The structure described by Li2VO2F is Caswellsilverite-derived structured and crystallizes in the monoclinic Cm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share corners with three equivalent Li(5)O4F2 octahedra, corners with three equivalent V(1)O5F octahedra,  an edgeedge with one Li(4)O3F3 octahedra,  an edgeedge with one Li(5)O4F2 octahedra,  an edgeedge with one Li(6)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(3)O5F octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(1)O3F3 octahedra, and edges with two equivalent Li(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent F(1) atoms to form distorted LiO4F2 octahedra that share corners with three equivalent Li(6)O4F2 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Li(4)O3F3 octahedra,  an edgeedge with one V(3)O5F octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(5)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with four equivalent Li(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the third Li site, Li(3) is bonded to two equivalent O(3), one F(2), one F(3), and two equivalent F(1) atoms to form LiO2F4 octahedra that share corners with three equivalent Li(4)O3F3 octahedra, corners with three equivalent V(3)O5F octahedra,  an edgeedge with one Li(6)O4F2 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Li(5)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with four equivalent Li(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the fourth Li site, Li(4) is bonded to one O(5), two equivalent O(4), one F(3), and two equivalent F(1) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(3)O2F4 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Li(2)O4F2 octahedra,  an edgeedge with one V(3)O5F octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(6)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with four equivalent Li(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the fifth Li site, Li(5) is bonded to one O(2), one O(4), one O(5), one O(6), one F(1), and one F(3) atom to form distorted LiO4F2 octahedra that share corners with three equivalent Li(1)O3F3 octahedra, corners with three equivalent V(1)O5F octahedra,  an edgeedge with one Li(3)O2F4 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(2)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(3)O5F octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent Li(5)O4F2 octahedra, and edges with two equivalent Li(6)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the sixth Li site, Li(6) is bonded to one O(2), one O(6), two equivalent O(4), and two equivalent F(1) atoms to form distorted LiO4F2 octahedra that share corners with three equivalent Li(2)O4F2 octahedra, corners with three equivalent V(3)O5F octahedra,  an edgeedge with one Li(3)O2F4 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with four equivalent Li(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one F(2) atom to form VO5F octahedra that share corners with three equivalent Li(1)O3F3 octahedra, corners with three equivalent Li(5)O4F2 octahedra,  an edgeedge with one Li(3)O2F4 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(4)O3F3 octahedra,  an edgeedge with one Li(2)O4F2 octahedra,  an edgeedge with one Li(5)O4F2 octahedra,  an edgeedge with one Li(6)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(3)O5F octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the second V site, V(2) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(4)O3F3 octahedra, corners with three equivalent Li(2)O4F2 octahedra,  an edgeedge with one Li(3)O2F4 octahedra,  an edgeedge with one Li(6)O4F2 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(5)O4F2 octahedra, edges with two equivalent V(3)O5F octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the third V site, V(3) is bonded to one O(6), two equivalent O(3), two equivalent O(4), and one F(2) atom to form VO5F octahedra that share corners with three equivalent Li(3)O2F4 octahedra, corners with three equivalent Li(6)O4F2 octahedra,  an edgeedge with one Li(4)O3F3 octahedra,  an edgeedge with one Li(2)O4F2 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(5)O4F2 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 4-13°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share corners with three equivalent O(5)Li3V3 octahedra, corners with three equivalent O(2)Li6 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent F(2)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Li(2), one Li(6), two equivalent Li(1), and two equivalent Li(5) atoms to form OLi6 octahedra that share corners with three equivalent O(1)Li3V3 octahedra, corners with three equivalent O(6)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent F(3)Li6 octahedra, and edges with four equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with three equivalent O(4)Li3V3 octahedra, corners with three equivalent F(1)Li6 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(2)Li6 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent F(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-16°. In the fourth O site, O(4) is bonded to one Li(4), one Li(5), one Li(6), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with three equivalent O(3)Li3V3 octahedra, corners with three equivalent F(1)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(2)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(5), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share corners with three equivalent O(1)Li3V3 octahedra, corners with three equivalent F(3)Li6 octahedra,  an edgeedge with one O(2)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the sixth O site, O(6) is bonded to one Li(6), two equivalent Li(5), one V(3), and two equivalent V(1) atoms to form OLi3V3 octahedra that share corners with