The compound described by Na4Ga2S5 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), one S(5), two equivalent S(3), and two equivalent S(4) atoms to form distorted NaS6 octahedra that share corners with three equivalent Na(3)S5 square pyramids,  a cornercorner with one Ga(2)S4 tetrahedra, corners with two equivalent Ga(1)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Ga(1)S4 tetrahedra, and edges with two equivalent Ga(2)S4 tetrahedra. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(2), one S(5), two equivalent S(1), and two equivalent S(4) atoms. In the third Na site, Na(3) is bonded to one S(3), one S(5), and three equivalent S(2) atoms to form distorted NaS5 square pyramids that share corners with three equivalent Na(1)S6 octahedra, corners with two equivalent Na(3)S5 square pyramids,  a cornercorner with one Ga(1)S4 tetrahedra, corners with three equivalent Ga(2)S4 tetrahedra, edges with two equivalent Na(3)S5 square pyramids, and  an edgeedge with one Ga(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-59°. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), and three equivalent S(5) atoms. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one S(3), one S(4), and two equivalent S(1) atoms to form distorted GaS4 tetrahedra that share corners with two equivalent Na(1)S6 octahedra,  a cornercorner with one Na(3)S5 square pyramid, corners with two equivalent Ga(2)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, and  an edgeedge with one Ga(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-51°. In the second Ga site, Ga(2) is bonded to one S(2), one S(3), one S(4), and one S(5) atom to form GaS4 tetrahedra that share  a cornercorner with one Na(1)S6 octahedra, corners with three equivalent Na(3)S5 square pyramids, corners with two equivalent Ga(1)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, and  an edgeedge with one Na(3)S5 square pyramid. The corner-sharing octahedral tilt angles are 32°. There are five inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one Na(3), one Na(4), two equivalent Na(1), one Ga(1), and one Ga(2) atom. In the second S site, S(4) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(2), one Ga(1), and one Ga(2) atom. In the third S site, S(5) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), three equivalent Na(4), and one Ga(2) atom. In the fourth S site, S(1) is bonded in a 6-coordinate geometry to one Na(1), one Na(4), two equivalent Na(2), and two equivalent Ga(1) atoms. In the fifth S site, S(2) is bonded to one Na(2), one Na(4), three equivalent Na(3), and one Ga(2) atom to form a mixture of distorted corner and edge-sharing SNa5Ga octahedra. The corner-sharing octahedral tilt angles are 10°. is represented by the CIF file [CIF]
data_Na4Ga2S5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.105
_cell_length_b   7.948
_cell_length_c   19.804
_cell_angle_alpha   88.811
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   960.717
_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
  Na  Na0  1  0.745  0.078  0.957  1.0
  Na  Na1  1  0.245  0.922  0.543  1.0
  Na  Na2  1  0.255  0.922  0.043  1.0
  Na  Na3  1  0.755  0.078  0.457  1.0
  Na  Na4  1  0.461  0.403  0.898  1.0
  Na  Na5  1  0.961  0.597  0.602  1.0
  Na  Na6  1  0.539  0.597  0.102  1.0
  Na  Na7  1  0.039  0.403  0.398  1.0
  Na  Na8  1  0.476  0.346  0.717  1.0
  Na  Na9  1  0.976  0.654  0.783  1.0
  Na  Na10  1  0.524  0.654  0.283  1.0
  Na  Na11  1  0.024  0.346  0.217  1.0
  Na  Na12  1  0.500  0.889  0.701  1.0
  Na  Na13  1  0.000  0.111  0.799  1.0
  Na  Na14  1  0.500  0.111  0.299  1.0
  Na  Na15  1  1.000  0.889  0.201  1.0
  Ga  Ga16  1  0.087  0.345  0.036  1.0
  Ga  Ga17  1  0.913  0.655  0.964  1.0
  Ga  Ga18  1  0.413  0.345  0.536  1.0
  Ga  Ga19  1  0.068  0.834  0.366  1.0
  Ga  Ga20  1  0.568  0.166  0.134  1.0
  Ga  Ga21  1  0.932  0.166  0.634  1.0
  Ga  Ga22  1  0.432  0.834  0.866  1.0
  Ga  Ga23  1  0.587  0.655  0.464  1.0
  S  S24  1  0.524  0.389  0.425  1.0
  S  S25  1  0.976  0.389  0.925  1.0
  S  S26  1  0.476  0.611  0.575  1.0
  S  S27  1  0.014  0.631  0.293  1.0
  S  S28  1  0.514  0.369  0.207  1.0
  S  S29  1  0.986  0.369  0.707  1.0
  S  S30  1  0.024  0.611  0.075  1.0
  S  S31  1  0.486  0.631  0.793  1.0
  S  S32  1  0.569  0.133  0.598  1.0
  S  S33  1  0.069  0.867  0.902  1.0
  S  S34  1  0.431  0.867  0.402  1.0
  S  S35  1  0.931  0.133  0.098  1.0
  S  S36  1  0.562  0.742  0.971  1.0
  S  S37  1  0.062  0.258  0.529  1.0
  S  S38  1  0.438  0.258  0.029  1.0
  S  S39  1  0.938  0.742  0.471  1.0
  S  S40  1  0.523  0.092  0.827  1.0
  S  S41  1  0.023  0.908  0.673  1.0
  S  S42  1  0.477  0.908  0.173  1.0
  S  S43  1  0.977  0.092  0.327  1.0
[/CIF]
.
