The structure described by Li20Si3P3S23Cl is Aluminum carbonitride-derived structured and crystallizes in the monoclinic Pm space group. There are twelve inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(10), one S(15), and one Cl(1) atom to form distorted LiS3Cl tetrahedra that share  a cornercorner with one Li(8)S5Cl octahedra,  a cornercorner with one Li(7)S6 octahedra,  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(3)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(6)S6 octahedra,  an edgeedge with one Li(11)S4 tetrahedra, and  an edgeedge with one Si(2)S3Cl tetrahedra. The corner-sharing octahedral tilt angles range from 59-61°. In the second Li site, Li(2) is bonded to one S(1), one S(14), one S(17), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(8)S5Cl octahedra,  a cornercorner with one Li(5)S6 octahedra,  a cornercorner with one Li(1)S3Cl tetrahedra,  a cornercorner with one Li(10)S4 tetrahedra,  a cornercorner with one Li(11)S4 tetrahedra,  a cornercorner with one Li(9)S4 tetrahedra,  a cornercorner with one Si(2)S3Cl tetrahedra,  a cornercorner with one Si(3)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra,  a cornercorner with one Li(12)S4 trigonal pyramid,  an edgeedge with one Li(6)S6 octahedra, and  an edgeedge with one P(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-61°. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one S(11), one S(13), one S(16), and one S(5) atom. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one S(12), one S(13), one S(16), and one S(6) atom. In the fifth Li site, Li(5) is bonded to one S(2), one S(3), two equivalent S(13), and two equivalent S(7) atoms to form LiS6 octahedra that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent P(3)S4 tetrahedra,  an edgeedge with one P(1)S4 tetrahedra,  an edgeedge with one P(2)S4 tetrahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. In the sixth Li site, Li(6) is bonded to one S(14), one S(15), one S(8), one S(9), and two equivalent S(1) atoms to form LiS6 octahedra that share corners with two equivalent Si(3)S4 tetrahedra,  an edgeedge with one P(1)S4 tetrahedra,  an edgeedge with one P(2)S4 tetrahedra, edges with two equivalent Li(1)S3Cl tetrahedra, edges with two equivalent Li(11)S4 tetrahedra, edges with two equivalent Li(2)S4 tetrahedra, and edges with two equivalent Li(12)S4 trigonal pyramids. In the seventh Li site, Li(7) is bonded to one S(5), one S(6), two equivalent S(10), and two equivalent S(16) atoms to form distorted LiS6 octahedra that share corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Si(3)S4 tetrahedra,  an edgeedge with one Si(2)S3Cl tetrahedra,  an edgeedge with one Si(1)S4 tetrahedra, edges with two equivalent Li(11)S4 tetrahedra, and edges with two equivalent Li(12)S4 trigonal pyramids. In the eighth Li site, Li(8) is bonded to one S(11), one S(12), one S(17), two equivalent S(4), and one Cl(1) atom to form distorted LiS5Cl octahedra that share corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent P(3)S4 tetrahedra,  an edgeedge with one Si(2)S3Cl tetrahedra,  an edgeedge with one Si(1)S4 tetrahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. In the ninth Li site, Li(9) is bonded to one S(11), one S(2), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(1)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(8)S5Cl octahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one P(3)S4 tetrahedra. In the tenth Li site, Li(10) is bonded to one S(12), one S(3), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(1)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(8)S5Cl octahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one P(3)S4 tetrahedra. In the eleventh Li site, Li(11) is bonded to one S(1), one S(10), one S(5), and one S(8) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(2)S3Cl tetrahedra,  a cornercorner with one P(1)S4 tetrahedra, corners with two equivalent Li(11)S4 tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(6)S6 octahedra,  an edgeedge with one Li(7)S6 octahedra,  an edgeedge with one Li(1)S3Cl tetrahedra, and  an edgeedge with one Si(3)S4 tetrahedra. In the twelfth Li site, Li(12) is bonded to one S(1), one S(10), one S(6), and one S(9) atom to form distorted LiS4 trigonal pyramids that share  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(2)S3Cl tetrahedra,  a cornercorner with one P(1)S4 tetrahedra, corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(11)S4 tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(6)S6 octahedra,  an edgeedge with one Li(7)S6 octahedra, and  an edgeedge with one Si(3)S4 tetrahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one S(11), one S(12), and two equivalent S(16) atoms to form SiS4 tetrahedra that share corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(8)S5Cl octahedra, and  an edgeedge with one Li(7)S6 octahedra. In the second Si site, Si(2) is bonded to one S(17), two equivalent S(10), and one Cl(1) atom to form SiS3Cl tetrahedra that share corners with two equivalent Li(11)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(8)S5Cl octahedra,  an edgeedge with one Li(7)S6 octahedra, and edges with two equivalent Li(1)S3Cl tetrahedra. In the third Si site, Si(3) is bonded to one S(5), one S(6), and two equivalent S(1) atoms to form SiS4 tetrahedra that share corners with two equivalent Li(6)S6 octahedra, corners with two equivalent Li(7)S6 octahedra, corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, edges with two equivalent Li(11)S4 tetrahedra, and edges with two equivalent Li(12)S4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 36-46°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one S(8), one S(9), and two equivalent S(13) atoms to form PS4 tetrahedra that share corners with two equivalent Li(11)S4 tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one Li(6)S6 octahedra. In the second P site, P(2) is bonded to one S(14), one S(15), and two equivalent S(7) atoms to form PS4 tetrahedra that share corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(5)S6 octahedra,  an edgeedge with one Li(6)S6 octahedra, and edges with two equivalent Li(2)S4 tetrahedra. In the third P site, P(3) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form PS4 tetrahedra that share corners with two equivalent Li(8)S5Cl octahedra, corners with two equivalent Li(5)S6 octahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-46°. There are seventeen inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(11), one Li(12), one Li(2), one Li(6), and one Si(3) atom to form distorted SLi5Si octahedra that share corners with two equivalent S(1)Li5Si octahedra,  a cornercorner with one S(17)Li3Si tetrahedra,  a cornercorner with one Cl(1)Li3Si trigonal pyramid,  an edgeedge with one S(5)Li5Si pentagonal pyramid,  an edgeedge with one S(15)Li3P trigonal pyramid,  an edgeedge with one S(8)Li3P trigonal pyramid, and  an edgeedge with one S(9)Li3P trigonal pyramid. The corner-sharing octahedral tilt angles range from 14-70°. In the second S site, S(2) is bonded to one Li(5), two equivalent Li(9), and one P(3) atom to form distorted SLi3P trigonal pyramids that share corners with two equivalent S(11)Li5Si pentagonal pyramids, corners with two equivalent S(13)Li3P tetrahedra, and edges with two equivalent S(4)Li3P trigonal pyramids. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Li(5), two equivalent Li(10), and one P(3) atom. In the fourth S site, S(4) is bonded to one Li(10), one Li(8), one Li(9), and one P(3) atom to form distorted SLi3P trigonal pyramids that share  a cornercorner with one S(17)Li3Si tetrahedra,  a cornercorner with one Cl(1)Li3Si trigonal pyramid, corners with two equivalent S(4)Li3P trigonal pyramids,  an edgeedge with one S(11)Li5Si pentagonal pyramid, and  an edgeedge with one S(2)Li3P trigonal pyramid. In the fifth S site, S(5) is bonded to one Li(7), two equivalent Li(11), two equivalent Li(3), and one Si(3) atom to form distorted SLi5Si pentagonal pyramids that share corners with two equivalent S(13)Li3P tetrahedra, corners with two equivalent S(8)Li3P trigonal pyramids, edges with two equivalent S(1)Li5Si octahedra,  an edgeedge with one S(11)Li5Si pentagonal pyramid, and edges with two equivalent S(16)Li3Si trigonal pyramids. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one Li(7), two equivalent Li(12), two equivalent Li(4), and one Si(3) atom. In the seventh S site, S(7) is bonded in a distorted pentagonal planar geometry to one Li(10), one Li(2), one Li(5), one Li(9), and one P(2) atom. In the eighth S site, S(8) is bonded to one Li(6), two equivalent Li(11), and one P(1) atom to form SLi3P trigonal pyramids that share corners with two equivalent S(5)Li5Si pentagonal pyramids, corners with two equivalent S(13)Li3P tetrahedra,  a cornercorner with one S(15)Li3P trigonal pyramid, edges with two equivalent S(1)Li5Si octahedra, and  an edgeedge with one S(9)Li3P trigonal pyramid. In the ninth S site, S(9) is bonded to one Li(6), two equivalent Li(12), and one P(1) atom to form SLi3P trigonal pyramids that share corners with two equivalent S(13)Li3P tetrahedra,  a cornercorner with one S(15)Li3P trigonal pyramid, edges with two equivalent S(1)Li5Si octahedra, and  an edgeedge with one S(8)Li3P trigonal pyramid. In the tenth S site, S(10) is bonded in a 5-coordinate geometry to one Li(1), one Li(11), one Li(12), one Li(7), and one Si(2) atom. In the eleventh S site, S(11) is bonded to one Li(8), two equivalent Li(3), two equivalent Li(9), and one Si(1) atom to form distorted SLi5Si pentagonal pyramids that share  a cornercorner with one S(17)Li3Si tetrahedra, corners with two equivalent S(13)Li3P tetrahedra,  a cornercorner with one Cl(1)Li3Si trigonal pyramid, corners with two equivalent S(2)Li3P trigonal pyramids,  an edgeedge with one S(5)Li5Si pentagonal pyramid, edges with two equivalent S(4)Li3P trigonal pyramids, and edges with two equivalent S(16)Li3Si trigonal pyramids. In the twelfth S site, S(12) is bonded in a distorted hexagonal planar geometry to one Li(8), two equivalent Li(10), two equivalent Li(4), and one Si(1) atom. In the thirteenth S site, S(13) is bonded to one Li(3), one Li(4), one Li(5), and one P(1) atom to form distorted SLi3P tetrahedra that share  a cornercorner with one S(11)Li5Si pentagonal pyramid,  a cornercorner with one S(5)Li5Si pentagonal pyramid,  a cornercorner with one S(2)Li3P trigonal pyramid,  a cornercorner with one S(8)Li3P trigonal pyramid,  a cornercorner with one S(9)Li3P trigonal pyramid, corners with two equivalent S(16)Li3Si trigonal pyramids, and  an edgeedge with one S(13)Li3P tetrahedra. In the fourteenth S site, S(14) is bonded in a rectangular see-saw-like geometry to one Li(6), two equivalent Li(2), and one P(2) atom. In the fifteenth S site, S(15) is bonded to one Li(6), two equivalent Li(1), and one P(2) atom to form SLi3P trigonal pyramids that share  a