Cs3AuGe4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 5-coordinate geometry to one Au(1), two equivalent Ge(1), and two equivalent Ge(2) atoms. In the second Cs site, Cs(2) is bonded to two equivalent Au(1) and four equivalent Ge(1) atoms to form a mixture of distorted edge and corner-sharing CsGe4Au2 octahedra. The corner-sharing octahedral tilt angles are 25°. Au(1) is bonded in a 8-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), two equivalent Ge(1), and two equivalent Ge(2) atoms. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Au(1) atom. In the second Ge site, Ge(2) is bonded in a 1-coordinate geometry to two equivalent Cs(1) and one Au(1) atom.
Cs3AuGe4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 5-coordinate geometry to one Au(1), two equivalent Ge(1), and two equivalent Ge(2) atoms. The Cs(1)-Au(1) bond length is 3.62 Å. Both Cs(1)-Ge(1) bond lengths are 3.87 Å. There is one shorter (3.70 Å) and one longer (3.79 Å) Cs(1)-Ge(2) bond length. In the second Cs site, Cs(2) is bonded to two equivalent Au(1) and four equivalent Ge(1) atoms to form a mixture of distorted edge and corner-sharing CsGe4Au2 octahedra. The corner-sharing octahedral tilt angles are 25°. Both Cs(2)-Au(1) bond lengths are 3.73 Å. There are two shorter (3.82 Å) and two longer (3.84 Å) Cs(2)-Ge(1) bond lengths. Au(1) is bonded in a 8-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), two equivalent Ge(1), and two equivalent Ge(2) atoms. Both Au(1)-Ge(1) bond lengths are 2.63 Å. Both Au(1)-Ge(2) bond lengths are 2.62 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Au(1) atom. In the second Ge site, Ge(2) is bonded in a 1-coordinate geometry to two equivalent Cs(1) and one Au(1) atom.