The material described by Na3(VSe2)5 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one Se(1), one Se(10), one Se(4), one Se(5), one Se(6), and one Se(7) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Se(2), one Se(3), one Se(6), one Se(7), one Se(8), and one Se(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one Se(1), one Se(10), one Se(4), one Se(5), one Se(8), and one Se(9) atom. There are five inequivalent V sites. In the first V site, V(1) is bonded to one Se(1), one Se(10), one Se(2), one Se(5), one Se(6), and one Se(9) atom to form edge-sharing VSe6 octahedra. In the second V site, V(2) is bonded to one Se(10), one Se(2), one Se(3), one Se(4), one Se(7), and one Se(8) atom to form edge-sharing VSe6 octahedra. In the third V site, V(3) is bonded to one Se(1), one Se(3), one Se(4), one Se(5), one Se(6), and one Se(9) atom to form edge-sharing VSe6 octahedra. In the fourth V site, V(4) is bonded to one Se(10), one Se(2), one Se(5), one Se(6), one Se(7), and one Se(8) atom to form edge-sharing VSe6 octahedra. In the fifth V site, V(5) is bonded to one Se(1), one Se(3), one Se(4), one Se(7), one Se(8), and one Se(9) atom to form edge-sharing VSe6 octahedra. There are ten inequivalent Se sites. In the first Se site, Se(1) is bonded to one Na(1), one Na(3), one V(1), one V(3), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids, corners with two equivalent Se(7)Na2V3 square pyramids, corners with two equivalent Se(9)Na2V3 square pyramids,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and edges with two equivalent Se(4)Na2V3 trigonal bipyramids. In the second Se site, Se(2) is bonded to one Na(2), one V(1), one V(2), and one V(4) atom to form a mixture of distorted corner and edge-sharing SeNaV3 trigonal pyramids. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one V(2), one V(3), and one V(5) atom. In the fourth Se site, Se(4) is bonded to one Na(1), one Na(3), one V(2), one V(3), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(5)Na2V3 square pyramid,  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with three equivalent Se(10)Na2V3 square pyramids,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and edges with two equivalent Se(1)Na2V3 trigonal bipyramids. In the fifth Se site, Se(5) is bonded to one Na(1), one Na(3), one V(1), one V(3), and one V(4) atom to form SeNa2V3 square pyramids that share  a cornercorner with one Se(9)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(6)Na2V3 trigonal bipyramids, corners with two equivalent Se(8)Na2V3 trigonal bipyramids,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid, edges with two equivalent Se(10)Na2V3 square pyramids,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the sixth Se site, Se(6) is bonded to one Na(1), one Na(2), one V(1), one V(3), and one V(4) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids,  a cornercorner with one Se(1)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the seventh Se site, Se(7) is bonded to one Na(1), one Na(2), one V(2), one V(4), and one V(5) atom to form distorted SeNa2V3 square pyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(8)Na2V3 trigonal bipyramids,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the eighth Se site, Se(8) is bonded to one Na(2), one Na(3), one V(2), one V(4), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids, corners with two equivalent Se(7)Na2V3 square pyramids,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the ninth Se site, Se(9) is bonded to one Na(2), one Na(3), one V(1), one V(3), and one V(5) atom to form SeNa2V3 square pyramids that share  a cornercorner with one Se(5)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(2)NaV3 trigonal pyramids,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(8)Na2V3 trigonal bipyramid. In the tenth Se site, Se(10) is bonded to one Na(1), one Na(3), one V(1), one V(2), and one V(4) atom to form distorted SeNa2V3 square pyramids that share  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(1)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid, corners with three equivalent Se(4)Na2V3 trigonal bipyramids,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid, edges with two equivalent Se(5)Na2V3 square pyramids,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. is represented by the CIF file [CIF]
data_Na3(VSe2)5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   38.017
_cell_length_b   22.300
_cell_length_c   14.771
_cell_angle_alpha   12.269
_cell_angle_beta   13.587
_cell_angle_gamma   9.062
_symmetry_Int_Tables_number   1
_cell_volume   409.724
_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  0.346  0.141  0.168  1.0
  Na  Na1  1  0.576  0.121  0.130  1.0
  Na  Na2  1  0.737  0.178  0.143  1.0
  V  V3  1  0.029  0.940  0.015  1.0
  V  V4  1  0.194  0.037  0.963  1.0
  V  V5  1  0.364  0.041  0.029  1.0
  V  V6  1  0.566  0.013  0.065  1.0
  V  V7  1  0.830  0.989  0.941  1.0
  Se  Se8  1  0.029  0.403  0.429  1.0
  Se  Se9  1  0.235  0.400  0.426  1.0
  Se  Se10  1  0.163  0.614  0.566  1.0
  Se  Se11  1  0.447  0.388  0.394  1.0
  Se  Se12  1  0.355  0.606  0.596  1.0
  Se  Se13  1  0.639  0.385  0.416  1.0
  Se  Se14  1  0.555  0.599  0.611  1.0
  Se  Se15  1  0.840  0.407  0.392  1.0
  Se  Se16  1  0.755  0.613  0.605  1.0
  Se  Se17  1  0.942  0.625  0.610  1.0
[/CIF]
.