three equivalent O(2)Li6 octahedra, corners with three equivalent F(2)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form FLi6 octahedra that share corners with three equivalent O(3)Li3V3 octahedra, corners with three equivalent O(4)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(2)Li6 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 8-16°. In the second F site, F(2) is bonded to one Li(3), two equivalent Li(1), one V(3), and two equivalent V(1) atoms to form FLi3V3 octahedra that share corners with three equivalent O(6)Li3V3 octahedra, corners with three equivalent F(3)Li6 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(2)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the third F site, F(3) is bonded to one Li(3), one Li(4), two equivalent Li(1), and two equivalent Li(5) atoms to form FLi6 octahedra that share corners with three equivalent O(5)Li3V3 octahedra, corners with three equivalent F(2)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(2)Li6 octahedra, and edges with four equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. is represented by the CIF file [CIF]
data_Li2VO2F
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.024
_cell_length_b   6.024
_cell_length_c   8.985
_cell_angle_alpha   59.949
_cell_angle_beta   59.949
_cell_angle_gamma   59.827
_symmetry_Int_Tables_number   1
_cell_volume   230.053
_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  0.246  0.766  0.136  1.0
  Li  Li1  1  0.773  0.773  0.146  1.0
  Li  Li2  1  0.766  0.246  0.136  1.0
  Li  Li3  1  0.267  0.267  0.144  1.0
  Li  Li4  1  0.743  0.743  0.848  1.0
  Li  Li5  1  0.225  0.762  0.855  1.0
  Li  Li6  1  0.224  0.224  0.860  1.0
  Li  Li7  1  0.762  0.225  0.855  1.0
  V  V8  1  0.740  0.253  0.508  1.0
  V  V9  1  0.250  0.250  0.499  1.0
  V  V10  1  0.253  0.740  0.508  1.0
  V  V11  1  0.743  0.743  0.506  1.0
  O  O12  1  0.490  0.490  0.355  1.0
  O  O13  1  0.999  0.999  0.001  1.0
  O  O14  1  0.986  0.490  0.353  1.0
  O  O15  1  0.516  0.005  0.647  1.0
  O  O16  1  0.008  0.008  0.646  1.0
  O  O17  1  0.005  0.516  0.647  1.0
  O  O18  1  0.490  0.986  0.353  1.0
  O  O19  1  0.504  0.504  0.658  1.0
  F  F20  1  0.498  0.997  0.002  1.0
  F  F21  1  0.997  0.498  0.002  1.0
  F  F22  1  0.001  0.001  0.336  1.0
  F  F23  1  0.501  0.501  1.000  1.0
[/CIF]
.
The structure described by Li2VO2F is Caswellsilverite-derived structured and crystallizes in the monoclinic Cm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share corners with three equivalent Li(5)O4F2 octahedra, corners with three equivalent V(1)O5F octahedra,  an edgeedge with one Li(4)O3F3 octahedra,  an edgeedge with one Li(5)O4F2 octahedra,  an edgeedge with one Li(6)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(3)O5F octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(1)O3F3 octahedra, and edges with two equivalent Li(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent F(1) atoms to form distorted LiO4F2 octahedra that share corners with three equivalent Li(6)O4F2 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Li(4)O3F3 octahedra,  an edgeedge with one V(3)O5F octahedra, edges with two equivalent Li(3)O2F4 octahedra, edges with two equivalent Li(5)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with four equivalent Li(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the third Li site, Li(3) is bonded to two equivalent O(3), one F(2), one F(3), and two equivalent F(1) atoms to form LiO2F4 octahedra that share corners with three equivalent Li(4)O3F3 octahedra, corners with three equivalent V(3)O5F octahedra,  an edgeedge with one Li(6)O4F2 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(2)O4F2 octahedra, edges with two equivalent Li(5)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with four equivalent Li(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the fourth Li site, Li(4) is bonded to one O(5), two equivalent O(4), one F(3), and two equivalent F(1) atoms to form LiO3F3 octahedra that share corners with three equivalent Li(3)O2F4 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Li(2)O4F2 octahedra,  an edgeedge with one V(3)O5F octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(6)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with four equivalent Li(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the fifth Li site, Li(5) is bonded to one O(2), one O(4), one O(5), one O(6), one F(1), and one F(3) atom to form distorted LiO4F2 octahedra that share corners with three equivalent Li(1)O3F3 octahedra, corners with three equivalent V(1)O5F octahedra,  an edgeedge with one Li(3)O2F4 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(2)O4F2 octahedra,  an edgeedge with one V(1)O5F octahedra,  an edgeedge with one V(3)O5F octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent Li(5)O4F2 octahedra, and edges with two equivalent Li(6)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. In the sixth Li site, Li(6) is bonded to one O(2), one O(6), two equivalent O(4), and two equivalent F(1) atoms to form distorted LiO4F2 octahedra that share corners with three equivalent Li(2)O4F2 octahedra, corners with three equivalent V(3)O5F octahedra,  an edgeedge with one Li(3)O2F4 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(4)O3F3 octahedra, edges with two equivalent V(1)O5F octahedra, and edges with four equivalent Li(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 1-13°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one F(2) atom to form VO5F octahedra that share corners with three equivalent Li(1)O3F3 octahedra, corners with three equivalent Li(5)O4F2 octahedra,  an edgeedge with one Li(3)O2F4 octahedra,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Li(4)O3F3 octahedra,  