The compound described by RbBi3S5 crystallizes in the orthorhombic Pnnm space group. Rb(1) is bonded in a 6-coordinate geometry to one S(1), one S(3), one S(6), two equivalent S(2), and two equivalent S(4) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(4), one S(5), two equivalent S(2), and two equivalent S(3) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(1)S6 octahedra, corners with four equivalent Bi(2)S5 square pyramids, edges with two equivalent Bi(1)S6 octahedra, edges with four equivalent Bi(3)S6 octahedra, and  an edgeedge with one Bi(2)S5 square pyramid. The corner-sharing octahedra are not tilted. In the second Bi site, Bi(2) is bonded to one S(1), two equivalent S(3), and two equivalent S(4) atoms to form BiS5 square pyramids that share corners with four equivalent Bi(1)S6 octahedra,  an edgeedge with one Bi(1)S6 octahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with two equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 1-75°. In the third Bi site, Bi(3) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(5) atoms to form BiS6 octahedra that share corners with two equivalent Bi(3)S6 octahedra, edges with three equivalent Bi(3)S6 octahedra, edges with four equivalent Bi(1)S6 octahedra, and edges with two equivalent Bi(2)S5 square pyramids. The corner-sharing octahedra are not tilted. There are six inequivalent S sites. In the first S site, S(5) is bonded to two equivalent Bi(1) and four equivalent Bi(3) atoms to form SBi6 octahedra that share corners with two equivalent S(4)Rb2Bi3 square pyramids, edges with two equivalent S(5)Bi6 octahedra, edges with four equivalent S(3)RbBi5 octahedra, and edges with four equivalent S(2)Rb2Bi3 square pyramids. In the second S site, S(6) is bonded in a square co-planar geometry to two equivalent Rb(1) and two equivalent S(1) atoms. In the third S site, S(1) is bonded in a 5-coordinate geometry to one Rb(1), one Bi(2), two equivalent Bi(3), and one S(6) atom. In the fourth S site, S(2) is bonded to two equivalent Rb(1), one Bi(3), and two equivalent Bi(1) atoms to form SRb2Bi3 square pyramids that share corners with five equivalent S(3)RbBi5 octahedra, corners with four equivalent S(4)Rb2Bi3 square pyramids,  an edgeedge with one S(3)RbBi5 octahedra, edges with two equivalent S(5)Bi6 octahedra,  an edgeedge with one S(4)Rb2Bi3 square pyramid, and edges with two equivalent S(2)Rb2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 5-85°. In the fifth S site, S(3) is bonded to one Rb(1), one Bi(3), two equivalent Bi(1), and two equivalent Bi(2) atoms to form SRbBi5 octahedra that share corners with two equivalent S(4)Rb2Bi3 square pyramids, corners with five equivalent S(2)Rb2Bi3 square pyramids, edges with two equivalent S(5)Bi6 octahedra, edges with two equivalent S(3)RbBi5 octahedra,  an edgeedge with one S(2)Rb2Bi3 square pyramid, and edges with three equivalent S(4)Rb2Bi3 square pyramids. In the sixth S site, S(4) is bonded to two equivalent Rb(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted SRb2Bi3 square pyramids that share  a cornercorner with one S(5)Bi6 octahedra, corners with two equivalent S(3)RbBi5 octahedra, corners with four equivalent S(2)Rb2Bi3 square pyramids, edges with three equivalent S(3)RbBi5 octahedra,  an edgeedge with one S(2)Rb2Bi3 square pyramid, and edges with two equivalent S(4)Rb2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 3-5°. is represented by the CIF file [CIF]
data_RbBi3S5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   4.228
_cell_length_b   12.728
