Li2GeF6 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 Ge(2)F6 octahedra, corners with six equivalent Li(2)F6 octahedra, and edges with two equivalent Ge(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. 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 Ge(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra, and  an edgeedge with one Ge(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form GeF6 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 46-50°. In the second Ge site, Ge(2) is bonded to six equivalent F(1) atoms to form GeF6 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 51°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Ge(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Ge(1) 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 Ge(1) atom.
Li2GeF6 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 Ge(2)F6 octahedra, corners with six equivalent Li(2)F6 octahedra, and edges with two equivalent Ge(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. Both Li(1)-F(1) bond lengths are 1.93 Å. Both Li(1)-F(2) bond lengths are 2.00 Å. Both Li(1)-F(3) bond lengths are 2.09 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 Ge(1)F6 octahedra, corners with six equivalent Li(1)F6 octahedra, and  an edgeedge with one Ge(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. Both Li(2)-F(1) bond lengths are 2.12 Å. Both Li(2)-F(2) bond lengths are 2.07 Å. Both Li(2)-F(3) bond lengths are 1.96 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to three equivalent F(2) and three equivalent F(3) atoms to form GeF6 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 46-50°. All Ge(1)-F(2) bond lengths are 1.81 Å. All Ge(1)-F(3) bond lengths are 1.81 Å. In the second Ge site, Ge(2) is bonded to six equivalent F(1) atoms to form GeF6 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 51°. All Ge(2)-F(1) bond lengths are 1.81 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Ge(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one Li(2), and one Ge(1) 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 Ge(1) atom.