The compound described by Na4Ga2S5 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), one S(5), two equivalent S(3), and two equivalent S(4) atoms to form distorted NaS6 octahedra that share corners with three equivalent Na(3)S5 square pyramids,  a cornercorner with one Ga(2)S4 tetrahedra, corners with two equivalent Ga(1)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Ga(1)S4 tetrahedra, and edges with two equivalent Ga(2)S4 tetrahedra. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(2), one S(5), two equivalent S(1), and two equivalent S(4) atoms. In the third Na site, Na(3) is bonded to one S(3), one S(5), and three equivalent S(2) atoms to form distorted NaS5 square pyramids that share corners with three equivalent Na(1)S6 octahedra, corners with two equivalent Na(3)S5 square pyramids,  a cornercorner with one Ga(1)S4 tetrahedra, corners with three equivalent Ga(2)S4 tetrahedra, edges with two equivalent Na(3)S5 square pyramids, and  an edgeedge with one Ga(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-59°. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one S(1), one S(2), one S(3), and three equivalent S(5) atoms. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one S(3), one S(4), and two equivalent S(1) atoms to form distorted GaS4 tetrahedra that share corners with two equivalent Na(1)S6 octahedra,  a cornercorner with one Na(3)S5 square pyramid, corners with two equivalent Ga(2)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, and  an edgeedge with one Ga(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-51°. In the second Ga site, Ga(2) is bonded to one S(2), one S(3), one S(4), and one S(5) atom to form GaS4 tetrahedra that share  a cornercorner with one Na(1)S6 octahedra, corners with three equivalent Na(3)S5 square pyramids, corners with two equivalent Ga(1)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, and  an edgeedge with one Na(3)S5 square pyramid. The corner-sharing octahedral tilt angles are 32°. There are five inequivalent S sites. In the first S site, S(3) is bonded in a 6-coordinate geometry to one Na(3), one Na(4), two equivalent Na(1), one Ga(1), and one Ga(2) atom. In the second S site, S(4) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(2), one Ga(1), and one Ga(2) atom. In the third S site, S(5) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), three equivalent Na(4), and one Ga(2) atom. In the fourth S site, S(1) is bonded in a 6-coordinate geometry to one Na(1), one Na(4), two equivalent Na(2), and two equivalent Ga(1) atoms. In the fifth S site, S(2) is bonded to one Na(2), one Na(4), three equivalent Na(3), and one Ga(2) atom to form a mixture of distorted corner and edge-sharing SNa5Ga octahedra. The corner-sharing octahedral tilt angles are 10°. is represented by the CIF file [CIF]
data_Na4Ga2S5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.105
_cell_length_b   7.948
_cell_length_c   19.804
_cell_angle_alpha   88.811
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   960.717
_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
  Na  Na0  1  0.745  0.078  0.957  1.0
  Na  Na1  1  0.245  0.922  0.543  1.0
  Na  Na2  1  0.255  0.922  0.043  1.0
  Na  Na3  1  0.755  0.078  0.457  1.0
  Na  Na4  1  0.461  0.403  0.898  1.0
  Na  Na5  1  0.961  0.597  0.602  1.0
  Na  Na6  1  0.539  0.597  0.102  1.0
  Na  Na7  1  0.039  0.403  0.398  1.0
  Na  Na8  1  0.476  0.346  0.717  1.0
  Na  Na9  1  0.976  0.654  0.783  1.0
  Na  Na10  1  0.524  0.654  0.283  1.0
  Na  Na11  1  0.024  0.346  0.217  1.0
  Na  Na12  1  0.500  0.889  0.701  1.0
  Na  Na13  1  0.000  0.111  0.799  1.0
  Na  Na14  1  0.500  0.111  0.299  1.0
  Na  Na15  1  1.000  0.889  0.201  1.0
  Ga  Ga16  1  0.087  0.345  0.036  1.0
  Ga  Ga17  1  0.913  0.655  0.964  1.0
  Ga  Ga18  1  0.413  0.345  0.536  1.0
  Ga  Ga19  1  0.068  0.834  0.366  1.0
  Ga  Ga20  1  0.568  0.166  0.134  1.0
  Ga  Ga21  1  0.932  0.166  0.634  1.0
  Ga  Ga22  1  0.432  0.834  0.866  1.0
  Ga  Ga23  1  0.587  0.655  0.464  1.0
  S  S24  1  0.524  0.389  0.425  1.0
  S  S25  1  0.976  0.389  0.925  1.0
  S  S26  1  0.476  0.611  0.575  1.0
  S  S27  1  0.014  0.631  0.293  1.0
  S  S28  1  0.514  0.369  0.207  1.0
  S  S29  1  0.986  0.369  0.707  1.0
  S  S30  1  0.024  0.611  0.075  1.0
  S  S31  1  0.486  0.631  0.793  1.0
  S  S32  1  0.569  0.133  0.598  1.0
  S  S33  1  0.069  0.867  0.902  1.0
  S  S34  1  0.431  0.867  0.402  1.0
  S  S35  1  0.931  0.133  0.098  1.0
  S  S36  1  0.562  0.742  0.971  1.0
  S  S37  1  0.062  0.258  0.529  1.0
  S  S38  1  0.438  0.258  0.029  1.0
  S  S39  1  0.938  0.742  0.471  1.0
  S  S40  1  0.523  0.092  0.827  1.0
  S  S41  1  0.023  0.908  0.673  1.0
  S  S42  1  0.477  0.908  0.173  1.0
  S  S43  1  0.977  0.092  0.327  1.0
[/CIF]
.