cornercorner with one S(8)Li3P trigonal pyramid,  a cornercorner with one S(9)Li3P trigonal pyramid, corners with two equivalent Cl(1)Li3Si trigonal pyramids, and edges with two equivalent S(1)Li5Si octahedra. In the sixteenth S site, S(16) is bonded to one Li(3), one Li(4), one Li(7), and one Si(1) atom to form distorted SLi3Si trigonal pyramids that share corners with two equivalent S(13)Li3P tetrahedra,  an edgeedge with one S(11)Li5Si pentagonal pyramid,  an edgeedge with one S(5)Li5Si pentagonal pyramid, and  an edgeedge with one S(16)Li3Si trigonal pyramid. In the seventeenth S site, S(17) is bonded to one Li(8), two equivalent Li(2), and one Si(2) atom to form SLi3Si tetrahedra that share corners with two equivalent S(1)Li5Si octahedra,  a cornercorner with one S(11)Li5Si pentagonal pyramid, corners with two equivalent S(4)Li3P trigonal pyramids, and  an edgeedge with one Cl(1)Li3Si trigonal pyramid. The corner-sharing octahedral tilt angles are 63°. Cl(1) is bonded to one Li(8), two equivalent Li(1), and one Si(2) atom to form ClLi3Si trigonal pyramids that share corners with two equivalent S(1)Li5Si octahedra,  a cornercorner with one S(11)Li5Si pentagonal pyramid, corners with two equivalent S(15)Li3P trigonal pyramids, corners with two equivalent S(4)Li3P trigonal pyramids, and  an edgeedge with one S(17)Li3Si tetrahedra. The corner-sharing octahedral tilt angles are 71°. is represented by the CIF file [CIF]
data_Li20Si3P3S23Cl
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   8.772
_cell_length_b   8.898
_cell_length_c   12.793
_cell_angle_alpha   89.843
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   998.528
_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  0.238  0.757  0.310  1.0
  Li  Li1  1  0.782  0.158  0.261  1.0
  Li  Li2  1  0.819  0.774  0.766  1.0
  Li  Li3  1  0.221  0.260  0.772  1.0
  Li  Li4  1  0.762  0.757  0.310  1.0
  Li  Li5  1  0.218  0.158  0.261  1.0
  Li  Li6  1  0.181  0.774  0.766  1.0
  Li  Li7  1  0.779  0.260  0.772  1.0
  Li  Li8  1  0.500  0.999  0.937  1.0
  Li  Li9  1  0.500  1.000  0.441  1.0
  Li  Li10  1  0.000  0.508  0.581  1.0
  Li  Li11  1  0.000  0.488  0.056  1.0
  Li  Li12  1  0.740  0.739  0.008  1.0
  Li  Li13  1  0.263  0.262  0.011  1.0
  Li  Li14  1  0.240  0.751  0.535  1.0
  Li  Li15  1  0.757  0.252  0.512  1.0
  Li  Li16  1  0.760  0.751  0.535  1.0
  Li  Li17  1  0.243  0.252  0.512  1.0
  Li  Li18  1  0.260  0.739  0.008  1.0
  Li  Li19  1  0.737  0.262  0.011  1.0
  Si  Si20  1  0.000  0.506  0.817  1.0
  Si  Si21  1  0.000  0.489  0.335  1.0
  Si  Si22  1  0.000  0.005  0.513  1.0
  P  P23  1  0.500  0.004  0.688  1.0
  P  P24  1  0.500  0.997  0.184  1.0
  P  P25  1  0.500  0.505  0.005  1.0
  S  S26  1  0.800  0.991  0.417  1.0
  S  S27  1  0.200  0.991  0.417  1.0
  S  S28  1  0.500  0.694  0.913  1.0
  S  S29  1  0.500  0.314  0.912  1.0
  S  S30  1  0.308  0.500  0.098  1.0
  S  S31  1  0.692  0.500  0.098  1.0
  S  S32  1  0.000  0.814  0.614  1.0
  S  S33  1  0.000  0.207  0.599  1.0
  S  S34  1  0.699  0.001  0.094  1.0
  S  S35  1  0.301  0.001  0.094  1.0
  S  S36  1  0.500  0.811  0.600  1.0
  S  S37  1  0.500  0.196  0.596  1.0
  S  S38  1  0.204  0.517  0.419  1.0
  S  S39  1  0.796  0.517  0.419  1.0
  S  S40  1  0.000  0.706  0.917  1.0
  S  S41  1  0.000  0.300  0.910  1.0
  S  S42  1  0.312  0.007  0.785  1.0
  S  S43  1  0.688  0.007  0.785  1.0
  S  S44  1  0.500  0.185  0.274  1.0
  S  S45  1  0.500  0.802  0.269  1.0
  S  S46  1  0.800  0.514  0.724  1.0
  S  S47  1  0.200  0.514  0.724  1.0
  S  S48  1  0.000  0.315  0.225  1.0
  Cl  Cl49  1  0.000  0.695  0.227  1.0
[/CIF]
.
