The material structure described by NaV5O8 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a 4-coordinate geometry to four equivalent O(2) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second V site, V(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form a mixture of distorted face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-59°. In the third V site, V(3) is bonded to one O(1), two equivalent O(4), and three equivalent O(3) atoms to form a mixture of face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-59°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one V(2), one V(3), and two equivalent V(1) atoms to form OV4 trigonal pyramids that share corners with two equivalent O(2)Na2V3 trigonal bipyramids, corners with four equivalent O(1)V4 trigonal pyramids, edges with two equivalent O(2)Na2V3 trigonal bipyramids, and  an edgeedge with one O(1)V4 trigonal pyramid. In the second O site, O(2) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form distorted ONa2V3 trigonal bipyramids that share corners with three equivalent O(2)Na2V3 trigonal bipyramids, corners with two equivalent O(1)V4 trigonal pyramids, edges with three equivalent O(2)Na2V3 trigonal bipyramids, and edges with two equivalent O(1)V4 trigonal pyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent V(3) and three equivalent V(2) atoms. is represented by the Crystallographic Information File (CIF) [CIF]
data_NaV5O8
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   3.058
_cell_length_b   7.257
_cell_length_c   7.882
_cell_angle_alpha   105.884
_cell_angle_beta   101.184
_cell_angle_gamma   90.001
_symmetry_Int_Tables_number   1
_cell_volume   164.762
_cell_formula_units_Z   1
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  0.000  0.000  1.000  1.0
  O  O1  1  0.918  0.376  0.837  1.0
  O  O2  1  0.082  0.624  0.163  1.0
  O  O3  1  0.424  0.699  0.849  1.0
  O  O4  1  0.576  0.301  0.151  1.0
  O  O5  1  0.326  0.019  0.653  1.0
  O  O6  1  0.674  0.981  0.347  1.0
  O  O7  1  0.269  0.358  0.539  1.0
  O  O8  1  0.731  0.642  0.461  1.0
  V  V9  1  0.500  0.500  1.000  1.0
  V  V10  1  0.846  0.571  0.693  1.0
  V  V11  1  0.154  0.429  0.307  1.0
  V  V12  1  0.798  0.168  0.596  1.0
  V  V13  1  0.202  0.832  0.404  1.0
[/CIF]
.
The material structure described by NaV5O8 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a 4-coordinate geometry to four equivalent O(2) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the second V site, V(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form a mixture of distorted face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-59°. In the third V site, V(3) is bonded to one O(1), two equivalent O(4), and three equivalent O(3) atoms to form a mixture of face, corner, and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 42-59°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one V(2), one V(3), and two equivalent V(1) atoms to form OV4 trigonal pyramids that share corners with two equivalent O(2)Na2V3 trigonal bipyramids, corners with four equivalent O(1)V4 trigonal pyramids, edges with two equivalent O(2)Na2V3 trigonal bipyramids, and  an edgeedge with one O(1)V4 trigonal pyramid. In the second O site, O(2) is bonded to two equivalent Na(1), one V(1), and two equivalent V(2) atoms to form distorted ONa2V3 trigonal bipyramids that share corners with three equivalent O(2)Na2V3 trigonal bipyramids, corners with two equivalent O(1)V4 trigonal pyramids, edges with three equivalent O(2)Na2V3 trigonal bipyramids, and edges with two equivalent O(1)V4 trigonal pyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent V(3) and three equivalent V(2) atoms. is represented by the Crystallographic Information File (CIF) [CIF]
data_NaV5O8
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   3.058
_cell_length_b   7.257
_cell_length_c   7.882
_cell_angle_alpha   105.884
_cell_angle_beta   101.184
_cell_angle_gamma   90.001
_symmetry_Int_Tables_number   1
_cell_volume   164.762
_cell_formula_units_Z   1
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  0.000  0.000  1.000  1.0
  O  O1  1  0.918  0.376  0.837  1.0
  O  O2  1  0.082  0.624  0.163  1.0
  O  O3  1  0.424  0.699  0.849  1.0
  O  O4  1  0.576  0.301  0.151  1.0
  O  O5  1  0.326  0.019  0.653  1.0
  O  O6  1  0.674  0.981  0.347  1.0
  O  O7  1  0.269  0.358  0.539  1.0
  O  O8  1  0.731  0.642  0.461  1.0
  V  V9  1  0.500  0.500  1.000  1.0
  V  V10  1  0.846  0.571  0.693  1.0
  V  V11  1  0.154  0.429  0.307  1.0
  V  V12  1  0.798  0.168  0.596  1.0
  V  V13  1  0.202  0.832  0.404  1.0
[/CIF]
.