The material described by Li5V12O32 crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(18), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing LiO6 octahedra. In the second Li site, Li(2) is bonded to one O(19), one O(6), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing LiO6 octahedra. In the third Li site, Li(3) is bonded to one O(12), one O(13), one O(16), one O(17), one O(20), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra and edges with two equivalent Li(3)O6 octahedra. In the fourth Li site, Li(4) is bonded to one O(12), one O(2), and two equivalent O(22) atoms to form distorted corner-sharing LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 63°. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(15), one O(18), one O(3), one O(6), and two equivalent O(1) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(14), one O(19), one O(2), one O(7), and two equivalent O(1) atoms. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(21), one O(4), one O(5), one O(8), and one O(9) atom. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(2), one O(24), and two equivalent O(10) atoms. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(13), one O(15), one O(23), one O(3), and two equivalent O(10) atoms. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(14), one O(15), and one O(22) atom. In the seventh V site, V(7) is bonded in a 5-coordinate geometry to one O(16), one O(18), one O(4), and two equivalent O(21) atoms. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(17), one O(19), one O(5), and two equivalent O(21) atoms. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(10), one O(20), one O(22), one O(23), one O(24), and one O(8) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one V(6) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(4), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(1) and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(7) and two equivalent V(3) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(8) and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(3), one V(3), and one V(9) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one V(4), one V(5), one V(6), and one V(9) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(6) atom. In the twelfth O site, O(12) is bonded to one Li(4), two equivalent Li(3), and one V(4) atom to form distorted corner-sharing OLi3V tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(5) atom. In the fourteenth O site, O(14) is bonded to one V(2), one V(4), and two equivalent V(6) atoms to form distorted corner-sharing OV4 trigonal pyramids. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one V(1), one V(5), and two equivalent V(6) atoms. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(7) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(8) atom. In the eighteenth O site, O(18) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(7) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(8) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Li(3) and one V(9) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one V(7), and one V(8) atom. In the twenty-second O site, O(22) is bonded in a trigonal non-coplanar geometry to one Li(4), one V(6), and one V(9) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one V(5) and two equivalent V(9) atoms. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(9) atoms. is represented by the CIF file [CIF]
data_Li5V12O32
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   7.692
_cell_length_b   7.692
_cell_length_c   12.162
_cell_angle_alpha   74.299
_cell_angle_beta   74.299
_cell_angle_gamma   56.490
_symmetry_Int_Tables_number   1
_cell_volume   570.961
_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
  Li  Li0  1  0.125  0.125  0.684  1.0
  Li  Li1  1  0.625  0.625  0.684  1.0
  Li  Li2  1  0.377  0.872  0.316  1.0
  Li  Li3  1  0.872  0.377  0.316  1.0
  Li  Li4  1  0.087  0.087  0.052  1.0
  V  V5  1  0.837  0.837  0.807  1.0
  V  V6  1  0.340  0.340  0.804  1.0
  V  V7  1  0.547  0.046  0.463  1.0
  V  V8  1  0.046  0.547  0.463  1.0
  V  V9  1  0.277  0.277  0.079  1.0
  V  V10  1  0.772  0.772  0.080  1.0
  V  V11  1  0.727  0.228  0.919  1.0
  V  V12  1  0.228  0.727  0.919  1.0
  V  V13  1  0.954  0.954  0.537  1.0
  V  V14  1  0.453  0.453  0.537  1.0
  V  V15  1  0.659  0.159  0.197  1.0
  V  V16  1  0.159  0.659  0.197  1.0
  O  O17  1  0.120  0.619  0.826  1.0
  O  O18  1  0.619  0.120  0.826  1.0
  O  O19  1  0.234  0.234  0.955  1.0
  O  O20  1  0.734  0.734  0.953  1.0
  O  O21  1  0.841  0.841  0.460  1.0
  O  O22  1  0.341  0.341  0.460  1.0
  O  O23  1  0.764  0.764  0.721  1.0
  O  O24  1  0.264  0.264  0.722  1.0
  O  O25  1  0.524  0.026  0.327  1.0
  O  O26  1  0.026  0.524  0.327  1.0
  O  O27  1  0.932  0.432  0.562  1.0
  O  O28  1  0.432  0.932  0.562  1.0
  O  O29  1  0.566  0.065  0.072  1.0
  O  O30  1  0.065  0.566  0.072  1.0
  O  O31  1  0.334  0.836  0.810  1.0
  O  O32  1  0.836  0.334  0.810  1.0
  O  O33  1  0.163  0.163  0.182  1.0
  O  O34  1  0.665  0.665  0.189  1.0
  O  O35  1  0.435  0.435  0.931  1.0
  O  O36  1  0.936  0.936  0.928  1.0
  O  O37  1  0.068  0.068  0.438  1.0
  O  O38  1  0.568  0.568  0.438  1.0
  O  O39  1  0.974  0.974  0.673  1.0
  O  O40  1  0.474  0.474  0.674  1.0
  O  O41  1  0.737  0.235  0.279  1.0
  O  O42  1  0.235  0.737  0.279  1.0
  O  O43  1  0.659  0.159  0.540  1.0
  O  O44  1  0.159  0.659  0.540  1.0
  O  O45  1  0.257  0.778  0.046  1.0
  O  O46  1  0.778  0.257  0.046  1.0
  O  O47  1  0.881  0.881  0.175  1.0
  O  O48  1  0.382  0.382  0.173  1.0
[/CIF]
.
