Na2TiF6 is Hydrophilite-derived structured and crystallizes in the trigonal P321 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with four equivalent Ti(1)F6 octahedra, corners with six equivalent Na(2)F6 octahedra, and  an edgeedge with one Ti(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. In the second Na site, Na(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with two equivalent Ti(2)F6 octahedra, corners with six equivalent Na(1)F6 octahedra, and edges with two equivalent Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent F(1) and three equivalent F(3) atoms to form TiF6 octahedra that share corners with six equivalent Na(1)F6 octahedra and edges with three equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. In the second Ti site, Ti(2) is bonded to six equivalent F(2) atoms to form TiF6 octahedra that share corners with six equivalent Na(2)F6 octahedra and edges with three equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles are 52°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Ti(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Ti(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Ti(1) atom.
Na2TiF6 is Hydrophilite-derived structured and crystallizes in the trigonal P321 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with four equivalent Ti(1)F6 octahedra, corners with six equivalent Na(2)F6 octahedra, and  an edgeedge with one Ti(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. Both Na(1)-F(1) bond lengths are 2.30 Å. Both Na(1)-F(2) bond lengths are 2.36 Å. Both Na(1)-F(3) bond lengths are 2.27 Å. In the second Na site, Na(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with two equivalent Ti(2)F6 octahedra, corners with six equivalent Na(1)F6 octahedra, and edges with two equivalent Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. Both Na(2)-F(1) bond lengths are 2.29 Å. Both Na(2)-F(2) bond lengths are 2.20 Å. Both Na(2)-F(3) bond lengths are 2.30 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent F(1) and three equivalent F(3) atoms to form TiF6 octahedra that share corners with six equivalent Na(1)F6 octahedra and edges with three equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-47°. All Ti(1)-F(1) bond lengths are 1.88 Å. All Ti(1)-F(3) bond lengths are 1.88 Å. In the second Ti site, Ti(2) is bonded to six equivalent F(2) atoms to form TiF6 octahedra that share corners with six equivalent Na(2)F6 octahedra and edges with three equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles are 52°. All Ti(2)-F(2) bond lengths are 1.88 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Ti(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Ti(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one Ti(1) atom.