The crystal structure described by CsBi3S5 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(5), and three equivalent S(1) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 4-55°. In the second Bi site, Bi(2) is bonded to one S(5), two equivalent S(1), and three equivalent S(3) atoms to form a mixture of distorted corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the third Bi site, Bi(3) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 7-55°. There are five inequivalent S sites. In the first S site, S(5) is bonded to two equivalent Cs(1), one Bi(2), and two equivalent Bi(3) atoms to form distorted SCs2Bi3 trigonal bipyramids that share  a cornercorner with one S(3)Bi6 octahedra, corners with two equivalent S(1)Cs3Bi3 octahedra, corners with four equivalent S(4)CsBi3 tetrahedra, corners with four equivalent S(2)Cs2Bi3 trigonal bipyramids, edges with two equivalent S(3)Bi6 octahedra, edges with three equivalent S(1)Cs3Bi3 octahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-21°. In the second S site, S(1) is bonded to three equivalent Cs(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted SCs3Bi3 octahedra that share corners with two equivalent S(3)Bi6 octahedra,  a cornercorner with one S(4)CsBi3 tetrahedra, corners with two equivalent S(5)Cs2Bi3 trigonal bipyramids, corners with five equivalent S(2)Cs2Bi3 trigonal bipyramids, edges with three equivalent S(3)Bi6 octahedra, edges with four equivalent S(1)Cs3Bi3 octahedra, edges with two equivalent S(4)CsBi3 tetrahedra,  an edgeedge with one S(2)Cs2Bi3 trigonal bipyramid, and edges with three equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 7°. In the third S site, S(2) is bonded to two equivalent Cs(1), one Bi(1), and two equivalent Bi(3) atoms to form distorted SCs2Bi3 trigonal bipyramids that share corners with five equivalent S(1)Cs3Bi3 octahedra, corners with two equivalent S(4)CsBi3 tetrahedra, corners with four equivalent S(5)Cs2Bi3 trigonal bipyramids,  an edgeedge with one S(1)Cs3Bi3 octahedra, edges with two equivalent S(3)Bi6 octahedra, edges with two equivalent S(4)CsBi3 tetrahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-50°. In the fourth S site, S(3) is bonded to one Bi(3), two equivalent Bi(1), and three equivalent Bi(2) atoms to form SBi6 octahedra that share corners with two equivalent S(1)Cs3Bi3 octahedra, corners with three equivalent S(4)CsBi3 tetrahedra,  a cornercorner with one S(5)Cs2Bi3 trigonal bipyramid, edges with three equivalent S(1)Cs3Bi3 octahedra, edges with four equivalent S(3)Bi6 octahedra,  an edgeedge with one S(4)CsBi3 tetrahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 7°. In the fifth S site, S(4) is bonded to one Cs(1), one Bi(3), and two equivalent Bi(1) atoms to form distorted SCsBi3 tetrahedra that share  a cornercorner with one S(1)Cs3Bi3 octahedra, corners with three equivalent S(3)Bi6 octahedra, corners with two equivalent S(4)CsBi3 tetrahedra, corners with two equivalent S(2)Cs2Bi3 trigonal bipyramids, corners with four equivalent S(5)Cs2Bi3 trigonal bipyramids,  an edgeedge with one S(3)Bi6 octahedra, edges with two equivalent S(1)Cs3Bi3 octahedra, and edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 7-17°. is represented by the Crystallographic Information File (CIF) [CIF]