_cell_length_c   19.054
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   1025.371
_cell_formula_units_Z   4
loop_
 _symmetry_equiv_pos_site_id
 _symmetry_equiv_pos_as_xyz
  1  'x, y, z'
loop_
 _atom_site_type_symbol
 _atom_site_label
 _atom_site_symmetry_multiplicity
 _atom_site_fract_x
 _atom_site_fract_y
 _atom_site_fract_z
 _atom_site_occupancy
  Rb  Rb0  1  0.000  0.398  0.149  1.0
  Rb  Rb1  1  0.000  0.602  0.851  1.0
  Rb  Rb2  1  0.500  0.898  0.351  1.0
  Rb  Rb3  1  0.500  0.102  0.649  1.0
  Bi  Bi4  1  0.000  0.051  0.151  1.0
  Bi  Bi5  1  0.000  0.949  0.849  1.0
  Bi  Bi6  1  0.500  0.551  0.349  1.0
  Bi  Bi7  1  0.500  0.449  0.651  1.0
  Bi  Bi8  1  0.000  0.274  0.814  1.0
  Bi  Bi9  1  0.000  0.726  0.186  1.0
  Bi  Bi10  1  0.500  0.774  0.686  1.0
  Bi  Bi11  1  0.500  0.226  0.314  1.0
  Bi  Bi12  1  0.000  0.331  0.478  1.0
  Bi  Bi13  1  0.000  0.669  0.522  1.0
  Bi  Bi14  1  0.500  0.831  0.022  1.0
  Bi  Bi15  1  0.500  0.169  0.978  1.0
  S  S16  1  0.000  0.677  0.046  1.0
  S  S17  1  0.000  0.323  0.954  1.0
  S  S18  1  0.500  0.177  0.454  1.0
  S  S19  1  0.500  0.823  0.546  1.0
  S  S20  1  0.000  0.309  0.628  1.0
  S  S21  1  0.000  0.691  0.372  1.0
  S  S22  1  0.500  0.809  0.872  1.0
  S  S23  1  0.500  0.191  0.128  1.0
  S  S24  1  0.000  0.389  0.333  1.0
  S  S25  1  0.000  0.611  0.667  1.0
  S  S26  1  0.500  0.889  0.167  1.0
  S  S27  1  0.500  0.111  0.833  1.0
  S  S28  1  0.000  0.089  0.293  1.0
  S  S29  1  0.000  0.911  0.707  1.0
  S  S30  1  0.500  0.589  0.207  1.0
  S  S31  1  0.500  0.411  0.793  1.0
  S  S32  1  0.000  0.000  0.000  1.0
  S  S33  1  0.500  0.500  0.500  1.0
  S  S34  1  0.500  0.000  0.500  1.0
  S  S35  1  0.000  0.500  0.000  1.0
[/CIF]
.
The compound described by RbBi3S5 crystallizes in the orthorhombic Pnnm space group. Rb(1) is bonded in a 6-coordinate geometry to one S(1), one S(3), one S(6), two equivalent S(2), and two equivalent S(4) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(4), one S(5), two equivalent S(2), and two equivalent S(3) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(1)S6 octahedra, corners with four equivalent Bi(2)S5 square pyramids, edges with two equivalent Bi(1)S6 octahedra, edges with four equivalent Bi(3)S6 octahedra, and  an edgeedge with one Bi(2)S5 square pyramid. The corner-sharing octahedra are not tilted. In the second Bi site, Bi(2) is bonded to one S(1), two equivalent S(3), and two equivalent S(4) atoms to form BiS5 square pyramids that share corners with four equivalent Bi(1)S6 octahedra,  an edgeedge with one Bi(1)S6 octahedra, edges with two equivalent Bi(3)S6 octahedra, and edges with two equivalent Bi(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 1-75°. In the third Bi site, Bi(3) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(5) atoms to form BiS6 octahedra that share corners with two equivalent Bi(3)S6 octahedra, edges with three equivalent Bi(3)S6 octahedra, edges with four equivalent Bi(1)S6 octahedra, and edges with two equivalent Bi(2)S5 square pyramids. The corner-sharing octahedra are not tilted. There are six inequivalent S sites. In the first S site, S(5) is bonded to two equivalent Bi(1) and four equivalent Bi(3) atoms to form SBi6 octahedra that share corners with two equivalent S(4)Rb2Bi3 square pyramids, edges with two equivalent S(5)Bi6 octahedra, edges with four equivalent S(3)RbBi5 octahedra, and edges with four equivalent S(2)Rb2Bi3 square pyramids. In the second S site, S(6) is bonded in a square