The structure described by Na2CaV12O36 crystallizes in the monoclinic Cm space group. Na(1) is bonded to one O(10), one O(11), one O(15), one O(25), one O(26), and one O(6) atom to form NaO6 octahedra that share  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(7)O6 trigonal bipyramid, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. Ca(1) is bonded in an octahedral geometry to one O(14), one O(5), two equivalent O(12), and two equivalent O(27) atoms. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(22), one O(4), one O(8), and two equivalent O(24) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(23), one O(5), one O(7), and two equivalent O(24) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(22), one O(23), one O(24), one O(3), one O(6), and one O(9) atom. In the fourth V site, V(4) is bonded to one O(13), one O(17), one O(20), one O(25), and two equivalent O(18) atoms to form distorted VO6 octahedra that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(14), one O(16), one O(19), one O(26), and two equivalent O(18) atoms. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(17), one O(18), one O(21), and one O(27) atom. In the seventh V site, V(7) is bonded to one O(10), one O(19), one O(23), one O(7), and two equivalent O(3) atoms to form distorted VO6 trigonal bipyramids that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one O(11), one O(20), one O(22), one O(8), and two equivalent O(3) atoms. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(2), one O(21), one O(24), and one O(9) atom. There are twenty-seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(2) and two equivalent V(9) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(9) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one V(8) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one V(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Ca(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Na(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(2) and one V(7) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(8) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(3) and one V(9) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(7) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(8) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and one V(9) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one V(4) atom. In the fourteenth O site, O(14) is bonded in a linear geometry to one Ca(1) and one V(5) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Na(1) and one V(6) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(6) atoms. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(6) atoms. In the eighteenth O site, O(18) is bonded in a distorted trigonal non-coplanar geometry to one V(4), one V(5), and one V(6) atom. In the nineteenth O site, O(19) is bonded in a linear geometry to one V(5) and one V(7) atom. In the twentieth O site, O(20) is bonded in a linear geometry to one V(4) and one V(8) atom. In the twenty-first O site, O(21) is bonded in a linear geometry to one V(6) and one V(9) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one V(1), one V(8), and two equivalent V(3) atoms. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one V(2), one V(7), and two equivalent V(3) atoms. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one V(1), one V(2), one V(3), and one V(9) atom. In the twenty-fifth O site, O(25) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(4) atom. In the twenty-sixth O site, O(26) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(5) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 120 degrees geometry to one Ca(1) and one V(6) atom. is represented by the Crystallographic Information File (CIF) [CIF]
data_Na2CaV12O36
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   7.260
_cell_length_b   13.401
_cell_length_c   8.634
_cell_angle_alpha   100.870
_cell_angle_beta   114.864
_cell_angle_gamma   74.283
_symmetry_Int_Tables_number   1
_cell_volume   730.957
