The compound described by RbTiPS5 crystallizes in the monoclinic C2/m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to one S(5), two equivalent S(2), two equivalent S(6), and three equivalent S(1) atoms to form distorted RbS8 hexagonal bipyramids that share corners with two equivalent Rb(1)S8 hexagonal bipyramids, corners with two equivalent Ti(2)S6 octahedra, corners with four equivalent Ti(1)S6 octahedra, edges with two equivalent Rb(1)S8 hexagonal bipyramids,  an edgeedge with one P(1)S4 tetrahedra, and edges with three equivalent P(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-71°. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one S(4), one S(7), two equivalent S(2), two equivalent S(6), and three equivalent S(8) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(5), two equivalent S(6), and two equivalent S(7) atoms to form distorted TiS6 octahedra that share corners with four equivalent Rb(1)S8 hexagonal bipyramids, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent P(2)S4 tetrahedra. In the second Ti site, Ti(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form distorted TiS6 octahedra that share corners with two equivalent Rb(1)S8 hexagonal bipyramids, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent P(1)S4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one S(4), one S(8), and two equivalent S(2) atoms to form PS4 tetrahedra that share  an edgeedge with one Rb(1)S8 hexagonal bipyramid and edges with two equivalent Ti(2)S6 octahedra. In the second P site, P(2) is bonded to one S(1), one S(5), and two equivalent S(6) atoms to form PS4 tetrahedra that share edges with three equivalent Rb(1)S8 hexagonal bipyramids and edges with two equivalent Ti(1)S6 octahedra. There are eight inequivalent S sites. In the first S site, S(7) is bonded in a distorted L-shaped geometry to one Rb(2) and two equivalent Ti(1) atoms. In the second S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Rb(2) and one P(1) atom. In the third S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Rb(1) and one P(2) atom. In the fourth S site, S(2) is bonded to one Rb(1), one Rb(2), one Ti(2), and one P(1) atom to form distorted SRb2TiP trigonal pyramids that share  a cornercorner with one S(5)RbTi2P trigonal pyramid, corners with two equivalent S(2)Rb2TiP trigonal pyramids, corners with two equivalent S(4)RbTi2P trigonal pyramids,  an edgeedge with one S(2)Rb2TiP trigonal pyramid, and  an edgeedge with one S(4)RbTi2P trigonal pyramid. In the fifth S site, S(3) is bonded in an L-shaped geometry to two equivalent Ti(2) atoms. In the sixth S site, S(4) is bonded to one Rb(2), two equivalent Ti(2), and one P(1) atom to form distorted SRbTi2P trigonal pyramids that share corners with four equivalent S(2)Rb2TiP trigonal pyramids,  an edgeedge with one S(4)RbTi2P trigonal pyramid, and edges with two equivalent S(2)Rb2TiP trigonal pyramids. In the seventh S site, S(5) is bonded to one Rb(1), two equivalent Ti(1), and one P(2) atom to form distorted SRbTi2P trigonal pyramids that share corners with two equivalent S(2)Rb2TiP trigonal pyramids and  an edgeedge with one S(5)RbTi2P trigonal pyramid. In the eighth S site, S(6) is bonded in a distorted L-shaped geometry to one Rb(1), one Rb(2), one Ti(1), and one P(2) atom. is represented by the Crystallographic Information File (CIF) [CIF]
data_RbTiPS5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   9.965
_cell_length_b   9.965
_cell_length_c   16.089
_cell_angle_alpha   59.351
_cell_angle_beta   59.351
_cell_angle_gamma   42.153
_symmetry_Int_Tables_number   1
_cell_volume   897.992
_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
  Rb  Rb0  1  0.664  0.664  0.137  1.0
  Rb  Rb1  1  0.702  0.702  0.642  1.0
  Rb  Rb2  1  0.298  0.298  0.358  1.0
  Rb  Rb3  1  0.336  0.336  0.863  1.0
  Ti  Ti4  1  0.725  0.275  0.000  1.0
  Ti  Ti5  1  0.275  0.725  0.000  1.0
  Ti  Ti6  1  0.780  0.220  0.500  1.0
  Ti  Ti7  1  0.220  0.780  0.500  1.0
  P  P8  1  0.333  0.333  0.595  1.0
  P  P9  1  0.075  0.075  0.098  1.0
  P  P10  1  0.925  0.925  0.902  1.0
  P  P11  1  0.667  0.667  0.405  1.0
  S  S12  1  0.172  0.172  0.117  1.0
  S  S13  1  0.591  0.123  0.653  1.0
  S  S14  1  0.123  0.591  0.653  1.0
  S  S15  1  0.977  0.977  0.415  1.0
  S  S16  1  0.440  0.440  0.448  1.0
  S  S17  1  0.109  0.109  0.950  1.0
  S  S18  1  0.765  0.230  0.153  1.0
  S  S19  1  0.230  0.765  0.153  1.0
  S  S20  1  0.606  0.606  0.913  1.0
  S  S21  1  0.220  0.220  0.610  1.0
  S  S22  1  0.780  0.780  0.390  1.0
  S  S23  1  0.394  0.394  0.087  1.0
  S  S24  1  0.235  0.770  0.847  1.0
  S  S25  1  0.770  0.235  0.847  1.0
  S  S26  1  0.891  0.891  0.050  1.0
  S  S27  1  0.560  0.560  0.552  1.0
  S  S28  1  0.023  0.023  0.585  1.0
  S  S29  1  0.877  0.409  0.347  1.0
  S  S30  1  0.409  0.877  0.347  1.0
  S  S31  1  0.828  0.828  0.883  1.0
[/CIF]
.
