The crystal structure described by Na4Bi2As(CO4)4 crystallizes in the orthorhombic Fddd space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-83°. In the second Na site, Na(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-83°. C(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. Bi(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form BiO6 octahedra that share edges with two equivalent Na(1)O6 octahedra and edges with two equivalent Na(2)O6 octahedra. As(1) is bonded to four equivalent O(2) atoms to form AsO4 tetrahedra that share edges with two equivalent Na(1)O6 octahedra and edges with two equivalent Na(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one As(1) atom. In the second O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one C(1), and one Bi(1) atom. In the third O site, O(1) is bonded in a distorted single-bond geometry to one Na(1), one C(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one C(1), and one Bi(1) atom. is represented by the CIF file [CIF]
data_Na4Bi2As(CO4)4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   10.704
_cell_length_b   10.604
_cell_length_c   10.324
_cell_angle_alpha   61.507
_cell_angle_beta   60.538
_cell_angle_gamma   57.955
_symmetry_Int_Tables_number   1
_cell_volume   826.932
_cell_formula_units_Z   2
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  0.954  0.546  0.954  1.0
  Na  Na1  1  0.956  0.544  0.544  1.0
  Na  Na2  1  0.706  0.294  0.294  1.0
  Na  Na3  1  0.704  0.296  0.704  1.0
  Na  Na4  1  0.546  0.954  0.546  1.0
  Na  Na5  1  0.544  0.956  0.956  1.0
  Na  Na6  1  0.294  0.706  0.706  1.0
  Na  Na7  1  0.296  0.704  0.296  1.0
  Bi  Bi8  1  0.125  0.625  0.125  1.0
  Bi  Bi9  1  0.625  0.125  0.125  1.0
  Bi  Bi10  1  0.125  0.125  0.125  1.0
  Bi  Bi11  1  0.125  0.125  0.625  1.0
  As  As12  1  0.500  0.500  0.500  1.0
  As  As13  1  0.750  0.750  0.750  1.0
  C  C14  1  0.896  0.283  0.913  1.0
  C  C15  1  0.967  0.354  0.342  1.0
  C  C16  1  0.913  0.908  0.896  1.0
  C  C17  1  0.908  0.913  0.283  1.0
  C  C18  1  0.342  0.337  0.967  1.0
  C  C19  1  0.337  0.342  0.354  1.0
  C  C20  1  0.283  0.896  0.908  1.0
  C  C21  1  0.354  0.967  0.337  1.0
  O  O22  1  0.006  0.291  0.926  1.0
  O  O23  1  0.558  0.559  0.299  1.0
  O  O24  1  0.774  0.272  0.033  1.0
  O  O25  1  0.978  0.476  0.330  1.0
  O  O26  1  0.033  0.920  0.774  1.0
  O  O27  1  0.961  0.343  0.224  1.0
  O  O28  1  0.299  0.584  0.558  1.0
  O  O29  1  0.559  0.558  0.584  1.0
  O  O30  1  0.471  0.224  0.343  1.0
  O  O31  1  0.920  0.033  0.272  1.0
  O  O32  1  0.959  0.244  0.473  1.0
  O  O33  1  0.584  0.299  0.559  1.0
  O  O34  1  0.926  0.777  0.006  1.0
  O  O35  1  0.777  0.926  0.291  1.0
  O  O36  1  0.907  0.289  0.779  1.0
  O  O37  1  0.224  0.471  0.961  1.0
  O  O38  1  0.026  0.779  0.289  1.0
  O  O39  1  0.343  0.961  0.471  1.0
  O  O40  1  0.473  0.324  0.959  1.0
  O  O41  1  0.324  0.473  0.244  1.0
  O  O42  1  0.666  0.951  0.691  1.0
  O  O43  1  0.291  0.006  0.777  1.0
  O  O44  1  0.330  0.217  0.978  1.0
  O  O45  1  0.779  0.026  0.907  1.0
  O  O46  1  0.691  0.692  0.666  1.0
  O  O47  1  0.951  0.666  0.692  1.0
  O  O48  1  0.289  0.907  0.026  1.0
  O  O49  1  0.217  0.330  0.476  1.0
  O  O50  1  0.272  0.774  0.920  1.0
  O  O51  1  0.476  0.978  0.217  1.0
  O  O52  1  0.692  0.691  0.951  1.0
  O  O53  1  0.244  0.959  0.324  1.0
[/CIF]
.