The material described by Na3(VSe2)5 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one Se(1), one Se(10), one Se(4), one Se(5), one Se(6), and one Se(7) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Se(2), one Se(3), one Se(6), one Se(7), one Se(8), and one Se(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one Se(1), one Se(10), one Se(4), one Se(5), one Se(8), and one Se(9) atom. There are five inequivalent V sites. In the first V site, V(1) is bonded to one Se(1), one Se(10), one Se(2), one Se(5), one Se(6), and one Se(9) atom to form edge-sharing VSe6 octahedra. In the second V site, V(2) is bonded to one Se(10), one Se(2), one Se(3), one Se(4), one Se(7), and one Se(8) atom to form edge-sharing VSe6 octahedra. In the third V site, V(3) is bonded to one Se(1), one Se(3), one Se(4), one Se(5), one Se(6), and one Se(9) atom to form edge-sharing VSe6 octahedra. In the fourth V site, V(4) is bonded to one Se(10), one Se(2), one Se(5), one Se(6), one Se(7), and one Se(8) atom to form edge-sharing VSe6 octahedra. In the fifth V site, V(5) is bonded to one Se(1), one Se(3), one Se(4), one Se(7), one Se(8), and one Se(9) atom to form edge-sharing VSe6 octahedra. There are ten inequivalent Se sites. In the first Se site, Se(1) is bonded to one Na(1), one Na(3), one V(1), one V(3), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids, corners with two equivalent Se(7)Na2V3 square pyramids, corners with two equivalent Se(9)Na2V3 square pyramids,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and edges with two equivalent Se(4)Na2V3 trigonal bipyramids. In the second Se site, Se(2) is bonded to one Na(2), one V(1), one V(2), and one V(4) atom to form a mixture of distorted corner and edge-sharing SeNaV3 trigonal pyramids. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one V(2), one V(3), and one V(5) atom. In the fourth Se site, Se(4) is bonded to one Na(1), one Na(3), one V(2), one V(3), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(5)Na2V3 square pyramid,  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with three equivalent Se(10)Na2V3 square pyramids,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and edges with two equivalent Se(1)Na2V3 trigonal bipyramids. In the fifth Se site, Se(5) is bonded to one Na(1), one Na(3), one V(1), one V(3), and one V(4) atom to form SeNa2V3 square pyramids that share  a cornercorner with one Se(9)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(6)Na2V3 trigonal bipyramids, corners with two equivalent Se(8)Na2V3 trigonal bipyramids,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid, edges with two equivalent Se(10)Na2V3 square pyramids,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the sixth Se site, Se(6) is bonded to one Na(1), one Na(2), one V(1), one V(3), and one V(4) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids,  a cornercorner with one Se(1)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the seventh Se site, Se(7) is bonded to one Na(1), one Na(2), one V(2), one V(4), and one V(5) atom to form distorted SeNa2V3 square pyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(8)Na2V3 trigonal bipyramids,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the eighth Se site, Se(8) is bonded to one Na(2), one Na(3), one V(2), one V(4), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids, corners with two equivalent Se(7)Na2V3 square pyramids,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the ninth Se site, Se(9) is bonded to one Na(2), one Na(3), one V(1), one V(3), and one V(5) atom to form SeNa2V3 square pyramids that share  a cornercorner with one Se(5)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(2)NaV3 trigonal pyramids,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(8)Na2V3 trigonal bipyramid. In the tenth Se site, Se(10) is bonded to one Na(1), one Na(3), one V(1), one V(2), and one V(4) atom to form distorted SeNa2V3 square pyramids that share  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(1)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid, corners with three equivalent Se(4)Na2V3 trigonal bipyramids,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid, edges with two equivalent Se(5)Na2V3 square pyramids,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. is represented by the CIF file [CIF]
data_Na3(VSe2)5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   38.017
_cell_length_b   22.300
_cell_length_c   14.771
_cell_angle_alpha   12.269
_cell_angle_beta   13.587
_cell_angle_gamma   9.062
_symmetry_Int_Tables_number   1
_cell_volume   409.724
_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  0.346  0.141  0.168  1.0
  Na  Na1  1  0.576  0.121  0.130  1.0
  Na  Na2  1  0.737  0.178  0.143  1.0
  V  V3  1  0.029  0.940  0.015  1.0
  V  V4  1  0.194  0.037  0.963  1.0
  V  V5  1  0.364  0.041  0.029  1.0
  V  V6  1  0.566  0.013  0.065  1.0
  V  V7  1  0.830  0.989  0.941  1.0
  Se  Se8  1  0.029  0.403  0.429  1.0
  Se  Se9  1  0.235  0.400  0.426  1.0
  Se  Se10  1  0.163  0.614  0.566  1.0
  Se  Se11  1  0.447  0.388  0.394  1.0
  Se  Se12  1  0.355  0.606  0.596  1.0
  Se  Se13  1  0.639  0.385  0.416  1.0
  Se  Se14  1  0.555  0.599  0.611  1.0
  Se  Se15  1  0.840  0.407  0.392  1.0
  Se  Se16  1  0.755  0.613  0.605  1.0
  Se  Se17  1  0.942  0.625  0.610  1.0
[/CIF]
.