Na3LiTi2F12 crystallizes in the tetragonal P-42_1c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Ti(1)F6 octahedra, and  an edgeedge with one Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to four equivalent F(1) and four equivalent F(3) atoms. Li(1) is bonded to four equivalent F(3) atoms to form LiF4 tetrahedra that share corners with four equivalent Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles are 51°. 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 four equivalent Na(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate 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 two equivalent Na(1) and one Ti(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Na(2), one Li(1), and one Ti(1) atom.
Na3LiTi2F12 crystallizes in the tetragonal P-42_1c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Ti(1)F6 octahedra, and  an edgeedge with one Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. Both Na(1)-F(1) bond lengths are 2.31 Å. There are two shorter (2.43 Å) and two longer (2.47 Å) Na(1)-F(2) bond lengths. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to four equivalent F(1) and four equivalent F(3) atoms. All Na(2)-F(1) bond lengths are 2.65 Å. All Na(2)-F(3) bond lengths are 2.35 Å. Li(1) is bonded to four equivalent F(3) atoms to form LiF4 tetrahedra that share corners with four equivalent Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles are 51°. All Li(1)-F(3) bond lengths are 1.94 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 four equivalent Na(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. Both Ti(1)-F(1) bond lengths are 1.88 Å. Both Ti(1)-F(2) bond lengths are 1.88 Å. Both Ti(1)-F(3) bond lengths are 1.93 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate 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 two equivalent Na(1) and one Ti(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Na(2), one Li(1), and one Ti(1) atom.