The compound described by Na4Zn3S5 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(2), and two equivalent S(4) atoms. In the second Na site, Na(2) is bonded to two equivalent S(1) and three equivalent S(3) atoms to form distorted NaS5 square pyramids that share corners with three equivalent Na(3)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, edges with four equivalent Na(2)S5 square pyramids,  an edgeedge with one Zn(2)S4 tetrahedra, and edges with three equivalent Zn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-54°. In the third Na site, Na(3) is bonded to one S(3), two equivalent S(4), and three equivalent S(5) atoms to form distorted NaS6 octahedra that share corners with three equivalent Na(2)S5 square pyramids,  a cornercorner with one Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, corners with two equivalent Zn(3)S4 tetrahedra, edges with four equivalent Na(3)S6 octahedra, edges with two equivalent Zn(1)S4 tetrahedra, and edges with three equivalent Zn(3)S4 tetrahedra. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(2), and two equivalent S(4) atoms. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one S(5), and two equivalent S(3) atoms to form ZnS4 tetrahedra that share  a cornercorner with one Na(3)S6 octahedra, corners with two equivalent Na(2)S5 square pyramids, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, corners with two equivalent Zn(3)S4 tetrahedra, edges with two equivalent Na(3)S6 octahedra, and edges with three equivalent Na(2)S5 square pyramids. The corner-sharing octahedral tilt angles are 15°. In the second Zn site, Zn(2) is bonded to one S(2), one S(4), and two equivalent S(1) atoms to form ZnS4 tetrahedra that share corners with two equivalent Na(3)S6 octahedra, corners with two equivalent Na(2)S5 square pyramids, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, corners with two equivalent Zn(3)S4 tetrahedra, and  an edgeedge with one Na(2)S5 square pyramid. The corner-sharing octahedral tilt angles are 48°. In the third Zn site, Zn(3) is bonded to one S(2), one S(4), and two equivalent S(5) atoms to form distorted ZnS4 tetrahedra that share corners with two equivalent Na(3)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, corners with two equivalent Zn(3)S4 tetrahedra, and edges with three equivalent Na(3)S6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are five inequivalent S sites. In the first S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(4), one Zn(2), and one Zn(3) atom. In the second S site, S(3) is bonded in a 7-coordinate geometry to one Na(3), one Na(4), three equivalent Na(2), and two equivalent Zn(1) atoms. In the third S site, S(4) is bonded in a 8-coordinate geometry to two equivalent Na(1), two equivalent Na(3), two equivalent Na(4), one Zn(2), and one Zn(3) atom. In the fourth S site, S(5) is bonded to three equivalent Na(3), one Zn(1), and two equivalent Zn(3) atoms to form a mixture of distorted corner and edge-sharing SNa3Zn3 octahedra. The corner-sharing octahedral tilt angles are 72°. In the fifth S site, S(1) is bonded to one Na(1), two equivalent Na(2), one Zn(1), and two equivalent Zn(2) atoms to form a mixture of distorted corner and edge-sharing SNa3Zn3 octahedra. The corner-sharing octahedral tilt angles are 72°. is represented by the Crystallographic Information File (CIF) [CIF]
data_Na4Zn3S5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   3.931
_cell_length_b   13.189
_cell_length_c   18.875
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   978.666
_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  0.250  0.998  0.765  1.0
  Na  Na1  1  0.250  0.498  0.735  1.0