co-planar geometry to two equivalent Rb(1) and two equivalent S(1) atoms. In the third S site, S(1) is bonded in a 5-coordinate geometry to one Rb(1), one Bi(2), two equivalent Bi(3), and one S(6) atom. In the fourth S site, S(2) is bonded to two equivalent Rb(1), one Bi(3), and two equivalent Bi(1) atoms to form SRb2Bi3 square pyramids that share corners with five equivalent S(3)RbBi5 octahedra, corners with four equivalent S(4)Rb2Bi3 square pyramids,  an edgeedge with one S(3)RbBi5 octahedra, edges with two equivalent S(5)Bi6 octahedra,  an edgeedge with one S(4)Rb2Bi3 square pyramid, and edges with two equivalent S(2)Rb2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 5-85°. In the fifth S site, S(3) is bonded to one Rb(1), one Bi(3), two equivalent Bi(1), and two equivalent Bi(2) atoms to form SRbBi5 octahedra that share corners with two equivalent S(4)Rb2Bi3 square pyramids, corners with five equivalent S(2)Rb2Bi3 square pyramids, edges with two equivalent S(5)Bi6 octahedra, edges with two equivalent S(3)RbBi5 octahedra,  an edgeedge with one S(2)Rb2Bi3 square pyramid, and edges with three equivalent S(4)Rb2Bi3 square pyramids. In the sixth S site, S(4) is bonded to two equivalent Rb(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted SRb2Bi3 square pyramids that share  a cornercorner with one S(5)Bi6 octahedra, corners with two equivalent S(3)RbBi5 octahedra, corners with four equivalent S(2)Rb2Bi3 square pyramids, edges with three equivalent S(3)RbBi5 octahedra,  an edgeedge with one S(2)Rb2Bi3 square pyramid, and edges with two equivalent S(4)Rb2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 3-5°. is represented by the CIF file [CIF]
data_RbBi3S5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   4.228
_cell_length_b   12.728
_cell_length_c   19.054
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   1025.371
_cell_formula_units_Z   4
loop_
 _symmetry_equiv_pos_site_id
 _symmetry_equiv_pos_as_xyz
  1  'x, y, z'
loop_
 _atom_site_type_symbol
 _atom_site_label
 _atom_site_symmetry_multiplicity
 _atom_site_fract_x
 _atom_site_fract_y
 _atom_site_fract_z
 _atom_site_occupancy
  Rb  Rb0  1  0.000  0.398  0.149  1.0
  Rb  Rb1  1  0.000  0.602  0.851  1.0
  Rb  Rb2  1  0.500  0.898  0.351  1.0
  Rb  Rb3  1  0.500  0.102  0.649  1.0
  Bi  Bi4  1  0.000  0.051  0.151  1.0
  Bi  Bi5  1  0.000  0.949  0.849  1.0
  Bi  Bi6  1  0.500  0.551  0.349  1.0
  Bi  Bi7  1  0.500  0.449  0.651  1.0
  Bi  Bi8  1  0.000  0.274  0.814  1.0
  Bi  Bi9  1  0.000  0.726  0.186  1.0
  Bi  Bi10  1  0.500  0.774  0.686  1.0
  Bi  Bi11  1  0.500  0.226  0.314  1.0
  Bi  Bi12  1  0.000  0.331  0.478  1.0
  Bi  Bi13  1  0.000  0.669  0.522  1.0
  Bi  Bi14  1  0.500  0.831  0.022  1.0
  Bi  Bi15  1  0.500  0.169  0.978  1.0
  S  S16  1  0.000  0.677  0.046  1.0
  S  S17  1  0.000  0.323  0.954  1.0
  S  S18  1  0.500  0.177  0.454  1.0
  S  S19  1  0.500  0.823  0.546  1.0
  S  S20  1  0.000  0.309  0.628  1.0
  S  S21  1  0.000  0.691  0.372  1.0
  S  S22  1  0.500  0.809  0.872  1.0
  S  S23  1  0.500  0.191  0.128  1.0
  S  S24  1  0.000  0.389  0.333  1.0
  S  S25  1  0.000  0.611  0.667  1.0
  S  S26  1  0.500  0.889  0.167  1.0
  S  S27  1  0.500  0.111  0.833  1.0
  S  S28  1  0.000  0.089  0.293  1.0
  S  S29  1  0.000  0.911  0.707  1.0
  S  S30  1  0.500  0.589  0.207  1.0
  S  S31  1  0.500  0.411  0.793  1.0
  S  S32  1  0.000  0.000  0.000  1.0
  S  S33  1  0.500  0.500  0.500  1.0
  S  S34  1  0.500  0.000  0.500  1.0
  S  S35  1  0.000  0.500  0.000  1.0
[/CIF]
.