The material described by Ca4N4S is Orthorhombic Perovskite-like structured and crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form distorted CaN4 trigonal pyramids that share corners with three equivalent Ca(2)N6 octahedra, corners with four equivalent Ca(4)N5 square pyramids, corners with two equivalent Ca(1)N4 trigonal pyramids, and edges with three equivalent Ca(2)N6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the second Ca site, Ca(2) is bonded to one N(1), two equivalent N(3), and three equivalent N(2) atoms to form CaN6 octahedra that share  a cornercorner with one Ca(4)N5 square pyramid, corners with three equivalent Ca(1)N4 trigonal pyramids, edges with four equivalent Ca(2)N6 octahedra, edges with two equivalent Ca(4)N5 square pyramids, and edges with three equivalent Ca(1)N4 trigonal pyramids. In the third Ca site, Ca(3) is bonded in a 6-coordinate geometry to one N(3), two equivalent N(1), two equivalent N(4), and one S(1) atom. In the fourth Ca site, Ca(4) is bonded to one N(2), two equivalent N(1), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share  a cornercorner with one Ca(2)N6 octahedra, corners with four equivalent Ca(1)N4 trigonal pyramids, edges with two equivalent Ca(2)N6 octahedra, and edges with two equivalent Ca(4)N5 square pyramids. The corner-sharing octahedral tilt angles are 11°. There are four inequivalent N sites. In the first N site, N(4) is bonded in a 5-coordinate geometry to two equivalent Ca(3), two equivalent Ca(4), and one S(1) atom. In the second N site, N(1) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), and two equivalent Ca(4) atoms to form a mixture of corner and edge-sharing NCa6 octahedra. The corner-sharing octahedral tilt angles range from 7-53°. In the third N site, N(2) is bonded to one Ca(4), two equivalent Ca(1), and three equivalent Ca(2) atoms to form a mixture of corner and edge-sharing NCa6 octahedra. The corner-sharing octahedral tilt angles range from 7-53°. In the fourth N site, N(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(2), and one S(1) atom. S(1) is bonded in a distorted bent 120 degrees geometry to one Ca(3), one N(3), and one N(4) atom. is represented by the Crystallographic Information File (CIF) [CIF]
data_Ca4SN4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   11.630
_cell_length_b   3.553
_cell_length_c   14.654
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   605.441
_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
  Ca  Ca0  1  0.111  0.250  0.171  1.0
  Ca  Ca1  1  0.611  0.250  0.329  1.0
  Ca  Ca2  1  0.889  0.750  0.829  1.0
  Ca  Ca3  1  0.389  0.750  0.671  1.0
  Ca  Ca4  1  0.881  0.250  0.038  1.0
  Ca  Ca5  1  0.381  0.250  0.462  1.0
  Ca  Ca6  1  0.119  0.750  0.962  1.0
  Ca  Ca7  1  0.619  0.750  0.538  1.0
  Ca  Ca8  1  0.377  0.250  0.875  1.0
  Ca  Ca9  1  0.877  0.250  0.625  1.0
  Ca  Ca10  1  0.623  0.750  0.125  1.0
  Ca  Ca11  1  0.123  0.750  0.375  1.0
  Ca  Ca12  1  0.141  0.250  0.767  1.0
  Ca  Ca13  1  0.641  0.250  0.733  1.0
  Ca  Ca14  1  0.859  0.750  0.233  1.0
  Ca  Ca15  1  0.359  0.750  0.267  1.0
  S  S16  1  0.387  0.250  0.064  1.0
  S  S17  1  0.887  0.250  0.436  1.0
  S  S18  1  0.613  0.750  0.936  1.0
  S  S19  1  0.113  0.750  0.564  1.0
  N  N20  1  0.731  0.250  0.184  1.0
  N  N21  1  0.231  0.250  0.316  1.0
  N  N22  1  0.269  0.750  0.816  1.0
  N  N23  1  0.769  0.750  0.684  1.0
  N  N24  1  0.001  0.250  0.887  1.0
  N  N25  1  0.501  0.250  0.613  1.0
  N  N26  1  0.999  0.750  0.113  1.0
  N  N27  1  0.499  0.750  0.387  1.0
  N  N28  1  0.256  0.250  0.049  1.0
  N  N29  1  0.756  0.250  0.451  1.0
  N  N30  1  0.744  0.750  0.951  1.0
  N  N31  1  0.244  0.750  0.549  1.0
  N  N32  1  0.449  0.250  0.157  1.0
  N  N33  1  0.949  0.250  0.343  1.0
  N  N34  1  0.551  0.750  0.843  1.0
  N  N35  1  0.051  0.750  0.657  1.0
[/CIF]
.