The structure described by Li20Si3P3S23Cl is Aluminum carbonitride-derived structured and crystallizes in the monoclinic Pm space group. There are twelve inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(10), one S(15), and one Cl(1) atom to form distorted LiS3Cl tetrahedra that share  a cornercorner with one Li(8)S5Cl octahedra,  a cornercorner with one Li(7)S6 octahedra,  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(3)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(6)S6 octahedra,  an edgeedge with one Li(11)S4 tetrahedra, and  an edgeedge with one Si(2)S3Cl tetrahedra. The corner-sharing octahedral tilt angles range from 59-61°. In the second Li site, Li(2) is bonded to one S(1), one S(14), one S(17), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(8)S5Cl octahedra,  a cornercorner with one Li(5)S6 octahedra,  a cornercorner with one Li(1)S3Cl tetrahedra,  a cornercorner with one Li(10)S4 tetrahedra,  a cornercorner with one Li(11)S4 tetrahedra,  a cornercorner with one Li(9)S4 tetrahedra,  a cornercorner with one Si(2)S3Cl tetrahedra,  a cornercorner with one Si(3)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra,  a cornercorner with one Li(12)S4 trigonal pyramid,  an edgeedge with one Li(6)S6 octahedra, and  an edgeedge with one P(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-61°. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one S(11), one S(13), one S(16), and one S(5) atom. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one S(12), one S(13), one S(16), and one S(6) atom. In the fifth Li site, Li(5) is bonded to one S(2), one S(3), two equivalent S(13), and two equivalent S(7) atoms to form LiS6 octahedra that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent P(3)S4 tetrahedra,  an edgeedge with one P(1)S4 tetrahedra,  an edgeedge with one P(2)S4 tetrahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. In the sixth Li site, Li(6) is bonded to one S(14), one S(15), one S(8), one S(9), and two equivalent S(1) atoms to form LiS6 octahedra that share corners with two equivalent Si(3)S4 tetrahedra,  an edgeedge with one P(1)S4 tetrahedra,  an edgeedge with one P(2)S4 tetrahedra, edges with two equivalent Li(1)S3Cl tetrahedra, edges with two equivalent Li(11)S4 tetrahedra, edges with two equivalent Li(2)S4 tetrahedra, and edges with two equivalent Li(12)S4 trigonal pyramids. In the seventh Li site, Li(7) is bonded to one S(5), one S(6), two equivalent S(10), and two equivalent S(16) atoms to form distorted LiS6 octahedra that share corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Si(3)S4 tetrahedra,  an edgeedge with one Si(2)S3Cl tetrahedra,  an edgeedge with one Si(1)S4 tetrahedra, edges with two equivalent Li(11)S4 tetrahedra, and edges with two equivalent Li(12)S4 trigonal pyramids. In the eighth Li site, Li(8) is bonded to one S(11), one S(12), one S(17), two equivalent S(4), and one Cl(1) atom to form distorted LiS5Cl octahedra that share corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent P(3)S4 tetrahedra,  an edgeedge with one Si(2)S3Cl tetrahedra,  an edgeedge with one Si(1)S4 tetrahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. In the ninth Li site, Li(9) is bonded to one S(11), one S(2), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(1)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(8)S5Cl octahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one P(3)S4 tetrahedra. In the tenth Li site, Li(10) is bonded to one S(12), one S(3), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(1)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(8)S5Cl octahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one