The crystal structure described by Li4FeF8 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with four equivalent Fe(1)F6 pentagonal pyramids,  an edgeedge with one Li(1)F6 octahedra, and edges with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 5-66°. In the second Li site, Li(2) is bonded to one F(1), one F(4), two equivalent F(2), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with two equivalent Fe(1)F6 pentagonal pyramids,  an edgeedge with one Li(2)F6 octahedra, edges with four equivalent Li(1)F6 octahedra, and  an edgeedge with one Fe(1)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 6-55°. Fe(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted FeF6 pentagonal pyramids that share corners with four equivalent Li(2)F6 octahedra, corners with eight equivalent Li(1)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 26-70°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Fe(1) atom. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form a mixture of corner and edge-sharing FLi3Fe trigonal pyramids. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to two equivalent Li(2) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Li(2) atoms. is represented by the Crystallographic Information File (CIF) [CIF]
data_Li4FeF8
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   5.655
_cell_length_b   9.627
_cell_length_c   9.872
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   537.369
_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  0.123  0.117  0.924  1.0
  Li  Li1  1  0.123  0.117  0.576  1.0
  Li  Li2  1  0.625  0.131  0.945  1.0
  Li  Li3  1  0.625  0.131  0.555  1.0
  Li  Li4  1  0.125  0.369  0.055  1.0
  Li  Li5  1  0.125  0.369  0.445  1.0
  Li  Li6  1  0.623  0.383  0.076  1.0
  Li  Li7  1  0.623  0.383  0.424  1.0
  Li  Li8  1  0.377  0.617  0.924  1.0
  Li  Li9  1  0.377  0.617  0.576  1.0
  Li  Li10  1  0.875  0.631  0.555  1.0
  Li  Li11  1  0.875  0.631  0.945  1.0
  Li  Li12  1  0.375  0.869  0.055  1.0
  Li  Li13  1  0.375  0.869  0.445  1.0
  Li  Li14  1  0.877  0.883  0.076  1.0
  Li  Li15  1  0.877  0.883  0.424  1.0
  Fe  Fe16  1  0.365  0.109  0.250  1.0
  Fe  Fe17  1  0.865  0.391  0.750  1.0
  Fe  Fe18  1  0.135  0.609  0.250  1.0
  Fe  Fe19  1  0.635  0.891  0.750  1.0
  F  F20  1  0.150  0.017  0.117  1.0
  F  F21  1  0.150  0.017  0.383  1.0
  F  F22  1  0.597  0.017  0.124  1.0
  F  F23  1  0.597  0.017  0.376  1.0
  F  F24  1  0.087  0.232  0.750  1.0
  F  F25  1  0.646  0.234  0.750  1.0
  F  F26  1  0.372  0.244  0.008  1.0
  F  F27  1  0.372  0.244  0.492  1.0
  F  F28  1  0.872  0.256  0.508  1.0
  F  F29  1  0.872  0.256  0.992  1.0
  F  F30  1  0.146  0.266  0.250  1.0
  F  F31  1  0.587  0.268  0.250  1.0
  F  F32  1  0.097  0.483  0.624  1.0
  F  F33  1  0.097  0.483  0.876  1.0
  F  F34  1  0.650  0.483  0.617  1.0
  F  F35  1  0.650  0.483  0.883  1.0
  F  F36  1  0.350  0.517  0.117  1.0
  F  F37  1  0.350  0.517  0.383  1.0
  F  F38  1  0.903  0.517  0.124  1.0
  F  F39  1  0.903  0.517  0.376  1.0
  F  F40  1  0.413  0.732  0.750  1.0
  F  F41  1  0.854  0.734  0.750  1.0
  F  F42  1  0.128  0.744  0.008  1.0
  F  F43  1  0.128  0.744  0.492  1.0
  F  F44  1  0.628  0.756  0.508  1.0
  F  F45  1  0.628  0.756  0.992  1.0
  F  F46  1  0.354  0.766  0.250  1.0
  F  F47  1  0.913  0.768  0.250  1.0
  F  F48  1  0.403  0.983  0.624  1.0
  F  F49  1  0.403  0.983  0.876  1.0
  F  F50  1  0.850  0.983  0.617  1.0
  F  F51  1  0.850  0.983  0.883  1.0
[/CIF]
.
