The compound described by Na3VO13I crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(11), one O(12), one O(3), and one O(9) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(3), and one O(7) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and two equivalent O(8) atoms. V(1) is bonded in a 6-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and two equivalent O(8) atoms. There are thirteen inequivalent O sites. In the first O site, O(12) is bonded in a water-like geometry to one Na(1) and one Na(2) atom. In the second O site, O(13) is bonded in a water-like geometry to one Na(2) and one O(11) atom. In the third O site, O(1) is bonded in a water-like geometry to one Na(2) and one I(1) atom. In the fourth O site, O(2) is bonded in a water-like geometry to one Na(2) and one I(1) atom. In the fifth O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and one I(1) atom to form a mixture of edge and corner-sharing ONa3I tetrahedra. In the sixth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(3) and one V(1) atom. In the seventh O site, O(5) is bonded in a distorted single-bond geometry to one Na(3) and one V(1) atom. In the eighth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Na(3), one V(1), and one I(1) atom. In the ninth O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one V(1), and one I(1) atom. In the tenth O site, O(8) is bonded to two equivalent Na(3), two equivalent V(1), and one I(1) atom to form distorted ONa2V2I trigonal bipyramids that share  a cornercorner with one O(3)Na3I tetrahedra,  an edgeedge with one O(3)Na3I tetrahedra, and edges with two equivalent O(8)Na2V2I trigonal bipyramids. In the eleventh O site, O(9) is bonded in a linear geometry to one Na(1) and one O(10) atom. In the twelfth O site, O(10) is bonded in a distorted single-bond geometry to one Na(3) and one O(9) atom. In the thirteenth O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one O(13) atom. I(1) is bonded in an octahedral geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom. is represented by the CIF file [CIF]
data_Na3VIO13
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.077
_cell_length_b   8.353
_cell_length_c   10.851
_cell_angle_alpha   77.951
_cell_angle_beta   88.693
_cell_angle_gamma   90.201
_symmetry_Int_Tables_number   1
_cell_volume   538.486
_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  0.704  0.460  0.333  1.0
  Na  Na1  1  0.296  0.540  0.667  1.0
  Na  Na2  1  0.350  0.883  0.346  1.0
  Na  Na3  1  0.650  0.117  0.654  1.0
  Na  Na4  1  0.392  0.778  0.060  1.0
  Na  Na5  1  0.608  0.222  0.940  1.0
  V  V6  1  0.075  0.183  0.048  1.0
  V  V7  1  0.925  0.817  0.952  1.0
  I  I8  1  0.151  0.129  0.772  1.0
  I  I9  1  0.849  0.871  0.228  1.0
  O  O10  1  0.298  0.985  0.695  1.0
  O  O11  1  0.702  0.015  0.305  1.0
  O  O12  1  0.011  0.244  0.626  1.0
  O  O13  1  0.989  0.756  0.374  1.0
  O  O14  1  0.392  0.274  0.759  1.0
  O  O15  1  0.608  0.726  0.241  1.0
  O  O16  1  0.318  0.286  0.061  1.0
  O  O17  1  0.682  0.714  0.939  1.0
  O  O18  1  0.890  0.301  0.106  1.0
  O  O19  1  0.110  0.699  0.894  1.0
  O  O20  1  0.991  0.263  0.877  1.0
  O  O21  1  0.009  0.737  0.123  1.0
  O  O22  1  0.886  0.987  0.807  1.0
  O  O23  1  0.114  0.013  0.193  1.0
  O  O24  1  0.219  0.017  0.945  1.0
  O  O25  1  0.781  0.983  0.055  1.0
  O  O26  1  0.099  0.439  0.215  1.0
  O  O27  1  0.901  0.561  0.785  1.0
  O  O28  1  0.289  0.430  0.181  1.0
  O  O29  1  0.711  0.570  0.819  1.0
  O  O30  1  0.439  0.217  0.439  1.0
  O  O31  1  0.561  0.783  0.561  1.0
  O  O32  1  0.268  0.578  0.438  1.0
  O  O33  1  0.732  0.422  0.562  1.0
  O  O34  1  0.249  0.173  0.427  1.0
  O  O35  1  0.751  0.827  0.573  1.0
[/CIF]
.
