The crystal structure described by PbBi4S7 crystallizes in the monoclinic Cm space group. Pb(1) is bonded in a 4-coordinate geometry to one S(5), one S(7), and two equivalent S(4) atoms. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(7) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(3)S6 octahedra, corners with two equivalent Bi(2)S6 octahedra, corners with two equivalent Bi(4)S5 square pyramids, edges with two equivalent Bi(1)S6 octahedra, and edges with three equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 17-62°. In the second Bi site, Bi(2) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(7) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 17-40°. In the third Bi site, Bi(3) is bonded to one S(3), one S(4), two equivalent S(5), and two equivalent S(6) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(1)S6 octahedra,  a cornercorner with one Bi(2)S6 octahedra, corners with two equivalent Bi(4)S5 square pyramids, edges with two equivalent Bi(3)S6 octahedra, and edges with three equivalent Bi(4)S5 square pyramids. The corner-sharing octahedral tilt angles range from 40-62°. In the fourth Bi site, Bi(4) is bonded to one S(6), two equivalent S(3), and two equivalent S(5) atoms to form BiS5 square pyramids that share corners with two equivalent Bi(1)S6 octahedra, corners with two equivalent Bi(3)S6 octahedra, edges with three equivalent Bi(3)S6 octahedra, and edges with two equivalent Bi(4)S5 square pyramids. The corner-sharing octahedral tilt angles range from 21-55°. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Bi(2) and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Bi(1) and two equivalent Bi(2) atoms. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Bi(1), one Bi(3), and two equivalent Bi(4) atoms. In the fourth S site, S(4) is bonded to two equivalent Pb(1), one Bi(2), and one Bi(3) atom to form distorted SBi2Pb2 trigonal pyramids that share corners with two equivalent S(4)Bi2Pb2 trigonal pyramids and edges with two equivalent S(5)Bi4Pb trigonal bipyramids. In the fifth S site, S(5) is bonded to one Pb(1), two equivalent Bi(3), and two equivalent Bi(4) atoms to form distorted SBi4Pb trigonal bipyramids that share edges with two equivalent S(5)Bi4Pb trigonal bipyramids and edges with two equivalent S(4)Bi2Pb2 trigonal pyramids. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Bi(4) and two equivalent Bi(3) atoms. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one Pb(1), two equivalent Bi(1), and two equivalent Bi(2) atoms. is represented by the Crystallographic Information File (CIF) [CIF]
data_Bi4PbS7
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.999
_cell_length_b   6.999
_cell_length_c   12.220
_cell_angle_alpha   75.320
_cell_angle_beta   75.320
_cell_angle_gamma   33.372
_symmetry_Int_Tables_number   1
_cell_volume   317.573
_cell_formula_units_Z   1
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
  Bi  Bi0  1  0.871  0.871  0.930  1.0
  Bi  Bi1  1  0.113  0.113  0.067  1.0
  Bi  Bi2  1  0.003  0.003  0.507  1.0
  Bi  Bi3  1  0.694  0.694  0.658  1.0
  Pb  Pb4  1  0.343  0.343  0.292  1.0
  S  S5  1  0.262  0.262  0.856  1.0
  S  S6  1  0.728  0.728  0.132  1.0
  S  S7  1  0.050  0.050  0.719  1.0
  S  S8  1  0.987  0.987  0.288  1.0
  S  S9  1  0.345  0.345  0.539  1.0
  S  S10  1  0.653  0.653  0.456  1.0
  S  S11  1  0.471  0.471  0.032  1.0
[/CIF]
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The crystal structure described by PbBi4S7 crystallizes in the monoclinic Cm space group. Pb(1) is bonded in a 4-coordinate geometry to one S(5), one S(7), and two equivalent S(4) atoms. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(7) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(3)S6 octahedra, corners with two equivalent Bi(2)S6 octahedra, corners with two equivalent Bi(4)S5 square pyramids, edges with two equivalent Bi(1)S6 octahedra, and edges with three equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 17-62°. In the second Bi site, Bi(2) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(7) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 17-40°. In the third Bi site, Bi(3) is bonded to one S(3), one S(4), two equivalent S(5), and two equivalent S(6) atoms to form BiS6 octahedra that share  a cornercorner with one Bi(1)S6 octahedra,  a cornercorner with one Bi(2)S6 octahedra, corners with two equivalent Bi(4)S5 square pyramids, edges with two equivalent Bi(3)S6 octahedra, and edges with three equivalent Bi(4)S5 square pyramids. The corner-sharing octahedral tilt angles range from 40-62°. In the fourth Bi site, Bi(4) is bonded to one S(6), two equivalent S(3), and two equivalent S(5) atoms to form BiS5 square pyramids that share corners with two equivalent Bi(1)S6 octahedra, corners with two equivalent Bi(3)S6 octahedra, edges with three equivalent Bi(3)S6 octahedra, and edges with two equivalent Bi(4)S5 square pyramids. The corner-sharing octahedral tilt angles range from 21-55°. There are seven inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Bi(2) and two equivalent Bi(1) atoms. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Bi(1) and two equivalent Bi(2) atoms. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Bi(1), one Bi(3), and two equivalent Bi(4) atoms. In the fourth S site, S(4) is bonded to two equivalent Pb(1), one Bi(2), and one Bi(3) atom to form distorted SBi2Pb2 trigonal pyramids that share corners with two equivalent S(4)Bi2Pb2 trigonal pyramids and edges with two equivalent S(5)Bi4Pb trigonal bipyramids. In the fifth S site, S(5) is bonded to one Pb(1), two equivalent Bi(3), and two equivalent Bi(4) atoms to form distorted SBi4Pb trigonal bipyramids that share edges with two equivalent S(5)Bi4Pb trigonal bipyramids and edges with two equivalent S(4)Bi2Pb2 trigonal pyramids. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Bi(4) and two equivalent Bi(3) atoms. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one Pb(1), two equivalent Bi(1), and two equivalent Bi(2) atoms. is represented by the Crystallographic Information File (CIF) [CIF]
data_Bi4PbS7
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.999
_cell_length_b   6.999
_cell_length_c   12.220
_cell_angle_alpha   75.320
_cell_angle_beta   75.320
_cell_angle_gamma   33.372
_symmetry_Int_Tables_number   1
_cell_volume   317.573
_cell_formula_units_Z   1
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
  Bi  Bi0  1  0.871  0.871  0.930  1.0
  Bi  Bi1  1  0.113  0.113  0.067  1.0
  Bi  Bi2  1  0.003  0.003  0.507  1.0
  Bi  Bi3  1  0.694  0.694  0.658  1.0
  Pb  Pb4  1  0.343  0.343  0.292  1.0
  S  S5  1  0.262  0.262  0.856  1.0
  S  S6  1  0.728  0.728  0.132  1.0
  S  S7  1  0.050  0.050  0.719  1.0
  S  S8  1  0.987  0.987  0.288  1.0
  S  S9  1  0.345  0.345  0.539  1.0
  S  S10  1  0.653  0.653  0.456  1.0
  S  S11  1  0.471  0.471  0.032  1.0
[/CIF]
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