The crystal structure described by Na4Bi2As(CO4)4 crystallizes in the orthorhombic Fddd space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-83°. In the second Na site, Na(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-83°. C(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. Bi(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form BiO6 octahedra that share edges with two equivalent Na(1)O6 octahedra and edges with two equivalent Na(2)O6 octahedra. As(1) is bonded to four equivalent O(2) atoms to form AsO4 tetrahedra that share edges with two equivalent Na(1)O6 octahedra and edges with two equivalent Na(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one As(1) atom. In the second O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one C(1), and one Bi(1) atom. In the third O site, O(1) is bonded in a distorted single-bond geometry to one Na(1), one C(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one C(1), and one Bi(1) atom. is represented by the CIF file [CIF]
data_Na4Bi2As(CO4)4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   10.704
_cell_length_b   10.604
_cell_length_c   10.324
_cell_angle_alpha   61.507
_cell_angle_beta   60.538
_cell_angle_gamma   57.955
_symmetry_Int_Tables_number   1
_cell_volume   826.932
_cell_formula_units_Z   2
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  0.954  0.546  0.954  1.0
  Na  Na1  1  0.956  0.544  0.544  1.0
  Na  Na2  1  0.706  0.294  0.294  1.0
  Na  Na3  1  0.704  0.296  0.704  1.0
  Na  Na4  1  0.546  0.954  0.546  1.0
  Na  Na5  1  0.544  0.956  0.956  1.0
  Na  Na6  1  0.294  0.706  0.706  1.0
  Na  Na7  1  0.296  0.704  0.296  1.0
  Bi  Bi8  1  0.125  0.625  0.125  1.0
  Bi  Bi9  1  0.625  0.125  0.125  1.0
  Bi  Bi10  1  0.125  0.125  0.125  1.0
  Bi  Bi11  1  0.125  0.125  0.625  1.0
  As  As12  1  0.500  0.500  0.500  1.0
  As  As13  1  0.750  0.750  0.750  1.0
  C  C14  1  0.896  0.283  0.913  1.0
  C  C15  1  0.967  0.354  0.342  1.0
  C  C16  1  0.913  0.908  0.896  1.0
  C  C17  1  0.908  0.913  0.283  1.0
  C  C18  1  0.342  0.337  0.967  1.0
  C  C19  1  0.337  0.342  0.354  1.0
  C  C20  1  0.283  0.896  0.908  1.0
  C  C21  1  0.354  0.967  0.337  1.0
  O  O22  1  0.006  0.291  0.926  1.0
  O  O23  1  0.558  0.559  0.299  1.0
  O  O24  1  0.774  0.272  0.033  1.0
  O  O25  1  0.978  0.476  0.330  1.0
  O  O26  1  0.033  0.920  0.774  1.0
  O  O27  1  0.961  0.343  0.224  1.0
  O  O28  1  0.299  0.584  0.558  1.0
  O  O29  1  0.559  0.558  0.584  1.0
  O  O30  1  0.471  0.224  0.343  1.0
  O  O31  1  0.920  0.033  0.272  1.0
  O  O32  1  0.959  0.244  0.473  1.0
  O  O33  1  0.584  0.299  0.559  1.0
  O  O34  1  0.926  0.777  0.006  1.0
  O  O35  1  0.777  0.926  0.291  1.0
  O  O36  1  0.907  0.289  0.779  1.0
  O  O37  1  0.224  0.471  0.961  1.0
  O  O38  1  0.026  0.779  0.289  1.0
  O  O39  1  0.343  0.961  0.471  1.0
  O  O40  1  0.473  0.324  0.959  1.0
  O  O41  1  0.324  0.473  0.244  1.0
  O  O42  1  0.666  0.951  0.691  1.0
  O  O43  1  0.291  0.006  0.777  1.0
  O  O44  1  0.330  0.217  0.978  1.0
  O  O45  1  0.779  0.026  0.907  1.0
  O  O46  1  0.691  0.692  0.666  1.0
  O  O47  1  0.951  0.666  0.692  1.0
  O  O48  1  0.289  0.907  0.026  1.0
  O  O49  1  0.217  0.330  0.476  1.0
  O  O50  1  0.272  0.774  0.920  1.0
  O  O51  1  0.476  0.978  0.217  1.0
  O  O52  1  0.692  0.691  0.951  1.0
  O  O53  1  0.244  0.959  0.324  1.0
[/CIF]
.