data_CsBi3S5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   4.087
_cell_length_b   12.229
_cell_length_c   21.309
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   1065.043
_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
  Cs  Cs0  1  0.750  0.004  0.889  1.0
  Cs  Cs1  1  0.250  0.996  0.111  1.0
  Cs  Cs2  1  0.750  0.504  0.611  1.0
  Cs  Cs3  1  0.250  0.496  0.389  1.0
  Bi  Bi4  1  0.250  0.871  0.647  1.0
  Bi  Bi5  1  0.750  0.129  0.353  1.0
  Bi  Bi6  1  0.250  0.371  0.853  1.0
  Bi  Bi7  1  0.750  0.629  0.147  1.0
  Bi  Bi8  1  0.250  0.665  0.974  1.0
  Bi  Bi9  1  0.750  0.335  0.026  1.0
  Bi  Bi10  1  0.250  0.165  0.526  1.0
  Bi  Bi11  1  0.750  0.835  0.474  1.0
  Bi  Bi12  1  0.750  0.647  0.808  1.0
  Bi  Bi13  1  0.250  0.353  0.192  1.0
  Bi  Bi14  1  0.750  0.147  0.692  1.0
  Bi  Bi15  1  0.250  0.853  0.308  1.0
  S  S16  1  0.250  0.720  0.527  1.0
  S  S17  1  0.750  0.280  0.473  1.0
  S  S18  1  0.250  0.220  0.973  1.0
  S  S19  1  0.750  0.780  0.027  1.0
  S  S20  1  0.250  0.014  0.741  1.0
  S  S21  1  0.750  0.986  0.259  1.0
  S  S22  1  0.250  0.514  0.759  1.0
  S  S23  1  0.750  0.486  0.241  1.0
  S  S24  1  0.250  0.989  0.417  1.0
  S  S25  1  0.750  0.011  0.583  1.0
  S  S26  1  0.250  0.489  0.083  1.0
  S  S27  1  0.750  0.511  0.917  1.0
  S  S28  1  0.250  0.749  0.192  1.0
  S  S29  1  0.750  0.251  0.808  1.0
  S  S30  1  0.250  0.249  0.308  1.0
  S  S31  1  0.750  0.751  0.692  1.0
  S  S32  1  0.750  0.727  0.368  1.0
  S  S33  1  0.250  0.273  0.632  1.0
  S  S34  1  0.750  0.227  0.132  1.0
  S  S35  1  0.250  0.773  0.868  1.0
[/CIF]
.
The crystal structure described by CsBi3S5 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(5), and three equivalent S(1) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 4-55°. In the second Bi site, Bi(2) is bonded to one S(5), two equivalent S(1), and three equivalent S(3) atoms to form a mixture of distorted corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the third Bi site, Bi(3) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 7-55°. There are five inequivalent S sites. In the first S site, S(5) is bonded to two equivalent Cs(1), one Bi(2), and two equivalent Bi(3) atoms to form distorted SCs2Bi3 trigonal bipyramids that share  a cornercorner with one S(3)Bi6 octahedra, corners with two equivalent S(1)Cs3Bi3 octahedra, corners with four equivalent S(4)CsBi3 tetrahedra, corners with four equivalent S(2)Cs2Bi3 trigonal bipyramids, edges with two equivalent S(3)Bi6 octahedra, edges with three equivalent S(1)Cs3Bi3 octahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-21°. In the second S site, S(1) is bonded to three equivalent Cs(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted SCs3Bi3 octahedra that share corners with two equivalent S(3)Bi6 octahedra,  a cornercorner with one S(4)CsBi3 tetrahedra, corners with two equivalent S(5)Cs2Bi3 trigonal bipyramids, corners with five equivalent S(2)Cs2Bi3 trigonal bipyramids, edges with three equivalent S(3)Bi6 octahedra, edges with four equivalent S(1)Cs3Bi3 octahedra, edges with two equivalent S(4)CsBi3 tetrahedra,  an edgeedge with one S(2)Cs2Bi3 trigonal bipyramid, and edges with three equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 