The material described by Ca4N4S is Orthorhombic Perovskite-like structured and crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form distorted CaN4 trigonal pyramids that share corners with three equivalent Ca(2)N6 octahedra, corners with four equivalent Ca(4)N5 square pyramids, corners with two equivalent Ca(1)N4 trigonal pyramids, and edges with three equivalent Ca(2)N6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the second Ca site, Ca(2) is bonded to one N(1), two equivalent N(3), and three equivalent N(2) atoms to form CaN6 octahedra that share  a cornercorner with one Ca(4)N5 square pyramid, corners with three equivalent Ca(1)N4 trigonal pyramids, edges with four equivalent Ca(2)N6 octahedra, edges with two equivalent Ca(4)N5 square pyramids, and edges with three equivalent Ca(1)N4 trigonal pyramids. In the third Ca site, Ca(3) is bonded in a 6-coordinate geometry to one N(3), two equivalent N(1), two equivalent N(4), and one S(1) atom. In the fourth Ca site, Ca(4) is bonded to one N(2), two equivalent N(1), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share  a cornercorner with one Ca(2)N6 octahedra, corners with four equivalent Ca(1)N4 trigonal pyramids, edges with two equivalent Ca(2)N6 octahedra, and edges with two equivalent Ca(4)N5 square pyramids. The corner-sharing octahedral tilt angles are 11°. There are four inequivalent N sites. In the first N site, N(4) is bonded in a 5-coordinate geometry to two equivalent Ca(3), two equivalent Ca(4), and one S(1) atom. In the second N site, N(1) is bonded to one Ca(1), one Ca(2), two equivalent Ca(3), and two equivalent Ca(4) atoms to form a mixture of corner and edge-sharing NCa6 octahedra. The corner-sharing octahedral tilt angles range from 7-53°. In the third N site, N(2) is bonded to one Ca(4), two equivalent Ca(1), and three equivalent Ca(2) atoms to form a mixture of corner and edge-sharing NCa6 octahedra. The corner-sharing octahedral tilt angles range from 7-53°. In the fourth N site, N(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(3), two equivalent Ca(2), and one S(1) atom. S(1) is bonded in a distorted bent 120 degrees geometry to one Ca(3), one N(3), and one N(4) atom. is represented by the Crystallographic Information File (CIF) [CIF]
data_Ca4SN4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   11.630
_cell_length_b   3.553
_cell_length_c   14.654
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   605.441
_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
  Ca  Ca0  1  0.111  0.250  0.171  1.0
  Ca  Ca1  1  0.611  0.250  0.329  1.0
  Ca  Ca2  1  0.889  0.750  0.829  1.0
  Ca  Ca3  1  0.389  0.750  0.671  1.0
  Ca  Ca4  1  0.881  0.250  0.038  1.0
  Ca  Ca5  1  0.381  0.250  0.462  1.0
  Ca  Ca6  1  0.119  0.750  0.962  1.0
  Ca  Ca7  1  0.619  0.750  0.538  1.0
  Ca  Ca8  1  0.377  0.250  0.875  1.0
  Ca  Ca9  1  0.877  0.250  0.625  1.0
  Ca  Ca10  1  0.623  0.750  0.125  1.0
  Ca  Ca11  1  0.123  0.750  0.375  1.0
  Ca  Ca12  1  0.141  0.250  0.767  1.0
  Ca  Ca13  1  0.641  0.250  0.733  1.0
  Ca  Ca14  1  0.859  0.750  0.233  1.0
  Ca  Ca15  1  0.359  0.750  0.267  1.0
  S  S16  1  0.387  0.250  0.064  1.0
  S  S17  1  0.887  0.250  0.436  1.0
  S  S18  1  0.613  0.750  0.936  1.0
  S  S19  1  0.113  0.750  0.564  1.0
  N  N20  1  0.731  0.250  0.184  1.0
  N  N21  1  0.231  0.250  0.316  1.0
  N  N22  1  0.269  0.750  0.816  1.0
  N  N23  1  0.769  0.750  0.684  1.0
  N  N24  1  0.001  0.250  0.887  1.0
  N  N25  1  0.501  0.250  0.613  1.0
  N  N26  1  0.999  0.750  0.113  1.0
  N  N27  1  0.499  0.750  0.387  1.0
  N  N28  1  0.256  0.250  0.049  1.0
  N  N29  1  0.756  0.250  0.451  1.0
  N  N30  1  0.744  0.750  0.951  1.0
  N  N31  1  0.244  0.750  0.549  1.0
  N  N32  1  0.449  0.250  0.157  1.0
  N  N33  1  0.949  0.250  0.343  1.0
  N  N34  1  0.551  0.750  0.843  1.0
  N  N35  1  0.051  0.750  0.657  1.0
[/CIF]
.