Ge19Sb4(I)4 crystallizes in the cubic P-43n space group. The structure consists of eight hydriodic acid atoms inside a Ge19Sb4 framework. In the Ge19Sb4 framework, there are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to three equivalent Ge(2) and one Sb(1) atom to form distorted GeGe3Sb tetrahedra that share corners with three equivalent Ge(3)Ge4 tetrahedra, corners with three equivalent Sb(1)Ge4 tetrahedra, and corners with six equivalent Ge(2)Ge3Sb tetrahedra. In the second Ge site, Ge(2) is bonded to one Ge(1), one Ge(2), one Ge(3), and one Sb(1) atom to form GeGe3Sb tetrahedra that share  a cornercorner with one Ge(3)Ge4 tetrahedra, corners with two equivalent Ge(1)Ge3Sb tetrahedra, corners with two equivalent Sb(1)Ge4 tetrahedra, and corners with seven equivalent Ge(2)Ge3Sb tetrahedra. In the third Ge site, Ge(3) is bonded to four equivalent Ge(2) atoms to form GeGe4 tetrahedra that share corners with four equivalent Ge(1)Ge3Sb tetrahedra, corners with four equivalent Ge(2)Ge3Sb tetrahedra, and corners with four equivalent Sb(1)Ge4 tetrahedra. Sb(1) is bonded to one Ge(1) and three equivalent Ge(2) atoms to form SbGe4 tetrahedra that share corners with three equivalent Ge(1)Ge3Sb tetrahedra, corners with three equivalent Ge(3)Ge4 tetrahedra, and corners with six equivalent Ge(2)Ge3Sb tetrahedra.
Ge19Sb4(I)4 crystallizes in the cubic P-43n space group. The structure consists of eight hydriodic acid atoms inside a Ge19Sb4 framework. In the Ge19Sb4 framework, there are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to three equivalent Ge(2) and one Sb(1) atom to form distorted GeGe3Sb tetrahedra that share corners with three equivalent Ge(3)Ge4 tetrahedra, corners with three equivalent Sb(1)Ge4 tetrahedra, and corners with six equivalent Ge(2)Ge3Sb tetrahedra. All Ge(1)-Ge(2) bond lengths are 2.50 Å. The Ge(1)-Sb(1) bond length is 2.67 Å. In the second Ge site, Ge(2) is bonded to one Ge(1), one Ge(2), one Ge(3), and one Sb(1) atom to form GeGe3Sb tetrahedra that share  a cornercorner with one Ge(3)Ge4 tetrahedra, corners with two equivalent Ge(1)Ge3Sb tetrahedra, corners with two equivalent Sb(1)Ge4 tetrahedra, and corners with seven equivalent Ge(2)Ge3Sb tetrahedra. The Ge(2)-Ge(2) bond length is 2.56 Å. The Ge(2)-Ge(3) bond length is 2.55 Å. The Ge(2)-Sb(1) bond length is 2.71 Å. In the third Ge site, Ge(3) is bonded to four equivalent Ge(2) atoms to form GeGe4 tetrahedra that share corners with four equivalent Ge(1)Ge3Sb tetrahedra, corners with four equivalent Ge(2)Ge3Sb tetrahedra, and corners with four equivalent Sb(1)Ge4 tetrahedra. Sb(1) is bonded to one Ge(1) and three equivalent Ge(2) atoms to form SbGe4 tetrahedra that share corners with three equivalent Ge(1)Ge3Sb tetrahedra, corners with three equivalent Ge(3)Ge4 tetrahedra, and corners with six equivalent Ge(2)Ge3Sb tetrahedra.