The crystal structure described by Li4FeF8 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with four equivalent Fe(1)F6 pentagonal pyramids,  an edgeedge with one Li(1)F6 octahedra, and edges with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 5-66°. In the second Li site, Li(2) is bonded to one F(1), one F(4), two equivalent F(2), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with three equivalent Li(2)F6 octahedra, corners with two equivalent Fe(1)F6 pentagonal pyramids,  an edgeedge with one Li(2)F6 octahedra, edges with four equivalent Li(1)F6 octahedra, and  an edgeedge with one Fe(1)F6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 6-55°. Fe(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form distorted FeF6 pentagonal pyramids that share corners with four equivalent Li(2)F6 octahedra, corners with eight equivalent Li(1)F6 octahedra, and edges with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 26-70°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Fe(1) atom. In the second F site, F(2) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form a mixture of corner and edge-sharing FLi3Fe trigonal pyramids. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to two equivalent Li(2) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Li(2) atoms. is represented by the Crystallographic Information File (CIF) [CIF]
data_Li4FeF8
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   5.655
_cell_length_b   9.627
_cell_length_c   9.872
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   537.369
_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  0.123  0.117  0.924  1.0
  Li  Li1  1  0.123  0.117  0.576  1.0
  Li  Li2  1  0.625  0.131  0.945  1.0
  Li  Li3  1  0.625  0.131  0.555  1.0
  Li  Li4  1  0.125  0.369  0.055  1.0
  Li  Li5  1  0.125  0.369  0.445  1.0
  Li  Li6  1  0.623  0.383  0.076  1.0
  Li  Li7  1  0.623  0.383  0.424  1.0
  Li  Li8  1  0.377  0.617  0.924  1.0
  Li  Li9  1  0.377  0.617  0.576  1.0
  Li  Li10  1  0.875  0.631  0.555  1.0
  Li  Li11  1  0.875  0.631  0.945  1.0
  Li  Li12  1  0.375  0.869  0.055  1.0
  Li  Li13  1  0.375  0.869  0.445  1.0
  Li  Li14  1  0.877  0.883  0.076  1.0
  Li  Li15  1  0.877  0.883  0.424  1.0
  Fe  Fe16  1  0.365  0.109  0.250  1.0
  Fe  Fe17  1  0.865  0.391  0.750  1.0
  Fe  Fe18  1  0.135  0.609  0.250  1.0
  Fe  Fe19  1  0.635  0.891  0.750  1.0
  F  F20  1  0.150  0.017  0.117  1.0
  F  F21  1  0.150  0.017  0.383  1.0
  F  F22  1  0.597  0.017  0.124  1.0
  F  F23  1  0.597  0.017  0.376  1.0
  F  F24  1  0.087  0.232  0.750  1.0
  F  F25  1  0.646  0.234  0.750  1.0
  F  F26  1  0.372  0.244  0.008  1.0
  F  F27  1  0.372  0.244  0.492  1.0
  F  F28  1  0.872  0.256  0.508  1.0
  F  F29  1  0.872  0.256  0.992  1.0
  F  F30  1  0.146  0.266  0.250  1.0
  F  F31  1  0.587  0.268  0.250  1.0
  F  F32  1  0.097  0.483  0.624  1.0
  F  F33  1  0.097  0.483  0.876  1.0
  F  F34  1  0.650  0.483  0.617  1.0
  F  F35  1  0.650  0.483  0.883  1.0
  F  F36  1  0.350  0.517  0.117  1.0
  F  F37  1  0.350  0.517  0.383  1.0
  F  F38  1  0.903  0.517  0.124  1.0
  F  F39  1  0.903  0.517  0.376  1.0
  F  F40  1  0.413  0.732  0.750  1.0
  F  F41  1  0.854  0.734  0.750  1.0
  F  F42  1  0.128  0.744  0.008  1.0
  F  F43  1  0.128  0.744  0.492  1.0
  F  F44  1  0.628  0.756  0.508  1.0
  F  F45  1  0.628  0.756  0.992  1.0
  F  F46  1  0.354  0.766  0.250  1.0
  F  F47  1  0.913  0.768  0.250  1.0
  F  F48  1  0.403  0.983  0.624  1.0
  F  F49  1  0.403  0.983  0.876  1.0
  F  F50  1  0.850  0.983  0.617  1.0
  F  F51  1  0.850  0.983  0.883  1.0
[/CIF]
.