The crystal structure described by Li3VF6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(4), and one F(5) atom to form distorted LiF4 trigonal pyramids that share corners with two equivalent V(2)F6 octahedra, corners with four equivalent Li(3)F5 trigonal bipyramids, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 70-72°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(4), one F(5), and two equivalent F(6) atoms. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiF5 trigonal bipyramids that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent V(2)F6 octahedra, and corners with four equivalent Li(1)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 24-53°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms to form VF6 octahedra that share corners with four equivalent Li(3)F5 trigonal bipyramids and edges with two equivalent Li(1)F4 trigonal pyramids. In the second V site, V(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with six equivalent Li(3)F5 trigonal bipyramids and corners with four equivalent Li(1)F4 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one V(2) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), and one V(2) atom to form distorted corner-sharing FLi3V trigonal pyramids. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one V(2) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), and one V(1) atom to form corner-sharing FLi3V trigonal pyramids. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one V(1) atom. is represented by the Crystallographic Information File (CIF) [CIF]
data_Li3VF6
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   9.148
_cell_length_b   9.148
_cell_length_c   9.432
_cell_angle_alpha   88.178
_cell_angle_beta   88.178
_cell_angle_gamma   33.902
_symmetry_Int_Tables_number   1
_cell_volume   440.069
_cell_formula_units_Z   4
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  0.139  0.701  0.950  1.0
  Li  Li1  1  0.701  0.139  0.450  1.0
  Li  Li2  1  0.608  0.039  0.820  1.0
  Li  Li3  1  0.179  0.604  0.601  1.0
  Li  Li4  1  0.039  0.608  0.320  1.0
  Li  Li5  1  0.604  0.179  0.101  1.0
  Li  Li6  1  0.396  0.821  0.899  1.0
  Li  Li7  1  0.961  0.392  0.680  1.0
  Li  Li8  1  0.821  0.396  0.399  1.0
  Li  Li9  1  0.392  0.961  0.180  1.0
  Li  Li10  1  0.299  0.861  0.550  1.0
  Li  Li11  1  0.861  0.299  0.050  1.0
  V  V12  1  0.500  0.000  0.500  1.0
  V  V13  1  0.000  0.500  0.000  1.0
  V  V14  1  0.796  0.204  0.750  1.0
  V  V15  1  0.204  0.796  0.250  1.0
  F  F16  1  0.749  0.216  0.962  1.0
  F  F17  1  0.998  0.849  0.760  1.0
  F  F18  1  0.501  0.323  0.714  1.0
  F  F19  1  0.216  0.749  0.462  1.0
  F  F20  1  0.849  0.998  0.260  1.0
  F  F21  1  0.323  0.501  0.214  1.0
  F  F22  1  0.323  0.349  0.960  1.0
  F  F23  1  0.349  0.323  0.460  1.0
  F  F24  1  0.846  0.824  0.515  1.0
  F  F25  1  0.824  0.846  0.015  1.0
  F  F26  1  0.892  0.610  0.805  1.0
  F  F27  1  0.390  0.108  0.695  1.0
  F  F28  1  0.610  0.892  0.305  1.0
  F  F29  1  0.108  0.390  0.195  1.0
  F  F30  1  0.176  0.154  0.985  1.0
  F  F31  1  0.154  0.176  0.485  1.0
  F  F32  1  0.651  0.677  0.540  1.0
  F  F33  1  0.677  0.651  0.040  1.0
  F  F34  1  0.677  0.499  0.786  1.0
  F  F35  1  0.151  0.002  0.740  1.0
  F  F36  1  0.784  0.251  0.538  1.0
  F  F37  1  0.499  0.677  0.286  1.0
  F  F38  1  0.002  0.151  0.240  1.0
  F  F39  1  0.251  0.784  0.038  1.0
[/CIF]
.
The crystal structure described by Li3VF6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(4), and one F(5) atom to form distorted LiF4 trigonal pyramids that share corners with two equivalent V(2)F6 octahedra, corners with four equivalent Li(3)F5 trigonal bipyramids, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 70-72°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one F(2), one F(3), one F(4), one F(5), and two equivalent F(6) atoms. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form LiF5 trigonal bipyramids that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent V(2)F6 octahedra, and corners with four equivalent Li(1)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 24-53°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(4), two equivalent F(5), and two equivalent F(6) atoms to form VF6 octahedra that share corners with four equivalent Li(3)F5 trigonal bipyramids and edges with two equivalent Li(1)F4 trigonal pyramids. In the second V site, V(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with six equivalent Li(3)F5 trigonal bipyramids and corners with four equivalent Li(1)F4 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one V(2) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(3), and one V(2) atom to form distorted corner-sharing FLi3V trigonal pyramids. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one V(2) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(2), one Li(3), and one V(1) atom to form corner-sharing FLi3V trigonal pyramids. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one V(1) atom. is represented by the Crystallographic Information File (CIF) [CIF]
data_Li3VF6
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   9.148
_cell_length_b   9.148
_cell_length_c   9.432
_cell_angle_alpha   88.178
_cell_angle_beta   88.178
_cell_angle_gamma   33.902
_symmetry_Int_Tables_number   1
_cell_volume   440.069
_cell_formula_units_Z   4
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  0.139  0.701  0.950  1.0
  Li  Li1  1  0.701  0.139  0.450  1.0
  Li  Li2  1  0.608  0.039  0.820  1.0
  Li  Li3  1  0.179  0.604  0.601  1.0
  Li  Li4  1  0.039  0.608  0.320  1.0
  Li  Li5  1  0.604  0.179  0.101  1.0
  Li  Li6  1  0.396  0.821  0.899  1.0
  Li  Li7  1  0.961  0.392  0.680  1.0
  Li  Li8  1  0.821  0.396  0.399  1.0
  Li  Li9  1  0.392  0.961  0.180  1.0
  Li  Li10  1  0.299  0.861  0.550  1.0
  Li  Li11  1  0.861  0.299  0.050  1.0
  V  V12  1  0.500  0.000  0.500  1.0
  V  V13  1  0.000  0.500  0.000  1.0
  V  V14  1  0.796  0.204  0.750  1.0
  V  V15  1  0.204  0.796  0.250  1.0
  F  F16  1  0.749  0.216  0.962  1.0
  F  F17  1  0.998  0.849  0.760  1.0
  F  F18  1  0.501  0.323  0.714  1.0
  F  F19  1  0.216  0.749  0.462  1.0
  F  F20  1  0.849  0.998  0.260  1.0
  F  F21  1  0.323  0.501  0.214  1.0
  F  F22  1  0.323  0.349  0.960  1.0
  F  F23  1  0.349  0.323  0.460  1.0
  F  F24  1  0.846  0.824  0.515  1.0
  F  F25  1  0.824  0.846  0.015  1.0
  F  F26  1  0.892  0.610  0.805  1.0
  F  F27  1  0.390  0.108  0.695  1.0
  F  F28  1  0.610  0.892  0.305  1.0
  F  F29  1  0.108  0.390  0.195  1.0
  F  F30  1  0.176  0.154  0.985  1.0
  F  F31  1  0.154  0.176  0.485  1.0
  F  F32  1  0.651  0.677  0.540  1.0
  F  F33  1  0.677  0.651  0.040  1.0
  F  F34  1  0.677  0.499  0.786  1.0
  F  F35  1  0.151  0.002  0.740  1.0
  F  F36  1  0.784  0.251  0.538  1.0
  F  F37  1  0.499  0.677  0.286  1.0
  F  F38  1  0.002  0.151  0.240  1.0
  F  F39  1  0.251  0.784  0.038  1.0
[/CIF]
.