Li2TiF6 is Rutile-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Ti(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. Ti(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form TiF6 octahedra that share corners with eight equivalent Li(1)F6 octahedra and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 46°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Ti(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Ti(1) atom.
Li2TiF6 is Rutile-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Ti(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Ti(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. Both Li(1)-F(1) bond lengths are 1.98 Å. There are two shorter (1.98 Å) and two longer (2.06 Å) Li(1)-F(2) bond lengths. Ti(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form TiF6 octahedra that share corners with eight equivalent Li(1)F6 octahedra and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both Ti(1)-F(1) bond lengths are 1.88 Å. All Ti(1)-F(2) bond lengths are 1.88 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Ti(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Ti(1) atom.