The compound described by RbTiPS5 crystallizes in the monoclinic C2/m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to one S(5), two equivalent S(2), two equivalent S(6), and three equivalent S(1) atoms to form distorted RbS8 hexagonal bipyramids that share corners with two equivalent Rb(1)S8 hexagonal bipyramids, corners with two equivalent Ti(2)S6 octahedra, corners with four equivalent Ti(1)S6 octahedra, edges with two equivalent Rb(1)S8 hexagonal bipyramids,  an edgeedge with one P(1)S4 tetrahedra, and edges with three equivalent P(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-71°. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one S(4), one S(7), two equivalent S(2), two equivalent S(6), and three equivalent S(8) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent S(5), two equivalent S(6), and two equivalent S(7) atoms to form distorted TiS6 octahedra that share corners with four equivalent Rb(1)S8 hexagonal bipyramids, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent P(2)S4 tetrahedra. In the second Ti site, Ti(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form distorted TiS6 octahedra that share corners with two equivalent Rb(1)S8 hexagonal bipyramids, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent P(1)S4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one S(4), one S(8), and two equivalent S(2) atoms to form PS4 tetrahedra that share  an edgeedge with one Rb(1)S8 hexagonal bipyramid and edges with two equivalent Ti(2)S6 octahedra. In the second P site, P(2) is bonded to one S(1), one S(5), and two equivalent S(6) atoms to form PS4 tetrahedra that share edges with three equivalent Rb(1)S8 hexagonal bipyramids and edges with two equivalent Ti(1)S6 octahedra. There are eight inequivalent S sites. In the first S site, S(7) is bonded in a distorted L-shaped geometry to one Rb(2) and two equivalent Ti(1) atoms. In the second S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Rb(2) and one P(1) atom. In the third S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Rb(1) and one P(2) atom. In the fourth S site, S(2) is bonded to one Rb(1), one Rb(2), one Ti(2), and one P(1) atom to form distorted SRb2TiP trigonal pyramids that share  a cornercorner with one S(5)RbTi2P trigonal pyramid, corners with two equivalent S(2)Rb2TiP trigonal pyramids, corners with two equivalent S(4)RbTi2P trigonal pyramids,  an edgeedge with one S(2)Rb2TiP trigonal pyramid, and  an edgeedge with one S(4)RbTi2P trigonal pyramid. In the fifth S site, S(3) is bonded in an L-shaped geometry to two equivalent Ti(2) atoms. In the sixth S site, S(4) is bonded to one Rb(2), two equivalent Ti(2), and one P(1) atom to form distorted SRbTi2P trigonal pyramids that share corners with four equivalent S(2)Rb2TiP trigonal pyramids,  an edgeedge with one S(4)RbTi2P trigonal pyramid, and edges with two equivalent S(2)Rb2TiP trigonal pyramids. In the seventh S site, S(5) is bonded to one Rb(1), two equivalent Ti(1), and one P(2) atom to form distorted SRbTi2P trigonal pyramids that share corners with two equivalent S(2)Rb2TiP trigonal pyramids and  an edgeedge with one S(5)RbTi2P trigonal pyramid. In the eighth S site, S(6) is bonded in a distorted L-shaped geometry to one Rb(1), one Rb(2), one Ti(1), and one P(2) atom. is represented by the Crystallographic Information File (CIF) [CIF]
data_RbTiPS5
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   9.965
_cell_length_b   9.965
_cell_length_c   16.089
_cell_angle_alpha   59.351
_cell_angle_beta   59.351
_cell_angle_gamma   42.153
_symmetry_Int_Tables_number   1
_cell_volume   897.992
_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
  Rb  Rb0  1  0.664  0.664  0.137  1.0
  Rb  Rb1  1  0.702  0.702  0.642  1.0
  Rb  Rb2  1  0.298  0.298  0.358  1.0
  Rb  Rb3  1  0.336  0.336  0.863  1.0
  Ti  Ti4  1  0.725  0.275  0.000  1.0
  Ti  Ti5  1  0.275  0.725  0.000  1.0
  Ti  Ti6  1  0.780  0.220  0.500  1.0
  Ti  Ti7  1  0.220  0.780  0.500  1.0
  P  P8  1  0.333  0.333  0.595  1.0
  P  P9  1  0.075  0.075  0.098  1.0
  P  P10  1  0.925  0.925  0.902  1.0
  P  P11  1  0.667  0.667  0.405  1.0
  S  S12  1  0.172  0.172  0.117  1.0
  S  S13  1  0.591  0.123  0.653  1.0
  S  S14  1  0.123  0.591  0.653  1.0
  S  S15  1  0.977  0.977  0.415  1.0
  S  S16  1  0.440  0.440  0.448  1.0
  S  S17  1  0.109  0.109  0.950  1.0
  S  S18  1  0.765  0.230  0.153  1.0
  S  S19  1  0.230  0.765  0.153  1.0
  S  S20  1  0.606  0.606  0.913  1.0
  S  S21  1  0.220  0.220  0.610  1.0
  S  S22  1  0.780  0.780  0.390  1.0
  S  S23  1  0.394  0.394  0.087  1.0
  S  S24  1  0.235  0.770  0.847  1.0
  S  S25  1  0.770  0.235  0.847  1.0
  S  S26  1  0.891  0.891  0.050  1.0
  S  S27  1  0.560  0.560  0.552  1.0
  S  S28  1  0.023  0.023  0.585  1.0
  S  S29  1  0.877  0.409  0.347  1.0
  S  S30  1  0.409  0.877  0.347  1.0
  S  S31  1  0.828  0.828  0.883  1.0
[/CIF]
.