  Na  Na2  1  0.750  0.002  0.235  1.0
  Na  Na3  1  0.750  0.502  0.265  1.0
  Na  Na4  1  0.250  0.007  0.417  1.0
  Na  Na5  1  0.250  0.507  0.083  1.0
  Na  Na6  1  0.750  0.993  0.583  1.0
  Na  Na7  1  0.750  0.493  0.917  1.0
  Na  Na8  1  0.250  0.109  0.951  1.0
  Na  Na9  1  0.250  0.609  0.549  1.0
  Na  Na10  1  0.750  0.891  0.049  1.0
  Na  Na11  1  0.750  0.391  0.451  1.0
  Na  Na12  1  0.250  0.273  0.834  1.0
  Na  Na13  1  0.250  0.773  0.666  1.0
  Na  Na14  1  0.750  0.727  0.166  1.0
  Na  Na15  1  0.750  0.227  0.334  1.0
  Zn  Zn16  1  0.250  0.209  0.541  1.0
  Zn  Zn17  1  0.250  0.709  0.959  1.0
  Zn  Zn18  1  0.750  0.791  0.459  1.0
  Zn  Zn19  1  0.750  0.291  0.041  1.0
  Zn  Zn20  1  0.250  0.319  0.217  1.0
  Zn  Zn21  1  0.250  0.819  0.283  1.0
  Zn  Zn22  1  0.750  0.681  0.783  1.0
  Zn  Zn23  1  0.750  0.181  0.717  1.0
  Zn  Zn24  1  0.250  0.576  0.369  1.0
  Zn  Zn25  1  0.250  0.076  0.131  1.0
  Zn  Zn26  1  0.750  0.424  0.631  1.0
  Zn  Zn27  1  0.750  0.924  0.869  1.0
  S  S28  1  0.250  0.125  0.653  1.0
  S  S29  1  0.250  0.625  0.847  1.0
  S  S30  1  0.750  0.875  0.347  1.0
  S  S31  1  0.750  0.375  0.153  1.0
  S  S32  1  0.250  0.148  0.245  1.0
  S  S33  1  0.250  0.648  0.255  1.0
  S  S34  1  0.750  0.852  0.755  1.0
  S  S35  1  0.750  0.352  0.745  1.0
  S  S36  1  0.250  0.343  0.977  1.0
  S  S37  1  0.250  0.843  0.523  1.0
  S  S38  1  0.750  0.657  0.023  1.0
  S  S39  1  0.750  0.157  0.477  1.0
  S  S40  1  0.250  0.393  0.338  1.0
  S  S41  1  0.250  0.893  0.162  1.0
  S  S42  1  0.750  0.607  0.662  1.0
  S  S43  1  0.750  0.107  0.838  1.0
  S  S44  1  0.250  0.388  0.563  1.0
  S  S45  1  0.250  0.888  0.937  1.0
  S  S46  1  0.750  0.612  0.437  1.0
  S  S47  1  0.750  0.112  0.063  1.0
[/CIF]
.
The compound described by Na4Zn3S5 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(2), and two equivalent S(4) atoms. In the second Na site, Na(2) is bonded to two equivalent S(1) and three equivalent S(3) atoms to form distorted NaS5 square pyramids that share corners with three equivalent Na(3)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, edges with four equivalent Na(2)S5 square pyramids,  an edgeedge with one Zn(2)S4 tetrahedra, and edges with three equivalent Zn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-54°. In the third Na site, Na(3) is bonded to one S(3), two equivalent S(4), and three equivalent S(5) atoms to form distorted NaS6 octahedra that share corners with three equivalent Na(2)S5 square pyramids,  a cornercorner with one Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, corners with two equivalent Zn(3)S4 tetrahedra, edges with four equivalent Na(3)S6 octahedra, edges with two equivalent Zn(1)S4 tetrahedra, and edges with three equivalent Zn(3)S4 tetrahedra. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(2), and two equivalent S(4) atoms. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one S(5), and two equivalent S(3) atoms to form ZnS4 tetrahedra that share  a cornercorner with one Na(3)S6 octahedra, corners with two equivalent Na(2)S5 square pyramids, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, corners with two equivalent Zn(3)S4 tetrahedra, edges with two equivalent Na(3)S6 octahedra, and edges with three equivalent Na(2)S5 square pyramids. The corner-sharing octahedral tilt angles are 15°. In the second Zn site, Zn(2) is bonded to one S(2), one S(4), and two equivalent S(1) atoms to form ZnS4 tetrahedra that share corners with two equivalent Na(3)S6 octahedra, corners with two equivalent Na(2)S5 square