb3F9 crystallizes in the triclinic P1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to one F(12), one F(13), one F(15), one F(3), one F(5), and one F(8) atom. The K(1)-F(12) bond length is 3.08 Å. The K(1)-F(13) bond length is 3.19 Å. The K(1)-F(15) bond length is 3.13 Å. The K(1)-F(3) bond length is 3.22 Å. The K(1)-F(5) bond length is 3.18 Å. The K(1)-F(8) bond length is 3.06 Å. In the second K site, K(2) is bonded in a 6-coordinate geometry to one F(11), one F(14), one F(16), one F(4), one F(6), and one F(7) atom. The K(2)-F(11) bond length is 3.14 Å. The K(2)-F(14) bond length is 3.13 Å. The K(2)-F(16) bond length is 3.22 Å. The K(2)-F(4) bond length is 3.29 Å. The K(2)-F(6) bond length is 3.20 Å. The K(2)-F(7) bond length is 3.09 Å. There are six inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one F(11), one F(12), one F(15), one F(17), one F(2), and one F(6) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 21-45°. The Nb(1)-F(11) bond length is 2.16 Å. The Nb(1)-F(12) bond length is 2.15 Å. The Nb(1)-F(15) bond length is 2.17 Å. The Nb(1)-F(17) bond length is 2.13 Å. The Nb(1)-F(2) bond length is 2.12 Å. The Nb(1)-F(6) bond length is 2.16 Å. In the second Nb site, Nb(2) is bonded to one F(1), one F(11), one F(12), one F(16), one F(18), and one F(5) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 20-45°. The Nb(2)-F(1) bond length is 2.12 Å. The Nb(2)-F(11) bond length is 2.15 Å. The Nb(2)-F(12) bond length is 2.15 Å. The Nb(2)-F(16) bond length is 2.16 Å. The Nb(2)-F(18) bond length is 2.12 Å. The Nb(2)-F(5) bond length is 2.17 Å. In the third Nb site, Nb(3) is bonded to one F(10), one F(13), one F(14), one F(3), one F(4), and one F(9) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 15-45°. The Nb(3)-F(10) bond length is 2.10 Å. The Nb(3)-F(13) bond length is 2.16 Å. The Nb(3)-F(14) bond length is 2.16 Å. The Nb(3)-F(3) bond length is 2.16 Å. The Nb(3)-F(4) bond length is 2.15 Å. The Nb(3)-F(9) bond length is 2.10 Å. In the fourth Nb site, Nb(4) is bonded to one F(10), one F(15), one F(16), one F(5), one F(6), and one F(9) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 15-45°. The Nb(4)-F(10) bond length is 2.11 Å. The Nb(4)-F(15) bond length is 2.17 Å. The Nb(4)-F(16) bond length is 2.16 Å. The Nb(4)-F(5) bond length is 2.17 Å. The Nb(4)-F(6) bond length is 2.15 Å. The Nb(4)-F(9) bond length is 2.10 Å. In the fifth Nb site, Nb(5) is bonded to one F(1), one F(14), one F(18), one F(3), one F(7), and one F(8) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 20-44°. The Nb(5)-F(1) bond length is 2.12 Å. The Nb(5)-F(14) bond length is 2.16 Å. The Nb(5)-F(18) bond length is 2.12 Å. The Nb(5)-F(3) bond length is 2.16 Å. The Nb(5)-F(7) bond length is 2.16 Å. The Nb(5)-F(8) bond length is 2.15 Å. In the sixth Nb site, Nb(6) is bonded to one F(13), one F(17), one F(2), one F(4), one F(7), and one F(8) atom to form corner-sharing NbF6 octahedra. The corner-sharing octahedral tilt angles range from 21-45°. The Nb(6)-F(13) bond length is 2.16 Å. The Nb(6)-F(17) bond length is 2.12 Å. The Nb(6)-F(2) bond length is 2.12 Å. The Nb(6)-F(4) bond length is 2.15 Å. The Nb(6)-F(7) bond length is 2.16 Å. The Nb(6)-F(8) bond length is 2.16 Å. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Nb(2) and one Nb(5) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Nb(1) and one Nb(6) atom. In the third F site, F(3) is bonded in a 2-coordinate geometry to one K(1), one Nb(3), and one Nb(5) atom. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one K(2), one Nb(3), and one Nb(6) atom. In the fifth F site, F(5) is bonded in a 2-coordinate geometry to one K(1), one Nb(2), and one Nb(4) atom. In the sixth F site, F(6) is bonded in a 2-coordinate geometry to one K(2), one Nb(1), and one Nb(4) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one K(2), one Nb(5), and one Nb(6) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one K(1), one Nb(5), and one Nb(6) atom. In the ninth F site, F(9) is bonded in a linear geometry to one Nb(3) and one Nb(4) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Nb(3) and one Nb(4) atom. In the eleventh F site, F(11) is bonded in a 2-coordinate geometry to one K(2), one Nb(1), and one Nb(2) atom. In the twelfth F site, F(12) is bonded in a 3-coordinate geometry to one K(1), one Nb(1), and one Nb(2) atom. In the thirteenth F site, F(13) is bonded in a 2-coordinate geometry to one K(1), one Nb(3), and one Nb(6) atom. In the fourteenth F site, F(14) is bonded in a 3-coordinate geometry to one K(2), one Nb(3), and one Nb(5) atom. In the fifteenth F site, F(15) is bonded in a 3-coordinate geometry to one K(1), one Nb(1), and one Nb(4) atom. In the sixteenth F site, F(16) is bonded in a 2-coordinate geometry to one K(2), one Nb(2), and one Nb(4) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one Nb(1) and one Nb(6) atom. In the eighteenth F site, F(18) is bonded in a bent 150 degrees geometry to one Nb(2) and one Nb(5) atom.