The crystal structure described by Li4TiS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted LiS6 octahedra that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent Ti(1)S4 tetrahedra, corners with six equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, edges with two equivalent Li(2)S4 tetrahedra, edges with two equivalent Ti(1)S4 tetrahedra, and faces with two equivalent Li(3)S4 trigonal pyramids. In the second Li site, Li(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form LiS4 tetrahedra that share corners with two equivalent Li(1)S6 octahedra, corners with two equivalent Ti(1)S4 tetrahedra, corners with eight equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, and  an edgeedge with one Ti(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. In the third Li site, Li(3) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted LiS4 trigonal pyramids that share corners with three equivalent Li(1)S6 octahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with four equivalent Ti(1)S4 tetrahedra, corners with four equivalent Li(3)S4 trigonal pyramids, and  a faceface with one Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 18-51°. Ti(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form TiS4 tetrahedra that share corners with two equivalent Li(1)S6 octahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with eight equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, and  an edgeedge with one Li(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Ti(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Ti(1) atom. In the third S site, S(3) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Ti(1) atom to form distorted corner-sharing SLi4Ti trigonal bipyramids. is represented by the CIF card [CIF]
data_Li4TiS4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.186
_cell_length_b   7.766
_cell_length_c   14.179
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   681.142
_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  0.500  0.000  0.000  1.0
  Li  Li1  1  0.500  0.500  0.000  1.0
  Li  Li2  1  0.870  0.250  0.088  1.0
  Li  Li3  1  0.309  0.498  0.178  1.0
  Li  Li4  1  0.309  0.002  0.178  1.0
  Li  Li5  1  0.809  0.998  0.322  1.0
  Li  Li6  1  0.809  0.502  0.322  1.0
  Li  Li7  1  0.370  0.750  0.412  1.0
  Li  Li8  1  0.000  0.000  0.500  1.0
  Li  Li9  1  0.000  0.500  0.500  1.0
  Li  Li10  1  0.630  0.250  0.588  1.0
  Li  Li11  1  0.191  0.498  0.678  1.0
  Li  Li12  1  0.191  0.002  0.678  1.0
  Li  Li13  1  0.691  0.998  0.822  1.0
  Li  Li14  1  0.691  0.502  0.822  1.0
  Li  Li15  1  0.130  0.750  0.912  1.0
  Ti  Ti16  1  0.851  0.750  0.088  1.0
  Ti  Ti17  1  0.351  0.250  0.412  1.0
  Ti  Ti18  1  0.649  0.750  0.588  1.0
  Ti  Ti19  1  0.149  0.250  0.912  1.0
  S  S20  1  0.262  0.250  0.064  1.0
  S  S21  1  0.216  0.750  0.082  1.0
  S  S22  1  0.717  0.509  0.157  1.0
  S  S23  1  0.717  0.991  0.157  1.0
  S  S24  1  0.217  0.009  0.343  1.0
  S  S25  1  0.217  0.491  0.343  1.0
  S  S26  1  0.716  0.250  0.418  1.0
  S  S27  1  0.762  0.750  0.436  1.0
  S  S28  1  0.238  0.250  0.564  1.0
  S  S29  1  0.284  0.750  0.582  1.0
  S  S30  1  0.783  0.509  0.657  1.0
  S  S31  1  0.783  0.991  0.657  1.0
  S  S32  1  0.283  0.009  0.843  1.0
  S  S33  1  0.283  0.491  0.843  1.0
  S  S34  1  0.784  0.250  0.918  1.0
  S  S35  1  0.738  0.750  0.936  1.0
[/CIF]
.
The crystal structure described by Li4TiS4 is Aluminum carbonitride-like structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted LiS6 octahedra that share corners with two equivalent Li(2)S4 tetrahedra, corners with two equivalent Ti(1)S4 tetrahedra, corners with six equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, edges with two equivalent Li(2)S4 tetrahedra, edges with two equivalent Ti(1)S4 tetrahedra, and faces with two equivalent Li(3)S4 trigonal pyramids. In the second Li site, Li(2) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form LiS4 tetrahedra that share corners with two equivalent Li(1)S6 octahedra, corners with two equivalent Ti(1)S4 tetrahedra, corners with eight equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, and  an edgeedge with one Ti(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. In the third Li site, Li(3) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted LiS4 trigonal pyramids that share corners with three equivalent Li(1)S6 octahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with four equivalent Ti(1)S4 tetrahedra, corners with four equivalent Li(3)S4 trigonal pyramids, and  a faceface with one Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 18-51°. Ti(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form TiS4 tetrahedra that share corners with two equivalent Li(1)S6 octahedra, corners with two equivalent Li(2)S4 tetrahedra, corners with eight equivalent Li(3)S4 trigonal pyramids, edges with two equivalent Li(1)S6 octahedra, and  an edgeedge with one Li(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Ti(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Ti(1) atom. In the third S site, S(3) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Ti(1) atom to form distorted corner-sharing SLi4Ti trigonal bipyramids. is represented by the CIF card [CIF]
data_Li4TiS4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.186
_cell_length_b   7.766
_cell_length_c   14.179
_cell_angle_alpha   90.000
_cell_angle_beta   90.000
_cell_angle_gamma   90.000
_symmetry_Int_Tables_number   1
_cell_volume   681.142
_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  0.500  0.000  0.000  1.0
  Li  Li1  1  0.500  0.500  0.000  1.0
  Li  Li2  1  0.870  0.250  0.088  1.0
  Li  Li3  1  0.309  0.498  0.178  1.0
  Li  Li4  1  0.309  0.002  0.178  1.0
  Li  Li5  1  0.809  0.998  0.322  1.0
  Li  Li6  1  0.809  0.502  0.322  1.0
  Li  Li7  1  0.370  0.750  0.412  1.0
  Li  Li8  1  0.000  0.000  0.500  1.0
  Li  Li9  1  0.000  0.500  0.500  1.0
  Li  Li10  1  0.630  0.250  0.588  1.0
  Li  Li11  1  0.191  0.498  0.678  1.0
  Li  Li12  1  0.191  0.002  0.678  1.0
  Li  Li13  1  0.691  0.998  0.822  1.0
  Li  Li14  1  0.691  0.502  0.822  1.0
  Li  Li15  1  0.130  0.750  0.912  1.0
  Ti  Ti16  1  0.851  0.750  0.088  1.0
  Ti  Ti17  1  0.351  0.250  0.412  1.0
  Ti  Ti18  1  0.649  0.750  0.588  1.0
  Ti  Ti19  1  0.149  0.250  0.912  1.0
  S  S20  1  0.262  0.250  0.064  1.0
  S  S21  1  0.216  0.750  0.082  1.0
  S  S22  1  0.717  0.509  0.157  1.0
  S  S23  1  0.717  0.991  0.157  1.0
  S  S24  1  0.217  0.009  0.343  1.0
  S  S25  1  0.217  0.491  0.343  1.0
  S  S26  1  0.716  0.250  0.418  1.0
  S  S27  1  0.762  0.750  0.436  1.0
  S  S28  1  0.238  0.250  0.564  1.0
  S  S29  1  0.284  0.750  0.582  1.0
  S  S30  1  0.783  0.509  0.657  1.0
  S  S31  1  0.783  0.991  0.657  1.0
  S  S32  1  0.283  0.009  0.843  1.0
  S  S33  1  0.283  0.491  0.843  1.0
  S  S34  1  0.784  0.250  0.918  1.0
  S  S35  1  0.738  0.750  0.936  1.0
[/CIF]
.