7°. In the third S site, S(2) is bonded to two equivalent Cs(1), one Bi(1), and two equivalent Bi(3) atoms to form distorted SCs2Bi3 trigonal bipyramids that share corners with five equivalent S(1)Cs3Bi3 octahedra, corners with two equivalent S(4)CsBi3 tetrahedra, corners with four equivalent S(5)Cs2Bi3 trigonal bipyramids,  an edgeedge with one S(1)Cs3Bi3 octahedra, edges with two equivalent S(3)Bi6 octahedra, edges with two equivalent S(4)CsBi3 tetrahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-50°. In the fourth S site, S(3) is bonded to one Bi(3), two equivalent Bi(1), and three equivalent Bi(2) atoms to form SBi6 octahedra that share corners with two equivalent S(1)Cs3Bi3 octahedra, corners with three equivalent S(4)CsBi3 tetrahedra,  a cornercorner with one S(5)Cs2Bi3 trigonal bipyramid, edges with three equivalent S(1)Cs3Bi3 octahedra, edges with four equivalent S(3)Bi6 octahedra,  an edgeedge with one S(4)CsBi3 tetrahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 7°. In the fifth S site, S(4) is bonded to one Cs(1), one Bi(3), and two equivalent Bi(1) atoms to form distorted SCsBi3 tetrahedra that share  a cornercorner with one S(1)Cs3Bi3 octahedra, corners with three equivalent S(3)Bi6 octahedra, corners with two equivalent S(4)CsBi3 tetrahedra, corners with two equivalent S(2)Cs2Bi3 trigonal bipyramids, corners with four equivalent S(5)Cs2Bi3 trigonal bipyramids,  an edgeedge with one S(3)Bi6 octahedra, edges with two equivalent S(1)Cs3Bi3 octahedra, and edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 7-17°. is represented by the Crystallographic Information File (CIF) [CIF]
data_CsBi3S5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   4.087
_cell_length_b   12.229
_cell_length_c   21.309
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   1065.043
_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
  Cs  Cs0  1  0.750  0.004  0.889  1.0
  Cs  Cs1  1  0.250  0.996  0.111  1.0
  Cs  Cs2  1  0.750  0.504  0.611  1.0
  Cs  Cs3  1  0.250  0.496  0.389  1.0
  Bi  Bi4  1  0.250  0.871  0.647  1.0
  Bi  Bi5  1  0.750  0.129  0.353  1.0
  Bi  Bi6  1  0.250  0.371  0.853  1.0
  Bi  Bi7  1  0.750  0.629  0.147  1.0
  Bi  Bi8  1  0.250  0.665  0.974  1.0
  Bi  Bi9  1  0.750  0.335  0.026  1.0
  Bi  Bi10  1  0.250  0.165  0.526  1.0
  Bi  Bi11  1  0.750  0.835  0.474  1.0
  Bi  Bi12  1  0.750  0.647  0.808  1.0
  Bi  Bi13  1  0.250  0.353  0.192  1.0
  Bi  Bi14  1  0.750  0.147  0.692  1.0
  Bi  Bi15  1  0.250  0.853  0.308  1.0
  S  S16  1  0.250  0.720  0.527  1.0
  S  S17  1  0.750  0.280  0.473  1.0
  S  S18  1  0.250  0.220  0.973  1.0
  S  S19  1  0.750  0.780  0.027  1.0
  S  S20  1  0.250  0.014  0.741  1.0
  S  S21  1  0.750  0.986  0.259  1.0
  S  S22  1  0.250  0.514  0.759  1.0
  S  S23  1  0.750  0.486  0.241  1.0
  S  S24  1  0.250  0.989  0.417  1.0
  S  S25  1  0.750  0.011  0.583  1.0
  S  S26  1  0.250  0.489  0.083  1.0
  S  S27  1  0.750  0.511  0.917  1.0
  S  S28  1  0.250  0.749  0.192  1.0
  S  S29  1  0.750  0.251  0.808  1.0
  S  S30  1  0.250  0.249  0.308  1.0
  S  S31  1  0.750  0.751  0.692  1.0
  S  S32  1  0.750  0.727  0.368  1.0
  S  S33  1  0.250  0.273  0.632  1.0
  S  S34  1  0.750  0.227  0.132  1.0
  S  S35  1  0.250  0.773  0.868  1.0
[/CIF]
.