P(3)S4 tetrahedra. In the eleventh Li site, Li(11) is bonded to one S(1), one S(10), one S(5), and one S(8) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(2)S3Cl tetrahedra,  a cornercorner with one P(1)S4 tetrahedra, corners with two equivalent Li(11)S4 tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(6)S6 octahedra,  an edgeedge with one Li(7)S6 octahedra,  an edgeedge with one Li(1)S3Cl tetrahedra, and  an edgeedge with one Si(3)S4 tetrahedra. In the twelfth Li site, Li(12) is bonded to one S(1), one S(10), one S(6), and one S(9) atom to form distorted LiS4 trigonal pyramids that share  a cornercorner with one Li(2)S4 tetrahedra,  a cornercorner with one Si(2)S3Cl tetrahedra,  a cornercorner with one P(1)S4 tetrahedra, corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(11)S4 tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(6)S6 octahedra,  an edgeedge with one Li(7)S6 octahedra, and  an edgeedge with one Si(3)S4 tetrahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one S(11), one S(12), and two equivalent S(16) atoms to form SiS4 tetrahedra that share corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(8)S5Cl octahedra, and  an edgeedge with one Li(7)S6 octahedra. In the second Si site, Si(2) is bonded to one S(17), two equivalent S(10), and one Cl(1) atom to form SiS3Cl tetrahedra that share corners with two equivalent Li(11)S4 tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(8)S5Cl octahedra,  an edgeedge with one Li(7)S6 octahedra, and edges with two equivalent Li(1)S3Cl tetrahedra. In the third Si site, Si(3) is bonded to one S(5), one S(6), and two equivalent S(1) atoms to form SiS4 tetrahedra that share corners with two equivalent Li(6)S6 octahedra, corners with two equivalent Li(7)S6 octahedra, corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(2)S4 tetrahedra, edges with two equivalent Li(11)S4 tetrahedra, and edges with two equivalent Li(12)S4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 36-46°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one S(8), one S(9), and two equivalent S(13) atoms to form PS4 tetrahedra that share corners with two equivalent Li(11)S4 tetrahedra, corners with two equivalent Li(12)S4 trigonal pyramids,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one Li(6)S6 octahedra. In the second P site, P(2) is bonded to one S(14), one S(15), and two equivalent S(7) atoms to form PS4 tetrahedra that share corners with two equivalent Li(1)S3Cl tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(5)S6 octahedra,  an edgeedge with one Li(6)S6 octahedra, and edges with two equivalent Li(2)S4 tetrahedra. In the third P site, P(3) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form PS4 tetrahedra that share corners with two equivalent Li(8)S5Cl octahedra, corners with two equivalent Li(5)S6 octahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-46°. There are seventeen inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(11), one Li(12), one Li(2), one Li(6), and one Si(3) atom to form distorted SLi5Si octahedra that share corners with two equivalent S(1)Li5Si octahedra,  a cornercorner with one S(17)Li3Si tetrahedra,  a cornercorner with one Cl(1)Li3Si trigonal pyramid,  an edgeedge with one S(5)Li5Si pentagonal pyramid,  an edgeedge with one S(15)Li3P trigonal pyramid,  an edgeedge with one S(8)Li3P trigonal pyramid, and  an edgeedge with one S(9)Li3P trigonal pyramid. The corner-sharing octahedral tilt angles range from 14-70°. In the second S site, S(2) is bonded to one Li(5), two equivalent Li(9), and one P(3) atom to form distorted SLi3P trigonal pyramids that share corners with two equivalent S(11)Li5Si pentagonal pyramids, corners with two equivalent S(13)Li3P tetrahedra, and edges with two equivalent S(4)Li3P trigonal pyramids. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Li(5), two equivalent Li(10), and one P(3) atom. In the fourth S site, S(4) is bonded to one Li(10), one Li(8), one Li(9), and one P(3) atom to form distorted SLi3P trigonal pyramids that share  a cornercorner with one S(17)Li3Si tetrahedra,  a cornercorner with one Cl(1)Li3Si trigonal pyramid, corners with two equivalent S(4)Li3P trigonal pyramids,  an edgeedge with one S(11)Li5Si pentagonal pyramid, and  an edgeedge with one S(2)Li3P trigonal pyramid. In the fifth S site, S(5) is bonded to one Li(7), two equivalent Li(11), two equivalent Li(3), and one Si(3) atom to form distorted SLi5Si pentagonal pyramids that share corners with two equivalent S(13)Li3P tetrahedra, corners with two equivalent S(8)Li3P trigonal pyramids, edges with two equivalent S(1)Li5Si octahedra,  an edgeedge with one S(11)Li5Si pentagonal pyramid, and edges with two equivalent S(16)Li3Si trigonal pyramids. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one Li(7), two equivalent Li(12), two equivalent Li(4), and one Si(3) atom. In the seventh S site, S(7) is bonded in a distorted pentagonal planar geometry to one Li(10), one Li(2), one Li(5), one Li(9), and one P(2) atom. In the eighth S site, S(8) is bonded to one Li(6), two equivalent Li(11), and one P(1) atom to form SLi3P trigonal pyramids that share corners with two equivalent S(5)Li5Si pentagonal pyramids, corners with two equivalent S(13)Li3P tetrahedra,  a cornercorner with one S(15)Li3P trigonal pyramid, edges with two equivalent S(1)Li5Si octahedra, and  an edgeedge with one S(9)Li3P trigonal pyramid. In the ninth S site, S(9) is bonded to one Li(6), two equivalent Li(12), and one P(1) atom to form SLi3P trigonal pyramids that share corners with two equivalent S(13)Li3P tetrahedra,  a cornercorner with one S(15)Li3P trigonal pyramid, edges with two equivalent S(1)Li5Si octahedra, and  an edgeedge with one S(8)Li3P trigonal pyramid. In the tenth S site, S(10) is bonded in a 5-coordinate geometry to one Li(1), one Li(11), one Li(12), one Li(7), and one Si(2) atom. In the eleventh S site, S(11) is bonded to one Li(8), two equivalent Li(3), two equivalent Li(9), and one Si(1) atom to form distorted SLi5Si pentagonal pyramids that share  a cornercorner with one S(17)Li3Si tetrahedra, corners with two equivalent S(13)Li3P tetrahedra,  a cornercorner with one Cl(1)Li3Si trigonal pyramid, corners with two equivalent S(2)Li3P trigonal pyramids,  an edgeedge with one S(5)Li5Si pentagonal pyramid, edges with two equivalent S(4)Li3P trigonal pyramids, and edges with two equivalent S(16)Li3Si trigonal pyramids. In the twelfth S site, S(12) is bonded in a distorted hexagonal planar geometry to one Li(8), two equivalent Li(10), two equivalent Li(4), and one Si(1) atom. In the thirteenth S site, S(13) is bonded to one Li(3), one Li(4), one Li(5), and one P(1) atom to form distorted SLi3P tetrahedra that share  a cornercorner with one S(11)Li5Si pentagonal pyramid,  a cornercorner with one S(5)Li5Si pentagonal pyramid,  a cornercorner with one S(2)Li3P trigonal pyramid,  a cornercorner with one S(8)Li3P trigonal pyramid,  a cornercorner with one S(9)Li3P trigonal pyramid, corners with two equivalent S(16)Li3Si trigonal pyramids, and  an edgeedge with one S(13)Li3P tetrahedra. In the fourteenth S site, S(14) is bonded in a rectangular see-saw-like geometry to one Li(6), two equivalent Li(2), and one P(2) atom. In the fifteenth S site, S(15) is bonded to one Li(6), two equivalent Li(1), and one P(2) atom to form SLi3P