pyramids, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, corners with two equivalent Zn(3)S4 tetrahedra, and  an edgeedge with one Na(2)S5 square pyramid. The corner-sharing octahedral tilt angles are 48°. In the third Zn site, Zn(3) is bonded to one S(2), one S(4), and two equivalent S(5) atoms to form distorted ZnS4 tetrahedra that share corners with two equivalent Na(3)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, corners with two equivalent Zn(3)S4 tetrahedra, and edges with three equivalent Na(3)S6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are five inequivalent S sites. In the first S site, S(2) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(4), one Zn(2), and one Zn(3) atom. In the second S site, S(3) is bonded in a 7-coordinate geometry to one Na(3), one Na(4), three equivalent Na(2), and two equivalent Zn(1) atoms. In the third S site, S(4) is bonded in a 8-coordinate geometry to two equivalent Na(1), two equivalent Na(3), two equivalent Na(4), one Zn(2), and one Zn(3) atom. In the fourth S site, S(5) is bonded to three equivalent Na(3), one Zn(1), and two equivalent Zn(3) atoms to form a mixture of distorted corner and edge-sharing SNa3Zn3 octahedra. The corner-sharing octahedral tilt angles are 72°. In the fifth S site, S(1) is bonded to one Na(1), two equivalent Na(2), one Zn(1), and two equivalent Zn(2) atoms to form a mixture of distorted corner and edge-sharing SNa3Zn3 octahedra. The corner-sharing octahedral tilt angles are 72°. is represented by the Crystallographic Information File (CIF) [CIF]
data_Na4Zn3S5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   3.931
_cell_length_b   13.189
_cell_length_c   18.875
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   978.666
_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  0.250  0.998  0.765  1.0
  Na  Na1  1  0.250  0.498  0.735  1.0
  Na  Na2  1  0.750  0.002  0.235  1.0
  Na  Na3  1  0.750  0.502  0.265  1.0
  Na  Na4  1  0.250  0.007  0.417  1.0
  Na  Na5  1  0.250  0.507  0.083  1.0
  Na  Na6  1  0.750  0.993  0.583  1.0
  Na  Na7  1  0.750  0.493  0.917  1.0
  Na  Na8  1  0.250  0.109  0.951  1.0
  Na  Na9  1  0.250  0.609  0.549  1.0
  Na  Na10  1  0.750  0.891  0.049  1.0
  Na  Na11  1  0.750  0.391  0.451  1.0
  Na  Na12  1  0.250  0.273  0.834  1.0
  Na  Na13  1  0.250  0.773  0.666  1.0
  Na  Na14  1  0.750  0.727  0.166  1.0
  Na  Na15  1  0.750  0.227  0.334  1.0
  Zn  Zn16  1  0.250  0.209  0.541  1.0
  Zn  Zn17  1  0.250  0.709  0.959  1.0
  Zn  Zn18  1  0.750  0.791  0.459  1.0
  Zn  Zn19  1  0.750  0.291  0.041  1.0
  Zn  Zn20  1  0.250  0.319  0.217  1.0
  Zn  Zn21  1  0.250  0.819  0.283  1.0
  Zn  Zn22  1  0.750  0.681  0.783  1.0
  Zn  Zn23  1  0.750  0.181  0.717  1.0
  Zn  Zn24  1  0.250  0.576  0.369  1.0
  Zn  Zn25  1  0.250  0.076  0.131  1.0
  Zn  Zn26  1  0.750  0.424  0.631  1.0
  Zn  Zn27  1  0.750  0.924  0.869  1.0
  S  S28  1  0.250  0.125  0.653  1.0
  S  S29  1  0.250  0.625  0.847  1.0
  S  S30  1  0.750  0.875  0.347  1.0
  S  S31  1  0.750  0.375  0.153  1.0
  S  S32  1  0.250  0.148  0.245  1.0
  S  S33  1  0.250  0.648  0.255  1.0
  S  S34  1  0.750  0.852  0.755  1.0
  S  S35  1  0.750  0.352  0.745  1.0
  S  S36  1  0.250  0.343  0.977  1.0
  S  S37  1  0.250  0.843  0.523  1.0
  S  S38  1  0.750  0.657  0.023  1.0
  S  S39  1  0.750  0.157  0.477  1.0
  S  S40  1  0.250  0.393  0.338  1.0
  S  S41  1  0.250  0.893  0.162  1.0
  S  S42  1  0.750  0.607  0.662  1.0
  S  S43  1  0.750  0.107  0.838  1.0
  S  S44  1  0.250  0.388  0.563  1.0
  S  S45  1  0.250  0.888  0.937  1.0
  S  S46  1  0.750  0.612  0.437  1.0
  S  S47  1  0.750  0.112  0.063  1.0
[/CIF]
.