K2GeF6 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form distorted KF12 cuboctahedra that share corners with six equivalent K(1)F12 cuboctahedra, corners with three equivalent Ge(1)F6 octahedra, faces with two equivalent K(1)F12 cuboctahedra, faces with six equivalent K(2)F12 cuboctahedra, and faces with three equivalent Ge(1)F6 octahedra. The corner-sharing octahedral tilt angles are 17°. In the second K site, K(2) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form KF12 cuboctahedra that share corners with twelve equivalent K(2)F12 cuboctahedra, faces with six equivalent K(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 K(1)F12 cuboctahedra, faces with three equivalent K(1)F12 cuboctahedra, and faces with four equivalent K(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 K(1), two equivalent K(2), and one Ge(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent K(1), two equivalent K(2), and one Ge(1) atom.
K2GeF6 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form distorted KF12 cuboctahedra that share corners with six equivalent K(1)F12 cuboctahedra, corners with three equivalent Ge(1)F6 octahedra, faces with two equivalent K(1)F12 cuboctahedra, faces with six equivalent K(2)F12 cuboctahedra, and faces with three equivalent Ge(1)F6 octahedra. The corner-sharing octahedral tilt angles are 17°. All K(1)-F(1) bond lengths are 2.88 Å. There are three shorter (2.78 Å) and three longer (3.04 Å) K(1)-F(2) bond lengths. In the second K site, K(2) is bonded to six equivalent F(1) and six equivalent F(2) atoms to form KF12 cuboctahedra that share corners with twelve equivalent K(2)F12 cuboctahedra, faces with six equivalent K(1)F12 cuboctahedra, and faces with four equivalent Ge(1)F6 octahedra. There are three shorter (2.80 Å) and three longer (2.88 Å) K(2)-F(1) bond lengths. All K(2)-F(2) bond lengths are 2.85 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 K(1)F12 cuboctahedra, faces with three equivalent K(1)F12 cuboctahedra, and faces with four equivalent K(2)F12 cuboctahedra. All Ge(1)-F(1) bond lengths are 1.81 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 K(1), two equivalent K(2), and one Ge(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent K(1), two equivalent K(2), and one Ge(1) atom.