Li2SiF6 is Hydrophilite-derived structured and crystallizes in the trigonal P321 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Si(1)F6 octahedra, corners with six equivalent Li(2)F6 octahedra, and edges with two equivalent Si(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with four equivalent Si(2)F6 octahedra, corners with six equivalent Li(1)F6 octahedra, and  an edgeedge with one Si(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-58°. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to six equivalent F(1) atoms to form SiF6 octahedra that share corners with six equivalent Li(1)F6 octahedra and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 48°. In the second Si site, Si(2) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form SiF6 octahedra that share corners with six equivalent Li(2)F6 octahedra and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-47°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Si(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Si(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Si(2) atom.
Li2SiF6 is Hydrophilite-derived structured and crystallizes in the trigonal P321 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Si(1)F6 octahedra, corners with six equivalent Li(2)F6 octahedra, and edges with two equivalent Si(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. Both Li(1)-F(1) bond lengths are 1.91 Å. Both Li(1)-F(2) bond lengths are 2.07 Å. Both Li(1)-F(3) bond lengths are 1.98 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with four equivalent Si(2)F6 octahedra, corners with six equivalent Li(1)F6 octahedra, and  an edgeedge with one Si(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-58°. Both Li(2)-F(1) bond lengths are 2.12 Å. Both Li(2)-F(2) bond lengths are 1.95 Å. Both Li(2)-F(3) bond lengths are 2.07 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to six equivalent F(1) atoms to form SiF6 octahedra that share corners with six equivalent Li(1)F6 octahedra and edges with three equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles are 48°. All Si(1)-F(1) bond lengths are 1.69 Å. In the second Si site, Si(2) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form SiF6 octahedra that share corners with six equivalent Li(2)F6 octahedra and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-47°. All Si(2)-F(2) bond lengths are 1.70 Å. All Si(2)-F(3) bond lengths are 1.70 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Si(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Si(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one Si(2) atom.