Na3TiF8 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. In the second Na site, Na(2) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form NaF6 octahedra that share corners with four equivalent Ti(1)F6 octahedra and edges with two equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-56°. Ti(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form TiF6 octahedra that share corners with eight equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-56°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Na(2), and one Ti(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one Ti(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Ti(1) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Na(1) and two equivalent Na(2) atoms.
Na3TiF8 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. Both Na(1)-F(1) bond lengths are 2.74 Å. Both Na(1)-F(2) bond lengths are 2.40 Å. Both Na(1)-F(3) bond lengths are 2.69 Å. Both Na(1)-F(4) bond lengths are 2.30 Å. In the second Na site, Na(2) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form NaF6 octahedra that share corners with four equivalent Ti(1)F6 octahedra and edges with two equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-56°. The Na(2)-F(1) bond length is 2.15 Å. The Na(2)-F(2) bond length is 2.19 Å. Both Na(2)-F(3) bond lengths are 2.38 Å. Both Na(2)-F(4) bond lengths are 2.30 Å. Ti(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form TiF6 octahedra that share corners with eight equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-56°. Both Ti(1)-F(1) bond lengths are 1.85 Å. Both Ti(1)-F(2) bond lengths are 1.88 Å. Both Ti(1)-F(3) bond lengths are 1.89 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Na(2), and one Ti(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one Ti(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Ti(1) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Na(1) and two equivalent Na(2) atoms.