The material described by Li5V5Cl16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Aem2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(4), one Cl(8), and two equivalent Cl(10) atoms to form LiCl4 tetrahedra that share  a cornercorner with one Li(2)Cl6 octahedra,  a cornercorner with one V(2)Cl6 octahedra, corners with two equivalent V(1)Cl6 octahedra, corners with four equivalent Li(3)Cl6 octahedra, and corners with four equivalent V(3)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. In the second Li site, Li(2) is bonded to one Cl(1), one Cl(8), two equivalent Cl(2), and two equivalent Cl(6) atoms to form LiCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra, edges with two equivalent V(1)Cl6 octahedra, edges with two equivalent V(2)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the third Li site, Li(3) is bonded to one Cl(5), one Cl(9), two equivalent Cl(10), and two equivalent Cl(7) atoms to form LiCl6 octahedra that share  a cornercorner with one Li(4)Cl4 tetrahedra, corners with two equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Li(3)Cl6 octahedra, edges with two equivalent V(1)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the fourth Li site, Li(4) is bonded to two equivalent Cl(6) and two equivalent Cl(9) atoms to form LiCl4 tetrahedra that share corners with two equivalent Li(2)Cl6 octahedra, corners with two equivalent Li(3)Cl6 octahedra, corners with two equivalent V(2)Cl6 octahedra, corners with two equivalent V(3)Cl6 octahedra, and corners with four equivalent V(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one Cl(1), one Cl(10), one Cl(2), one Cl(3), and two equivalent Cl(9) atoms to form VCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra,  an edgeedge with one Li(2)Cl6 octahedra,  an edgeedge with one V(2)Cl6 octahedra, edges with two equivalent Li(3)Cl6 octahedra, and edges with two equivalent V(1)Cl6 octahedra. In the second V site, V(2) is bonded to one Cl(3), one Cl(4), two equivalent Cl(2), and two equivalent Cl(6) atoms to form VCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, edges with two equivalent V(1)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the third V site, V(3) is bonded to one Cl(4), one Cl(6), one Cl(7), one Cl(8), and two equivalent Cl(5) atoms to form VCl6 octahedra that share  a cornercorner with one Li(4)Cl4 tetrahedra, corners with two equivalent Li(1)Cl4 tetrahedra,  an edgeedge with one Li(2)Cl6 octahedra,  an edgeedge with one V(2)Cl6 octahedra, edges with two equivalent Li(3)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. There are ten inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent V(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one V(2) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth Cl site, Cl(4) is bonded to one Li(1), one V(2), and two equivalent V(3) atoms to form distorted ClLiV3 trigonal pyramids that share corners with two equivalent Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(8)Li2V2 trigonal pyramid,  an edgeedge with one Cl(8)Li2V2 trigonal pyramid, and edges with two equivalent Cl(6)Li2V2 trigonal pyramids. In the fifth Cl site, Cl(5) is bonded in a distorted T-shaped geometry to one Li(3) and two equivalent V(3) atoms. In the sixth Cl site, Cl(6) is bonded to one Li(2), one Li(4), one V(2), and one V(3) atom to form distorted ClLi2V2 trigonal pyramids that share  a cornercorner with one Cl(6)Li2V2 trigonal pyramid,  an edgeedge with one Cl(6)Li2V2 