The crystal structure described by Na2BiO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fdd2 space group. There are four 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(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the fourth Na site, Na(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second Bi site, Bi(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(4)O6 octahedra, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. is represented by the CIF file [CIF]
data_Na2BiO3
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   11.239
_cell_length_b   10.696
_cell_length_c   5.867
_cell_angle_alpha   79.674
_cell_angle_beta   69.430
_cell_angle_gamma   30.891
_symmetry_Int_Tables_number   1
_cell_volume   327.850
_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  0.995  0.995  0.505  1.0
  Na  Na1  1  0.419  0.419  0.581  1.0
  Na  Na2  1  0.829  0.829  0.671  1.0
  Na  Na3  1  0.250  0.251  0.750  1.0
  Na  Na4  1  0.745  0.745  0.255  1.0
  Na  Na5  1  0.669  0.669  0.830  1.0
  Na  Na6  1  0.579  0.579  0.421  1.0
  Na  Na7  1  0.501  0.500  1.000  1.0
  Bi  Bi8  1  0.915  0.914  0.085  1.0
  Bi  Bi9  1  0.332  0.332  0.168  1.0
  Bi  Bi10  1  0.165  0.164  0.336  1.0
  Bi  Bi11  1  0.082  0.082  0.918  1.0
  O  O12  1  0.136  0.689  0.308  1.0
  O  O13  1  0.689  0.136  0.867  1.0
  O  O14  1  0.075  0.606  0.932  1.0
  O  O15  1  0.606  0.075  0.387  1.0
  O  O16  1  0.021  0.462  0.485  1.0
  O  O17  1  0.462  0.020  0.033  1.0
  O  O18  1  0.383  0.942  0.561  1.0
  O  O19  1  0.942  0.383  0.114  1.0
  O  O20  1  0.863  0.318  0.644  1.0
  O  O21  1  0.318  0.863  0.175  1.0
  O  O22  1  0.217  0.765  0.788  1.0
  O  O23  1  0.765  0.217  0.230  1.0
[/CIF]
.
The crystal structure described by Na2BiO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fdd2 space group. There are four 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(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. In the fourth Na site, Na(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second Bi site, Bi(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(4)O6 octahedra, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. is represented by the CIF file [CIF]
data_Na2BiO3
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   11.239
_cell_length_b   10.696
_cell_length_c   5.867
_cell_angle_alpha   79.674
_cell_angle_beta   69.430
_cell_angle_gamma   30.891
_symmetry_Int_Tables_number   1
_cell_volume   327.850
_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  0.995  0.995  0.505  1.0
  Na  Na1  1  0.419  0.419  0.581  1.0
  Na  Na2  1  0.829  0.829  0.671  1.0
  Na  Na3  1  0.250  0.251  0.750  1.0
  Na  Na4  1  0.745  0.745  0.255  1.0
  Na  Na5  1  0.669  0.669  0.830  1.0
  Na  Na6  1  0.579  0.579  0.421  1.0
  Na  Na7  1  0.501  0.500  1.000  1.0
  Bi  Bi8  1  0.915  0.914  0.085  1.0
  Bi  Bi9  1  0.332  0.332  0.168  1.0
  Bi  Bi10  1  0.165  0.164  0.336  1.0
  Bi  Bi11  1  0.082  0.082  0.918  1.0
  O  O12  1  0.136  0.689  0.308  1.0
  O  O13  1  0.689  0.136  0.867  1.0
  O  O14  1  0.075  0.606  0.932  1.0
  O  O15  1  0.606  0.075  0.387  1.0
  O  O16  1  0.021  0.462  0.485  1.0
  O  O17  1  0.462  0.020  0.033  1.0
  O  O18  1  0.383  0.942  0.561  1.0
  O  O19  1  0.942  0.383  0.114  1.0
  O  O20  1  0.863  0.318  0.644  1.0
  O  O21  1  0.318  0.863  0.175  1.0
  O  O22  1  0.217  0.765  0.788  1.0
  O  O23  1  0.765  0.217  0.230  1.0
[/CIF]
.