The compound described by Na3VO13I crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(11), one O(12), one O(3), and one O(9) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(13), one O(2), one O(3), and one O(7) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and two equivalent O(8) atoms. V(1) is bonded in a 6-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and two equivalent O(8) atoms. There are thirteen inequivalent O sites. In the first O site, O(12) is bonded in a water-like geometry to one Na(1) and one Na(2) atom. In the second O site, O(13) is bonded in a water-like geometry to one Na(2) and one O(11) atom. In the third O site, O(1) is bonded in a water-like geometry to one Na(2) and one I(1) atom. In the fourth O site, O(2) is bonded in a water-like geometry to one Na(2) and one I(1) atom. In the fifth O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and one I(1) atom to form a mixture of edge and corner-sharing ONa3I tetrahedra. In the sixth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(3) and one V(1) atom. In the seventh O site, O(5) is bonded in a distorted single-bond geometry to one Na(3) and one V(1) atom. In the eighth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Na(3), one V(1), and one I(1) atom. In the ninth O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one V(1), and one I(1) atom. In the tenth O site, O(8) is bonded to two equivalent Na(3), two equivalent V(1), and one I(1) atom to form distorted ONa2V2I trigonal bipyramids that share  a cornercorner with one O(3)Na3I tetrahedra,  an edgeedge with one O(3)Na3I tetrahedra, and edges with two equivalent O(8)Na2V2I trigonal bipyramids. In the eleventh O site, O(9) is bonded in a linear geometry to one Na(1) and one O(10) atom. In the twelfth O site, O(10) is bonded in a distorted single-bond geometry to one Na(3) and one O(9) atom. In the thirteenth O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one O(13) atom. I(1) is bonded in an octahedral geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom. is represented by the CIF file [CIF]
data_Na3VIO13
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.077
_cell_length_b   8.353
_cell_length_c   10.851
_cell_angle_alpha   77.951
_cell_angle_beta   88.693
_cell_angle_gamma   90.201
_symmetry_Int_Tables_number   1
_cell_volume   538.486
_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  0.704  0.460  0.333  1.0
  Na  Na1  1  0.296  0.540  0.667  1.0
  Na  Na2  1  0.350  0.883  0.346  1.0
  Na  Na3  1  0.650  0.117  0.654  1.0
  Na  Na4  1  0.392  0.778  0.060  1.0
  Na  Na5  1  0.608  0.222  0.940  1.0
  V  V6  1  0.075  0.183  0.048  1.0
  V  V7  1  0.925  0.817  0.952  1.0
  I  I8  1  0.151  0.129  0.772  1.0
  I  I9  1  0.849  0.871  0.228  1.0
  O  O10  1  0.298  0.985  0.695  1.0
  O  O11  1  0.702  0.015  0.305  1.0
  O  O12  1  0.011  0.244  0.626  1.0
  O  O13  1  0.989  0.756  0.374  1.0
  O  O14  1  0.392  0.274  0.759  1.0
  O  O15  1  0.608  0.726  0.241  1.0
  O  O16  1  0.318  0.286  0.061  1.0
  O  O17  1  0.682  0.714  0.939  1.0
  O  O18  1  0.890  0.301  0.106  1.0
  O  O19  1  0.110  0.699  0.894  1.0
  O  O20  1  0.991  0.263  0.877  1.0
  O  O21  1  0.009  0.737  0.123  1.0
  O  O22  1  0.886  0.987  0.807  1.0
  O  O23  1  0.114  0.013  0.193  1.0
  O  O24  1  0.219  0.017  0.945  1.0
  O  O25  1  0.781  0.983  0.055  1.0
  O  O26  1  0.099  0.439  0.215  1.0
  O  O27  1  0.901  0.561  0.785  1.0
  O  O28  1  0.289  0.430  0.181  1.0
  O  O29  1  0.711  0.570  0.819  1.0
  O  O30  1  0.439  0.217  0.439  1.0
  O  O31  1  0.561  0.783  0.561  1.0
  O  O32  1  0.268  0.578  0.438  1.0
  O  O33  1  0.732  0.422  0.562  1.0
  O  O34  1  0.249  0.173  0.427  1.0
  O  O35  1  0.751  0.827  0.573  1.0
[/CIF]
.