RbGeBiS4 crystallizes in the monoclinic P2_1/c space group. Rb(1) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms. Ge(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form GeS4 tetrahedra that share  a cornercorner with one Bi(1)S5 square pyramid and edges with two equivalent Bi(1)S5 square pyramids. Bi(1) is bonded to one S(1), one S(2), one S(3), and two equivalent S(4) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(1)S5 square pyramids,  a cornercorner with one Ge(1)S4 tetrahedra, and edges with two equivalent Ge(1)S4 tetrahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Rb(1), one Ge(1), and one Bi(1) atom. In the second S site, S(2) is bonded to three equivalent Rb(1), one Ge(1), and one Bi(1) atom to form a mixture of distorted corner and edge-sharing SRb3GeBi trigonal bipyramids. In the third S site, S(3) is bonded in a 2-coordinate geometry to two equivalent Rb(1), one Ge(1), and one Bi(1) atom. In the fourth S site, S(4) is bonded in a distorted see-saw-like geometry to one Rb(1), one Ge(1), and two equivalent Bi(1) atoms.
RbGeBiS4 crystallizes in the monoclinic P2_1/c space group. Rb(1) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms. The Rb(1)-S(4) bond length is 3.40 Å. There is one shorter (3.49 Å) and one longer (3.56 Å) Rb(1)-S(1) bond length. There is one shorter (3.70 Å) and one longer (3.71 Å) Rb(1)-S(3) bond length. There are a spread of Rb(1)-S(2) bond distances ranging from 3.43-3.67 Å. Ge(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form GeS4 tetrahedra that share  a cornercorner with one Bi(1)S5 square pyramid and edges with two equivalent Bi(1)S5 square pyramids. The Ge(1)-S(1) bond length is 2.21 Å. The Ge(1)-S(2) bond length is 2.22 Å. The Ge(1)-S(3) bond length is 2.24 Å. The Ge(1)-S(4) bond length is 2.26 Å. Bi(1) is bonded to one S(1), one S(2), one S(3), and two equivalent S(4) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(1)S5 square pyramids,  a cornercorner with one Ge(1)S4 tetrahedra, and edges with two equivalent Ge(1)S4 tetrahedra. The Bi(1)-S(1) bond length is 2.91 Å. The Bi(1)-S(2) bond length is 2.82 Å. The Bi(1)-S(3) bond length is 2.72 Å. There is one shorter (2.74 Å) and one longer (3.05 Å) Bi(1)-S(4) bond length. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Rb(1), one Ge(1), and one Bi(1) atom. In the second S site, S(2) is bonded to three equivalent Rb(1), one Ge(1), and one Bi(1) atom to form a mixture of distorted corner and edge-sharing SRb3GeBi trigonal bipyramids. In the third S site, S(3) is bonded in a 2-coordinate geometry to two equivalent Rb(1), one Ge(1), and one Bi(1) atom. In the fourth S site, S(4) is bonded in a distorted see-saw-like geometry to one Rb(1), one Ge(1), and two equivalent Bi(1) atoms.