_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  0.541  0.692  0.520  1.0
  Na  Na1  1  0.037  0.692  0.520  1.0
  Ca  Ca2  1  0.960  0.311  0.481  1.0
  V  V3  1  0.404  0.084  0.142  1.0
  V  V4  1  0.916  0.068  0.151  1.0
  V  V5  1  0.089  0.932  0.861  1.0
  V  V6  1  0.591  0.932  0.861  1.0
  V  V7  1  0.532  0.542  0.855  1.0
  V  V8  1  0.030  0.543  0.852  1.0
  V  V9  1  0.969  0.460  0.148  1.0
  V  V10  1  0.469  0.460  0.148  1.0
  V  V11  1  0.048  0.818  0.164  1.0
  V  V12  1  0.547  0.804  0.147  1.0
  V  V13  1  0.454  0.181  0.840  1.0
  V  V14  1  0.956  0.181  0.840  1.0
  O  O15  1  0.737  0.168  0.891  1.0
  O  O16  1  0.255  0.164  0.923  1.0
  O  O17  1  0.759  0.836  0.093  1.0
  O  O18  1  0.249  0.836  0.093  1.0
  O  O19  1  0.444  0.169  0.306  1.0
  O  O20  1  0.939  0.167  0.296  1.0
  O  O21  1  0.077  0.832  0.720  1.0
  O  O22  1  0.561  0.832  0.720  1.0
  O  O23  1  0.030  0.961  0.271  1.0
  O  O24  1  0.512  0.962  0.237  1.0
  O  O25  1  0.466  0.039  0.737  1.0
  O  O26  1  0.983  0.039  0.737  1.0
  O  O27  1  0.166  0.762  0.344  1.0
  O  O28  1  0.664  0.766  0.343  1.0
  O  O29  1  0.308  0.236  0.661  1.0
  O  O30  1  0.868  0.236  0.661  1.0
  O  O31  1  0.504  0.444  0.702  1.0
  O  O32  1  0.998  0.447  0.694  1.0
  O  O33  1  0.997  0.555  0.302  1.0
  O  O34  1  0.500  0.555  0.302  1.0
  O  O35  1  0.184  0.457  0.074  1.0
  O  O36  1  0.679  0.461  0.069  1.0
  O  O37  1  0.316  0.541  0.927  1.0
  O  O38  1  0.820  0.541  0.927  1.0
  O  O39  1  0.037  0.693  0.017  1.0
  O  O40  1  0.539  0.690  0.018  1.0
  O  O41  1  0.469  0.304  0.986  1.0
  O  O42  1  0.963  0.304  0.986  1.0
  O  O43  1  0.380  0.933  0.944  1.0
  O  O44  1  0.870  0.940  0.931  1.0
  O  O45  1  0.121  0.071  0.071  1.0
  O  O46  1  0.629  0.071  0.071  1.0
  O  O47  1  0.408  0.630  0.696  1.0
  O  O48  1  0.913  0.645  0.720  1.0
  O  O49  1  0.063  0.357  0.279  1.0
  O  O50  1  0.609  0.357  0.279  1.0
[/CIF]
.
The structure described by Na2CaV12O36 crystallizes in the monoclinic Cm space group. Na(1) is bonded to one O(10), one O(11), one O(15), one O(25), one O(26), and one O(6) atom to form NaO6 octahedra that share  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(7)O6 trigonal bipyramid, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. Ca(1) is bonded in an octahedral geometry to one O(14), one O(5), two equivalent O(12), and two equivalent O(27) atoms. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(2), one O(22), one O(4), one O(8), and two equivalent O(24) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(23), one O(5), one O(7), and two equivalent O(24) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(22), one O(23), one O(24), one O(3), one O(6), and one O(9) atom. In the fourth V site, V(4) is bonded to one O(13), one O(17), one O(20), one O(25), and two equivalent O(18) atoms to form distorted VO6 octahedra that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(14), one O(16), one O(19), one O(26), and two equivalent O(18) atoms. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(17), one O(18), one O(21), and one O(27) atom. In the seventh V site, V(7) is bonded to one O(10), one O(19), one O(23), one O(7), and two equivalent O(3) atoms to form distorted VO6 trigonal bipyramids that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one O(11), one O(20), one O(22), one O(8), and two equivalent O(3) atoms. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(2), one O(21), one O(24), and one O(9) atom. There are twenty-seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(2) and two equivalent V(9) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(9) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(3), one V(7), and one V(8) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one V(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Ca(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Na(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one V(2) and one