Na5Ti3F14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to eight equivalent F(3) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), and four equivalent F(3) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form corner-sharing TiF6 octahedra. The corner-sharing octahedral tilt angles are 33°. In the second Ti site, Ti(2) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form corner-sharing TiF6 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 Na(2) and one Ti(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Na(2), one Ti(1), and one Ti(2) atom. In the third F site, F(3) is bonded to one Na(1), two equivalent Na(2), and one Ti(2) atom to form a mixture of distorted corner and edge-sharing FNa3Ti trigonal pyramids.
Na5Ti3F14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to eight equivalent F(3) atoms. All Na(1)-F(3) bond lengths are 2.73 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), and four equivalent F(3) atoms. Both Na(2)-F(1) bond lengths are 2.79 Å. Both Na(2)-F(2) bond lengths are 2.89 Å. There are two shorter (2.32 Å) and two longer (2.39 Å) Na(2)-F(3) bond lengths. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form corner-sharing TiF6 octahedra. The corner-sharing octahedral tilt angles are 33°. Both Ti(1)-F(1) bond lengths are 1.95 Å. All Ti(1)-F(2) bond lengths are 1.97 Å. In the second Ti site, Ti(2) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form corner-sharing TiF6 octahedra. The corner-sharing octahedral tilt angles are 33°. Both Ti(2)-F(2) bond lengths are 1.99 Å. All Ti(2)-F(3) bond lengths are 1.98 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 Na(2) and one Ti(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Na(2), one Ti(1), and one Ti(2) atom. In the third F site, F(3) is bonded to one Na(1), two equivalent Na(2), and one Ti(2) atom to form a mixture of distorted corner and edge-sharing FNa3Ti trigonal pyramids.