The material described by Li5V12O32 crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(18), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing LiO6 octahedra. In the second Li site, Li(2) is bonded to one O(19), one O(6), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing LiO6 octahedra. In the third Li site, Li(3) is bonded to one O(12), one O(13), one O(16), one O(17), one O(20), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra and edges with two equivalent Li(3)O6 octahedra. In the fourth Li site, Li(4) is bonded to one O(12), one O(2), and two equivalent O(22) atoms to form distorted corner-sharing LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 63°. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(15), one O(18), one O(3), one O(6), and two equivalent O(1) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(14), one O(19), one O(2), one O(7), and two equivalent O(1) atoms. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(21), one O(4), one O(5), one O(8), and one O(9) atom. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(2), one O(24), and two equivalent O(10) atoms. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(13), one O(15), one O(23), one O(3), and two equivalent O(10) atoms. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(14), one O(15), and one O(22) atom. In the seventh V site, V(7) is bonded in a 5-coordinate geometry to one O(16), one O(18), one O(4), and two equivalent O(21) atoms. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(17), one O(19), one O(5), and two equivalent O(21) atoms. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(10), one O(20), one O(22), one O(23), one O(24), and one O(8) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one V(6) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(4), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(1) and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(7) and two equivalent V(3) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(8) and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(3), one V(3), and one V(9) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one V(4), one V(5), one V(6), and one V(9) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(6) atom. In the twelfth O site, O(12) is bonded to one Li(4), two equivalent Li(3), and one V(4) atom to form distorted corner-sharing OLi3V tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(5) atom. In the fourteenth O site, O(14) is bonded to one V(2), one V(4), and two equivalent V(6) atoms to form distorted corner-sharing OV4 trigonal pyramids. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one V(1), one V(5), and two equivalent V(6) atoms. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(7) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(8) atom. In the eighteenth O site, O(18) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(7) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(8) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Li(3) and one V(9) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one V(7), and one V(8) atom. In the twenty-second O site, O(22) is bonded in a trigonal non-coplanar geometry to one Li(4), one V(6), and one V(9) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one V(5) and two equivalent V(9) atoms. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(9) atoms. is represented by the CIF file [CIF]
data_Li5V12O32
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   7.692
_cell_length_b   7.692
_cell_length_c   12.162
_cell_angle_alpha   74.299
_cell_angle_beta   74.299
_cell_angle_gamma   56.490
_symmetry_Int_Tables_number   1
_cell_volume   570.961
_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
  Li  Li0  1  0.125  0.125  0.684  1.0
  Li  Li1  1  0.625  0.625  0.684  1.0
  Li  Li2  1  0.377  0.872  0.316  1.0
  Li  Li3  1  0.872  0.377  0.316  1.0
  Li  Li4  1  0.087  0.087  0.052  1.0
  V  V5  1  0.837  0.837  0.807  1.0
  V  V6  1  0.340  0.340  0.804  1.0
  V  V7  1  0.547  0.046  0.463  1.0
  V  V8  1  0.046  0.547  0.463  1.0
  V  V9  1  0.277  0.277  0.079  1.0
  V  V10  1  0.772  0.772  0.080  1.0
  V  V11  1  0.727  0.228  0.919  1.0
  V  V12  1  0.228  0.727  0.919  1.0
  V  V13  1  0.954  0.954  0.537  1.0
  V  V14  1  0.453  0.453  0.537  1.0
  V  V15  1  0.659  0.159  0.197  1.0
  V  V16  1  0.159  0.659  0.197  1.0
  O  O17  1  0.120  0.619  0.826  1.0
  O  O18  1  0.619  0.120  0.826  1.0
  O  O19  1  0.234  0.234  0.955  1.0
  O  O20  1  0.734  0.734  0.953  1.0
  O  O21  1  0.841  0.841  0.460  1.0
  O  O22  1  0.341  0.341  0.460  1.0
  O  O23  1  0.764  0.764  0.721  1.0
  O  O24  1  0.264  0.264  0.722  1.0
  O  O25  1  0.524  0.026  0.327  1.0
  O  O26  1  0.026  0.524  0.327  1.0
  O  O27  1  0.932  0.432  0.562  1.0
  O  O28  1  0.432  0.932  0.562  1.0
  O  O29  1  0.566  0.065  0.072  1.0
  O  O30  1  0.065  0.566  0.072  1.0
  O  O31  1  0.334  0.836  0.810  1.0
  O  O32  1  0.836  0.334  0.810  1.0
  O  O33  1  0.163  0.163  0.182  1.0
  O  O34  1  0.665  0.665  0.189  1.0
  O  O35  1  0.435  0.435  0.931  1.0
  O  O36  1  0.936  0.936  0.928  1.0
  O  O37  1  0.068  0.068  0.438  1.0
  O  O38  1  0.568  0.568  0.438  1.0
  O  O39  1  0.974  0.974  0.673  1.0
  O  O40  1  0.474  0.474  0.674  1.0
  O  O41  1  0.737  0.235  0.279  1.0
  O  O42  1  0.235  0.737  0.279  1.0
  O  O43  1  0.659  0.159  0.540  1.0
  O  O44  1  0.159  0.659  0.540  1.0
  O  O45  1  0.257  0.778  0.046  1.0
  O  O46  1  0.778  0.257  0.046  1.0
  O  O47  1  0.881  0.881  0.175  1.0
  O  O48  1  0.382  0.382  0.173  1.0
[/CIF]
.