trigonal pyramids that share  a cornercorner with one S(8)Li3P trigonal pyramid,  a cornercorner with one S(9)Li3P trigonal pyramid, corners with two equivalent Cl(1)Li3Si trigonal pyramids, and edges with two equivalent S(1)Li5Si octahedra. In the sixteenth S site, S(16) is bonded to one Li(3), one Li(4), one Li(7), and one Si(1) atom to form distorted SLi3Si trigonal pyramids that share corners with two equivalent S(13)Li3P tetrahedra,  an edgeedge with one S(11)Li5Si pentagonal pyramid,  an edgeedge with one S(5)Li5Si pentagonal pyramid, and  an edgeedge with one S(16)Li3Si trigonal pyramid. In the seventeenth S site, S(17) is bonded to one Li(8), two equivalent Li(2), and one Si(2) atom to form SLi3Si tetrahedra that share corners with two equivalent S(1)Li5Si octahedra,  a cornercorner with one S(11)Li5Si pentagonal pyramid, corners with two equivalent S(4)Li3P trigonal pyramids, and  an edgeedge with one Cl(1)Li3Si trigonal pyramid. The corner-sharing octahedral tilt angles are 63°. Cl(1) is bonded to one Li(8), two equivalent Li(1), and one Si(2) atom to form ClLi3Si trigonal pyramids that share corners with two equivalent S(1)Li5Si octahedra,  a cornercorner with one S(11)Li5Si pentagonal pyramid, corners with two equivalent S(15)Li3P trigonal pyramids, corners with two equivalent S(4)Li3P trigonal pyramids, and  an edgeedge with one S(17)Li3Si tetrahedra. The corner-sharing octahedral tilt angles are 71°. is represented by the CIF file [CIF]
data_Li20Si3P3S23Cl
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   8.772
_cell_length_b   8.898
_cell_length_c   12.793
_cell_angle_alpha   89.843
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   998.528
_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  0.238  0.757  0.310  1.0
  Li  Li1  1  0.782  0.158  0.261  1.0
  Li  Li2  1  0.819  0.774  0.766  1.0
  Li  Li3  1  0.221  0.260  0.772  1.0
  Li  Li4  1  0.762  0.757  0.310  1.0
  Li  Li5  1  0.218  0.158  0.261  1.0
  Li  Li6  1  0.181  0.774  0.766  1.0
  Li  Li7  1  0.779  0.260  0.772  1.0
  Li  Li8  1  0.500  0.999  0.937  1.0
  Li  Li9  1  0.500  1.000  0.441  1.0
  Li  Li10  1  0.000  0.508  0.581  1.0
  Li  Li11  1  0.000  0.488  0.056  1.0
  Li  Li12  1  0.740  0.739  0.008  1.0
  Li  Li13  1  0.263  0.262  0.011  1.0
  Li  Li14  1  0.240  0.751  0.535  1.0
  Li  Li15  1  0.757  0.252  0.512  1.0
  Li  Li16  1  0.760  0.751  0.535  1.0
  Li  Li17  1  0.243  0.252  0.512  1.0
  Li  Li18  1  0.260  0.739  0.008  1.0
  Li  Li19  1  0.737  0.262  0.011  1.0
  Si  Si20  1  0.000  0.506  0.817  1.0
  Si  Si21  1  0.000  0.489  0.335  1.0
  Si  Si22  1  0.000  0.005  0.513  1.0
  P  P23  1  0.500  0.004  0.688  1.0
  P  P24  1  0.500  0.997  0.184  1.0
  P  P25  1  0.500  0.505  0.005  1.0
  S  S26  1  0.800  0.991  0.417  1.0
  S  S27  1  0.200  0.991  0.417  1.0
  S  S28  1  0.500  0.694  0.913  1.0
  S  S29  1  0.500  0.314  0.912  1.0
  S  S30  1  0.308  0.500  0.098  1.0
  S  S31  1  0.692  0.500  0.098  1.0
  S  S32  1  0.000  0.814  0.614  1.0
  S  S33  1  0.000  0.207  0.599  1.0
  S  S34  1  0.699  0.001  0.094  1.0
  S  S35  1  0.301  0.001  0.094  1.0
  S  S36  1  0.500  0.811  0.600  1.0
  S  S37  1  0.500  0.196  0.596  1.0
  S  S38  1  0.204  0.517  0.419  1.0
  S  S39  1  0.796  0.517  0.419  1.0
  S  S40  1  0.000  0.706  0.917  1.0
  S  S41  1  0.000  0.300  0.910  1.0
  S  S42  1  0.312  0.007  0.785  1.0
  S  S43  1  0.688  0.007  0.785  1.0
  S  S44  1  0.500  0.185  0.274  1.0
  S  S45  1  0.500  0.802  0.269  1.0
  S  S46  1  0.800  0.514  0.724  1.0
  S  S47  1  0.200  0.514  0.724  1.0
  S  S48  1  0.000  0.315  0.225  1.0
  Cl  Cl49  1  0.000  0.695  0.227  1.0
[/CIF]
.