V(7) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(8) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one V(3) and one V(9) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(7) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(8) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and one V(9) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one V(4) atom. In the fourteenth O site, O(14) is bonded in a linear geometry to one Ca(1) and one V(5) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Na(1) and one V(6) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal non-coplanar geometry to one V(5) and two equivalent V(6) atoms. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(6) atoms. In the eighteenth O site, O(18) is bonded in a distorted trigonal non-coplanar geometry to one V(4), one V(5), and one V(6) atom. In the nineteenth O site, O(19) is bonded in a linear geometry to one V(5) and one V(7) atom. In the twentieth O site, O(20) is bonded in a linear geometry to one V(4) and one V(8) atom. In the twenty-first O site, O(21) is bonded in a linear geometry to one V(6) and one V(9) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one V(1), one V(8), and two equivalent V(3) atoms. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one V(2), one V(7), and two equivalent V(3) atoms. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one V(1), one V(2), one V(3), and one V(9) atom. In the twenty-fifth O site, O(25) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(4) atom. In the twenty-sixth O site, O(26) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(5) atom. In the twenty-seventh O site, O(27) is bonded in a distorted bent 120 degrees geometry to one Ca(1) and one V(6) atom. is represented by the Crystallographic Information File (CIF) [CIF]
data_Na2CaV12O36
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   7.260
_cell_length_b   13.401
_cell_length_c   8.634
_cell_angle_alpha   100.870
_cell_angle_beta   114.864
_cell_angle_gamma   74.283
_symmetry_Int_Tables_number   1
_cell_volume   730.957
_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  0.541  0.692  0.520  1.0
  Na  Na1  1  0.037  0.692  0.520  1.0
  Ca  Ca2  1  0.960  0.311  0.481  1.0
  V  V3  1  0.404  0.084  0.142  1.0
  V  V4  1  0.916  0.068  0.151  1.0
  V  V5  1  0.089  0.932  0.861  1.0
  V  V6  1  0.591  0.932  0.861  1.0
  V  V7  1  0.532  0.542  0.855  1.0
  V  V8  1  0.030  0.543  0.852  1.0
  V  V9  1  0.969  0.460  0.148  1.0
  V  V10  1  0.469  0.460  0.148  1.0
  V  V11  1  0.048  0.818  0.164  1.0
  V  V12  1  0.547  0.804  0.147  1.0
  V  V13  1  0.454  0.181  0.840  1.0
  V  V14  1  0.956  0.181  0.840  1.0
  O  O15  1  0.737  0.168  0.891  1.0
  O  O16  1  0.255  0.164  0.923  1.0
  O  O17  1  0.759  0.836  0.093  1.0
  O  O18  1  0.249  0.836  0.093  1.0
  O  O19  1  0.444  0.169  0.306  1.0
  O  O20  1  0.939  0.167  0.296  1.0
  O  O21  1  0.077  0.832  0.720  1.0
  O  O22  1  0.561  0.832  0.720  1.0
  O  O23  1  0.030  0.961  0.271  1.0
  O  O24  1  0.512  0.962  0.237  1.0
  O  O25  1  0.466  0.039  0.737  1.0
  O  O26  1  0.983  0.039  0.737  1.0
  O  O27  1  0.166  0.762  0.344  1.0
  O  O28  1  0.664  0.766  0.343  1.0
  O  O29  1  0.308  0.236  0.661  1.0
  O  O30  1  0.868  0.236  0.661  1.0
  O  O31  1  0.504  0.444  0.702  1.0
  O  O32  1  0.998  0.447  0.694  1.0
  O  O33  1  0.997  0.555  0.302  1.0
  O  O34  1  0.500  0.555  0.302  1.0
  O  O35  1  0.184  0.457  0.074  1.0
  O  O36  1  0.679  0.461  0.069  1.0
  O  O37  1  0.316  0.541  0.927  1.0
  O  O38  1  0.820  0.541  0.927  1.0
  O  O39  1  0.037  0.693  0.017  1.0
  O  O40  1  0.539  0.690  0.018  1.0
  O  O41  1  0.469  0.304  0.986  1.0
  O  O42  1  0.963  0.304  0.986  1.0
  O  O43  1  0.380  0.933  0.944  1.0
  O  O44  1  0.870  0.940  0.931  1.0
  O  O45  1  0.121  0.071  0.071  1.0
  O  O46  1  0.629  0.071  0.071  1.0
  O  O47  1  0.408  0.630  0.696  1.0
  O  O48  1  0.913  0.645  0.720  1.0
  O  O49  1  0.063  0.357  0.279  1.0
  O  O50  1  0.609  0.357  0.279  1.0
[/CIF]
.