trigonal pyramid,  an edgeedge with one Cl(8)Li2V2 trigonal pyramid, and  an edgeedge with one Cl(4)LiV3 trigonal pyramid. In the seventh Cl site, Cl(7) is bonded in a distorted T-shaped geometry to two equivalent Li(3) and one V(3) atom. In the eighth Cl site, Cl(8) is bonded to one Li(1), one Li(2), and two equivalent V(3) atoms to form distorted ClLi2V2 trigonal pyramids that share corners with two equivalent Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(4)LiV3 trigonal pyramid,  an edgeedge with one Cl(4)LiV3 trigonal pyramid, and edges with two equivalent Cl(6)Li2V2 trigonal pyramids. In the ninth Cl site, Cl(9) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), and two equivalent V(1) atoms. In the tenth Cl site, Cl(10) is bonded to one Li(1), two equivalent Li(3), and one V(1) atom to form distorted ClLi3V tetrahedra that share  a cornercorner with one Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(8)Li2V2 trigonal pyramid,  a cornercorner with one Cl(4)LiV3 trigonal pyramid, and  an edgeedge with one Cl(10)Li3V tetrahedra. is represented by the CIF file [CIF]
data_Li5V5Cl16
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   12.749
_cell_length_b   12.749
_cell_length_c   7.363
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   109.544
_symmetry_Int_Tables_number   1
_cell_volume   1127.866
_cell_formula_units_Z   2
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  0.992  0.508  0.009  1.0
  Li  Li1  1  0.690  0.810  0.763  1.0
  Li  Li2  1  0.191  0.809  0.264  1.0
  Li  Li3  1  0.691  0.309  0.264  1.0
  Li  Li4  1  0.998  0.002  0.500  1.0
  Li  Li5  1  0.191  0.809  0.736  1.0
  Li  Li6  1  0.691  0.309  0.736  1.0
  Li  Li7  1  0.492  0.008  0.991  1.0
  Li  Li8  1  0.190  0.310  0.237  1.0
  Li  Li9  1  0.498  0.502  0.500  1.0
  V  V10  1  0.688  0.565  0.999  1.0
  V  V11  1  0.935  0.812  0.999  1.0
  V  V12  1  0.688  0.812  0.244  1.0
  V  V13  1  0.189  0.568  0.499  1.0
  V  V14  1  0.432  0.811  0.501  1.0
  V  V15  1  0.689  0.068  0.501  1.0
  V  V16  1  0.932  0.311  0.499  1.0
  V  V17  1  0.188  0.312  0.756  1.0
  V  V18  1  0.435  0.312  0.001  1.0
  V  V19  1  0.188  0.065  0.001  1.0
  Cl  Cl20  1  0.812  0.688  0.777  1.0
  Cl  Cl21  1  0.577  0.689  0.011  1.0
  Cl  Cl22  1  0.811  0.923  0.011  1.0
  Cl  Cl23  1  0.808  0.692  0.232  1.0
  Cl  Cl24  1  0.567  0.933  0.267  1.0
  Cl  Cl25  1  0.814  0.186  0.275  1.0
  Cl  Cl26  1  0.314  0.686  0.275  1.0
  Cl  Cl27  1  0.798  0.934  0.493  1.0
  Cl  Cl28  1  0.566  0.702  0.493  1.0
  Cl  Cl29  1  0.076  0.684  0.501  1.0
  Cl  Cl30  1  0.576  0.184  0.499  1.0
  Cl  Cl31  1  0.816  0.424  0.501  1.0
  Cl  Cl32  1  0.316  0.924  0.499  1.0
  Cl  Cl33  1  0.314  0.686  0.725  1.0
  Cl  Cl34  1  0.814  0.186  0.725  1.0
  Cl  Cl35  1  0.565  0.935  0.726  1.0
  Cl  Cl36  1  0.062  0.937  0.772  1.0
  Cl  Cl37  1  0.563  0.438  0.772  1.0
  Cl  Cl38  1  0.308  0.192  0.768  1.0
  Cl  Cl39  1  0.297  0.938  0.999  1.0
  Cl  Cl40  1  0.797  0.438  0.001  1.0
  Cl  Cl41  1  0.062  0.703  0.001  1.0
  Cl  Cl42  1  0.562  0.203  0.999  1.0
  Cl  Cl43  1  0.077  0.189  0.989  1.0
  Cl  Cl44  1  0.311  0.423  0.989  1.0
  Cl  Cl45  1  0.312  0.188  0.223  1.0
  Cl  Cl46  1  0.063  0.938  0.228  1.0
  Cl  Cl47  1  0.562  0.437  0.228  1.0
  Cl  Cl48  1  0.065  0.435  0.274  1.0
  Cl  Cl49  1  0.298  0.434  0.507  1.0
  Cl  Cl50  1  0.066  0.202  0.507  1.0
  Cl  Cl51  1  0.067  0.433  0.733  1.0
[/CIF]
.
