K5V3F14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to two equivalent F(1) and four equivalent F(3) atoms. In the second K site, K(2) is bonded in a body-centered cubic geometry to eight equivalent F(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 33°. In the second V site, V(2) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 33°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to four equivalent K(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one K(2), two equivalent K(1), and one V(2) atom.
K5V3F14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to two equivalent F(1) and four equivalent F(3) atoms. Both K(1)-F(1) bond lengths are 2.96 Å. There are two shorter (2.61 Å) and two longer (2.62 Å) K(1)-F(3) bond lengths. In the second K site, K(2) is bonded in a body-centered cubic geometry to eight equivalent F(3) atoms. All K(2)-F(3) bond lengths are 2.89 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 33°. Both V(1)-F(1) bond lengths are 1.96 Å. All V(1)-F(2) bond lengths are 2.01 Å. In the second V site, V(2) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles are 33°. Both V(2)-F(2) bond lengths are 2.05 Å. All V(2)-F(3) bond lengths are 1.95 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to four equivalent K(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one K(2), two equivalent K(1), and one V(2) atom.