an edgeedge with one Li(2)O4F2 octahedra,  an edgeedge with one Li(5)O4F2 octahedra,  an edgeedge with one Li(6)O4F2 octahedra, edges with two equivalent V(1)O5F octahedra, edges with two equivalent V(3)O5F octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the second V site, V(2) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(4)O3F3 octahedra, corners with three equivalent Li(2)O4F2 octahedra,  an edgeedge with one Li(3)O2F4 octahedra,  an edgeedge with one Li(6)O4F2 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(5)O4F2 octahedra, edges with two equivalent V(3)O5F octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the third V site, V(3) is bonded to one O(6), two equivalent O(3), two equivalent O(4), and one F(2) atom to form VO5F octahedra that share corners with three equivalent Li(3)O2F4 octahedra, corners with three equivalent Li(6)O4F2 octahedra,  an edgeedge with one Li(4)O3F3 octahedra,  an edgeedge with one Li(2)O4F2 octahedra, edges with two equivalent Li(1)O3F3 octahedra, edges with two equivalent Li(5)O4F2 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 4-13°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share corners with three equivalent O(5)Li3V3 octahedra, corners with three equivalent O(2)Li6 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent F(2)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Li(2), one Li(6), two equivalent Li(1), and two equivalent Li(5) atoms to form OLi6 octahedra that share corners with three equivalent O(1)Li3V3 octahedra, corners with three equivalent O(6)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent F(3)Li6 octahedra, and edges with four equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with three equivalent O(4)Li3V3 octahedra, corners with three equivalent F(1)Li6 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one O(2)Li6 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent F(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-16°. In the fourth O site, O(4) is bonded to one Li(4), one Li(5), one Li(6), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with three equivalent O(3)Li3V3 octahedra, corners with three equivalent F(1)Li6 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(2)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra,  an edgeedge with one F(1)Li6 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(5), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share corners with three equivalent O(1)Li3V3 octahedra, corners with three equivalent F(3)Li6 octahedra,  an edgeedge with one O(2)Li6 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(6)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the sixth O site, O(6) is bonded to one Li(6), two equivalent Li(5), one V(3), and two equivalent V(1) atoms to form OLi3V3 octahedra that share corners with three equivalent O(2)Li6 octahedra, corners with three equivalent F(2)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one F(3)Li6 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(5)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Li(6) atom to form FLi6 octahedra that share corners with three equivalent O(3)Li3V3 octahedra, corners with three equivalent O(4)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(3)Li3V3 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra,  an edgeedge with one F(2)Li3V3 octahedra, edges with two equivalent O(2)Li6 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with two equivalent F(3)Li6 octahedra. The corner-sharing octahedral tilt angles range from 8-16°. In the second F site, F(2) is bonded to one Li(3), two equivalent Li(1), one V(3), and two equivalent V(1) atoms to form FLi3V3 octahedra that share corners with three equivalent O(6)Li3V3 octahedra, corners with three equivalent F(3)Li6 octahedra,  an edgeedge with one O(5)Li3V3 octahedra,  an edgeedge with one O(2)Li6 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the third F site, F(3) is bonded to one Li(3), one Li(4), two equivalent Li(1), and two equivalent Li(5) atoms to form FLi6 octahedra that share corners with three equivalent O(5)Li3V3 octahedra, corners with three equivalent F(2)Li3V3 octahedra,  an edgeedge with one O(1)Li3V3 octahedra,  an edgeedge with one O(6)Li3V3 octahedra, edges with two equivalent O(3)Li3V3 octahedra, edges with two equivalent O(4)Li3V3 octahedra, edges with two equivalent O(2)Li6 octahedra, and edges with four equivalent F(1)Li6 octahedra. The corner-sharing octahedral tilt angles range from 6-13°. is represented by the CIF file [CIF]
data_Li2VO2F
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.024
_cell_length_b   6.024
_cell_length_c   8.985
_cell_angle_alpha   59.949
_cell_angle_beta   59.949
_cell_angle_gamma   59.827
_symmetry_Int_Tables_number   1
_cell_volume   230.053
_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  0.246  0.766  0.136  1.0
  Li  Li1  1  0.773  0.773  0.146  1.0
  Li  Li2  1  0.766  0.246  0.136  1.0
  Li  Li3  1  0.267  0.267  0.144  1.0
  Li  Li4  1  0.743  0.743  0.848  1.0
  Li  Li5  1  0.225  0.762  0.855  1.0
  Li  Li6  1  0.224  0.224  0.860  1.0
  Li  Li7  1  0.762  0.225  0.855  1.0
  V  V8  1  0.740  0.253  0.508  1.0
  V  V9  1  0.250  0.250  0.499  1.0
  V  V10  1  0.253  0.740  0.508  1.0
  V  V11  1  0.743  0.743  0.506  1.0
  O  O12  1  0.490  0.490  0.355  1.0
  O  O13  1  0.999  0.999  0.001  1.0
  O  O14  1  0.986  0.490  0.353  1.0
  O  O15  1  0.516  0.005  0.647  1.0
  O  O16  1  0.008  0.008  0.646  1.0
  O  O17  1  0.005  0.516  0.647  1.0
  O  O18  1  0.490  0.986  0.353  1.0
  O  O19  1  0.504  0.504  0.658  1.0
  F  F20  1  0.498  0.997  0.002  1.0
  F  F21  1  0.997  0.498  0.002  1.0
  F  F22  1  0.001  0.001  0.336  1.0
  F  F23  1  0.501  0.501  1.000  1.0
[/CIF]
.