The material described by Li5V5Cl16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Aem2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(4), one Cl(8), and two equivalent Cl(10) atoms to form LiCl4 tetrahedra that share  a cornercorner with one Li(2)Cl6 octahedra,  a cornercorner with one V(2)Cl6 octahedra, corners with two equivalent V(1)Cl6 octahedra, corners with four equivalent Li(3)Cl6 octahedra, and corners with four equivalent V(3)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. In the second Li site, Li(2) is bonded to one Cl(1), one Cl(8), two equivalent Cl(2), and two equivalent Cl(6) atoms to form LiCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra, edges with two equivalent V(1)Cl6 octahedra, edges with two equivalent V(2)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the third Li site, Li(3) is bonded to one Cl(5), one Cl(9), two equivalent Cl(10), and two equivalent Cl(7) atoms to form LiCl6 octahedra that share  a cornercorner with one Li(4)Cl4 tetrahedra, corners with two equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Li(3)Cl6 octahedra, edges with two equivalent V(1)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the fourth Li site, Li(4) is bonded to two equivalent Cl(6) and two equivalent Cl(9) atoms to form LiCl4 tetrahedra that share corners with two equivalent Li(2)Cl6 octahedra, corners with two equivalent Li(3)Cl6 octahedra, corners with two equivalent V(2)Cl6 octahedra, corners with two equivalent V(3)Cl6 octahedra, and corners with four equivalent V(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one Cl(1), one Cl(10), one Cl(2), one Cl(3), and two equivalent Cl(9) atoms to form VCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra,  an edgeedge with one Li(2)Cl6 octahedra,  an edgeedge with one V(2)Cl6 octahedra, edges with two equivalent Li(3)Cl6 octahedra, and edges with two equivalent V(1)Cl6 octahedra. In the second V site, V(2) is bonded to one Cl(3), one Cl(4), two equivalent Cl(2), and two equivalent Cl(6) atoms to form VCl6 octahedra that share  a cornercorner with one Li(1)Cl4 tetrahedra, corners with two equivalent Li(4)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, edges with two equivalent V(1)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. In the third V site, V(3) is bonded to one Cl(4), one Cl(6), one Cl(7), one Cl(8), and two equivalent Cl(5) atoms to form VCl6 octahedra that share  a cornercorner with one Li(4)Cl4 tetrahedra, corners with two equivalent Li(1)Cl4 tetrahedra,  an edgeedge with one Li(2)Cl6 octahedra,  an edgeedge with one V(2)Cl6 octahedra, edges with two equivalent Li(3)Cl6 octahedra, and edges with two equivalent V(3)Cl6 octahedra. There are ten inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent V(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one V(2) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth Cl site, Cl(4) is bonded to one Li(1), one V(2), and two equivalent V(3) atoms to form distorted ClLiV3 trigonal pyramids that share corners with two equivalent Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(8)Li2V2 trigonal pyramid,  an edgeedge with one Cl(8)Li2V2 trigonal pyramid, and edges with two equivalent Cl(6)Li2V2 trigonal pyramids. In the fifth Cl site, Cl(5) is bonded in a distorted T-shaped geometry to one Li(3) and two equivalent V(3) atoms. In the sixth Cl site, Cl(6) is bonded to one Li(2), one Li(4), one V(2), and one V(3) atom to form distorted ClLi2V2 trigonal pyramids that share  a cornercorner with one