Rb2GeF6 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form distorted RbF12 cuboctahedra that share corners with six equivalent Rb(1)F12 cuboctahedra, corners with three equivalent Ge(1)F6 octahedra, faces with two equivalent Rb(1)F12 cuboctahedra, faces with six equivalent Rb(2)F12 cuboctahedra, and faces with three equivalent Ge(1)F6 octahedra. The corner-sharing octahedral tilt angles are 16°. In the second Rb site, Rb(2) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form distorted RbF12 cuboctahedra that share corners with twelve equivalent Rb(2)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, and faces with four equivalent Ge(1)F6 octahedra. Ge(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form GeF6 octahedra that share corners with three equivalent Rb(1)F12 cuboctahedra, faces with three equivalent Rb(1)F12 cuboctahedra, and faces with four equivalent Rb(2)F12 cuboctahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one Ge(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one Ge(1) atom.
Rb2GeF6 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form distorted RbF12 cuboctahedra that share corners with six equivalent Rb(1)F12 cuboctahedra, corners with three equivalent Ge(1)F6 octahedra, faces with two equivalent Rb(1)F12 cuboctahedra, faces with six equivalent Rb(2)F12 cuboctahedra, and faces with three equivalent Ge(1)F6 octahedra. The corner-sharing octahedral tilt angles are 16°. All Rb(1)-F(1) bond lengths are 3.00 Å. There are three shorter (2.94 Å) and three longer (3.18 Å) Rb(1)-F(2) bond lengths. In the second Rb site, Rb(2) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form distorted RbF12 cuboctahedra that share corners with twelve equivalent Rb(2)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, and faces with four equivalent Ge(1)F6 octahedra. There are three shorter (2.91 Å) and three longer (2.99 Å) Rb(2)-F(1) bond lengths. All Rb(2)-F(2) bond lengths are 2.96 Å. Ge(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form GeF6 octahedra that share corners with three equivalent Rb(1)F12 cuboctahedra, faces with three equivalent Rb(1)F12 cuboctahedra, and faces with four equivalent Rb(2)F12 cuboctahedra. All Ge(1)-F(1) bond lengths are 1.82 Å. All Ge(1)-F(2) bond lengths are 1.81 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one Ge(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one Ge(1) atom.