The structure described by Li5BiS4 crystallizes in the orthorhombic Immm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1) and three equivalent S(2) atoms to form LiS4 tetrahedra that share  a cornercorner with one Bi(1)S6 octahedra, corners with ten equivalent Li(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the second Li site, Li(2) is bonded in a square co-planar geometry to four equivalent S(1) atoms. Bi(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form BiS6 octahedra that share corners with four equivalent Li(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with eight equivalent Li(1)S4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing SLi4Bi2 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded in a 7-coordinate geometry to six equivalent Li(1) and one Bi(1) atom. is represented by the CIF file [CIF]
data_Li5BiS4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   7.909
_cell_length_b   7.909
_cell_length_c   7.909
_cell_angle_alpha   151.099
_cell_angle_beta   125.598
_cell_angle_gamma   62.771
_symmetry_Int_Tables_number   1
_cell_volume   192.710
_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
  Li  Li0  1  0.975  0.180  0.795  1.0
  Li  Li1  1  0.385  0.180  0.205  1.0
  Li  Li2  1  0.615  0.820  0.795  1.0
  Li  Li3  1  0.025  0.820  0.205  1.0
  Li  Li4  1  0.500  0.500  0.000  1.0
  Bi  Bi5  1  0.000  0.500  0.500  1.0
  S  S6  1  0.275  0.000  0.275  1.0
  S  S7  1  0.214  0.714  0.500  1.0
  S  S8  1  0.786  0.286  0.500  1.0
  S  S9  1  0.725  0.000  0.725  1.0
[/CIF]
.
The structure described by Li5BiS4 crystallizes in the orthorhombic Immm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1) and three equivalent S(2) atoms to form LiS4 tetrahedra that share  a cornercorner with one Bi(1)S6 octahedra, corners with ten equivalent Li(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with three equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the second Li site, Li(2) is bonded in a square co-planar geometry to four equivalent S(1) atoms. Bi(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form BiS6 octahedra that share corners with four equivalent Li(1)S4 tetrahedra, edges with two equivalent Bi(1)S6 octahedra, and edges with eight equivalent Li(1)S4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing SLi4Bi2 octahedra. The corner-sharing octahedra are not tilted. In the second S site, S(2) is bonded in a 7-coordinate geometry to six equivalent Li(1) and one Bi(1) atom. is represented by the CIF file [CIF]
data_Li5BiS4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   7.909
_cell_length_b   7.909
_cell_length_c   7.909
_cell_angle_alpha   151.099
_cell_angle_beta   125.598
_cell_angle_gamma   62.771
_symmetry_Int_Tables_number   1
_cell_volume   192.710
_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
  Li  Li0  1  0.975  0.180  0.795  1.0
  Li  Li1  1  0.385  0.180  0.205  1.0
  Li  Li2  1  0.615  0.820  0.795  1.0
  Li  Li3  1  0.025  0.820  0.205  1.0
  Li  Li4  1  0.500  0.500  0.000  1.0
  Bi  Bi5  1  0.000  0.500  0.500  1.0
  S  S6  1  0.275  0.000  0.275  1.0
  S  S7  1  0.214  0.714  0.500  1.0
  S  S8  1  0.786  0.286  0.500  1.0
  S  S9  1  0.725  0.000  0.725  1.0
[/CIF]
.