Cl(6)Li2V2 trigonal pyramid,  an edgeedge with one Cl(6)Li2V2 trigonal pyramid,  an edgeedge with one Cl(8)Li2V2 trigonal pyramid, and  an edgeedge with one Cl(4)LiV3 trigonal pyramid. In the seventh Cl site, Cl(7) is bonded in a distorted T-shaped geometry to two equivalent Li(3) and one V(3) atom. In the eighth Cl site, Cl(8) is bonded to one Li(1), one Li(2), and two equivalent V(3) atoms to form distorted ClLi2V2 trigonal pyramids that share corners with two equivalent Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(4)LiV3 trigonal pyramid,  an edgeedge with one Cl(4)LiV3 trigonal pyramid, and edges with two equivalent Cl(6)Li2V2 trigonal pyramids. In the ninth Cl site, Cl(9) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), and two equivalent V(1) atoms. In the tenth Cl site, Cl(10) is bonded to one Li(1), two equivalent Li(3), and one V(1) atom to form distorted ClLi3V tetrahedra that share  a cornercorner with one Cl(10)Li3V tetrahedra,  a cornercorner with one Cl(8)Li2V2 trigonal pyramid,  a cornercorner with one Cl(4)LiV3 trigonal pyramid, and  an edgeedge with one Cl(10)Li3V tetrahedra. is represented by the CIF file [CIF]
data_Li5V5Cl16
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   12.749
_cell_length_b   12.749
_cell_length_c   7.363
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   109.544
_symmetry_Int_Tables_number   1
_cell_volume   1127.866
_cell_formula_units_Z   2
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  0.992  0.508  0.009  1.0
  Li  Li1  1  0.690  0.810  0.763  1.0
  Li  Li2  1  0.191  0.809  0.264  1.0
  Li  Li3  1  0.691  0.309  0.264  1.0
  Li  Li4  1  0.998  0.002  0.500  1.0
  Li  Li5  1  0.191  0.809  0.736  1.0
  Li  Li6  1  0.691  0.309  0.736  1.0
  Li  Li7  1  0.492  0.008  0.991  1.0
  Li  Li8  1  0.190  0.310  0.237  1.0
  Li  Li9  1  0.498  0.502  0.500  1.0
  V  V10  1  0.688  0.565  0.999  1.0
  V  V11  1  0.935  0.812  0.999  1.0
  V  V12  1  0.688  0.812  0.244  1.0
  V  V13  1  0.189  0.568  0.499  1.0
  V  V14  1  0.432  0.811  0.501  1.0
  V  V15  1  0.689  0.068  0.501  1.0
  V  V16  1  0.932  0.311  0.499  1.0
  V  V17  1  0.188  0.312  0.756  1.0
  V  V18  1  0.435  0.312  0.001  1.0
  V  V19  1  0.188  0.065  0.001  1.0
  Cl  Cl20  1  0.812  0.688  0.777  1.0
  Cl  Cl21  1  0.577  0.689  0.011  1.0
  Cl  Cl22  1  0.811  0.923  0.011  1.0
  Cl  Cl23  1  0.808  0.692  0.232  1.0
  Cl  Cl24  1  0.567  0.933  0.267  1.0
  Cl  Cl25  1  0.814  0.186  0.275  1.0
  Cl  Cl26  1  0.314  0.686  0.275  1.0
  Cl  Cl27  1  0.798  0.934  0.493  1.0
  Cl  Cl28  1  0.566  0.702  0.493  1.0
  Cl  Cl29  1  0.076  0.684  0.501  1.0
  Cl  Cl30  1  0.576  0.184  0.499  1.0
  Cl  Cl31  1  0.816  0.424  0.501  1.0
  Cl  Cl32  1  0.316  0.924  0.499  1.0
  Cl  Cl33  1  0.314  0.686  0.725  1.0
  Cl  Cl34  1  0.814  0.186  0.725  1.0
  Cl  Cl35  1  0.565  0.935  0.726  1.0
  Cl  Cl36  1  0.062  0.937  0.772  1.0
  Cl  Cl37  1  0.563  0.438  0.772  1.0
  Cl  Cl38  1  0.308  0.192  0.768  1.0
  Cl  Cl39  1  0.297  0.938  0.999  1.0
  Cl  Cl40  1  0.797  0.438  0.001  1.0
  Cl  Cl41  1  0.062  0.703  0.001  1.0
  Cl  Cl42  1  0.562  0.203  0.999  1.0
  Cl  Cl43  1  0.077  0.189  0.989  1.0
  Cl  Cl44  1  0.311  0.423  0.989  1.0
  Cl  Cl45  1  0.312  0.188  0.223  1.0
  Cl  Cl46  1  0.063  0.938  0.228  1.0
  Cl  Cl47  1  0.562  0.437  0.228  1.0
  Cl  Cl48  1  0.065  0.435  0.274  1.0
  Cl  Cl49  1  0.298  0.434  0.507  1.0
  Cl  Cl50  1  0.066  0.202  0.507  1.0
  Cl  Cl51  1  0.067  0.433  0.733  1.0
[/CIF]
.