The compound described by Tm15S22 crystallizes in the monoclinic C2/m space group. There are eight inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one S(8), two equivalent S(5), and three equivalent S(4) atoms to form TmS6 octahedra that share corners with three equivalent Tm(7)S6 octahedra,  a cornercorner with one Tm(6)S7 pentagonal bipyramid, edges with four equivalent Tm(1)S6 octahedra, and edges with two equivalent Tm(6)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 54-60°. In the second Tm site, Tm(2) is bonded to one S(7), one S(9), two equivalent S(11), and two equivalent S(2) atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. In the third Tm site, Tm(3) is bonded in a 8-coordinate geometry to one S(1), one S(6), two equivalent S(10), two equivalent S(11), and two equivalent S(3) atoms. In the fourth Tm site, Tm(4) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(7) atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. In the fifth Tm site, Tm(5) is bonded in a 7-coordinate geometry to one S(10), two equivalent S(1), two equivalent S(5), and two equivalent S(9) atoms. In the sixth Tm site, Tm(6) is bonded to one S(5), one S(6), two equivalent S(10), and three equivalent S(8) atoms to form distorted TmS7 pentagonal bipyramids that share  a cornercorner with one Tm(1)S6 octahedra, corners with two equivalent Tm(7)S6 octahedra, edges with two equivalent Tm(1)S6 octahedra, and edges with four equivalent Tm(6)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-50°. In the seventh Tm site, Tm(7) is bonded to one S(11), one S(4), two equivalent S(6), and two equivalent S(9) atoms to form TmS6 octahedra that share corners with three equivalent Tm(1)S6 octahedra, corners with two equivalent Tm(6)S7 pentagonal bipyramids, edges with two equivalent Tm(2)S6 octahedra, and edges with two equivalent Tm(7)S6 octahedra. The corner-sharing octahedral tilt angles range from 54-60°. In the eighth Tm site, Tm(8) is bonded to two equivalent S(7) and four equivalent S(3) atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 56°. There are eleven inequivalent S sites. In the first S site, S(1) is bonded to one Tm(3), two equivalent Tm(4), and two equivalent Tm(5) atoms to form distorted STm5 trigonal bipyramids that share corners with two equivalent S(11)Tm5 square pyramids, corners with two equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(9)Tm5 trigonal bipyramids,  a cornercorner with one S(6)Tm4 trigonal pyramid, edges with two equivalent S(3)Tm5 square pyramids,  an edgeedge with one S(5)Tm5 trigonal bipyramid,  an edgeedge with one S(9)Tm5 trigonal bipyramid, edges with two equivalent S(1)Tm5 trigonal bipyramids, and edges with two equivalent S(10)Tm5 trigonal bipyramids. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Tm(4) and two equivalent Tm(2) atoms. In the third S site, S(3) is bonded to one Tm(4), two equivalent Tm(3), and two equivalent Tm(8) atoms to form STm5 square pyramids that share corners with two equivalent S(11)Tm5 square pyramids, corners with two equivalent S(3)Tm5 square pyramids, corners with two equivalent S(10)Tm5 trigonal bipyramids, corners with two equivalent S(6)Tm4 trigonal pyramids,  an edgeedge with one S(11)Tm5 square pyramid, edges with three equivalent S(3)Tm5 square pyramids,  an edgeedge with one S(10)Tm5 trigonal bipyramid, and edges with two equivalent S(1)Tm5 trigonal bipyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Tm(7) and three equivalent Tm(1) atoms. In the fifth S site, S(5) is bonded to one Tm(6), two equivalent Tm(1), and two equivalent Tm(5) atoms to form STm5 trigonal bipyramids that share corners with two equivalent S(1)Tm5 trigonal bipyramids, corners with two equivalent S(9)Tm5 trigonal bipyramids,  a cornercorner with one S(6)Tm4 trigonal pyramid,  a cornercorner with one S(8)Tm4 trigonal pyramid,  an edgeedge with one S(1)Tm5 trigonal bipyramid,  an edgeedge with one S(9)Tm5 trigonal bipyramid, edges with two equivalent S(10)Tm5 trigonal bipyramids, edges with two equivalent S(5)Tm5 trigonal bipyramids, and edges with two equivalent S(8)Tm4 trigonal pyramids. In the sixth S site, S(6) is bonded to one Tm(3), one Tm(6), and two equivalent Tm(7) atoms to form distorted STm4 trigonal pyramids that share corners with two equivalent S(3)Tm5 square pyramids,  a cornercorner with one S(1)Tm5 trigonal bipyramid,  a cornercorner with one S(5)Tm5 trigonal bipyramid, corners with two equivalent S(9)Tm5 trigonal bipyramids, corners with two equivalent S(6)Tm4 trigonal pyramids, corners with three equivalent S(8)Tm4 trigonal pyramids, edges with two equivalent S(11)Tm5 square pyramids,  an edgeedge with one S(9)Tm5 trigonal bipyramid, and edges with two equivalent S(10)Tm5 trigonal bipyramids. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to one Tm(2), one Tm(8), and two equivalent Tm(4) atoms. In the eighth S site, S(8) is bonded to one Tm(1) and three equivalent Tm(6) atoms to form distorted STm4 trigonal pyramids that share  a cornercorner with one S(5)Tm5 trigonal bipyramid, corners with four equivalent S(10)Tm5 trigonal bipyramids, corners with two equivalent S(8)Tm4 trigonal pyramids, corners with three equivalent S(6)Tm4 trigonal pyramids,  an edgeedge with one S(10)Tm5 trigonal bipyramid, edges with two equivalent S(5)Tm5 trigonal bipyramids, and edges with two equivalent S(8)Tm4 trigonal pyramids. In the ninth S site, S(9) is bonded to one Tm(2), two equivalent Tm(5), and two equivalent Tm(7) atoms to form STm5 trigonal bipyramids that share corners with two equivalent S(1)Tm5 trigonal bipyramids, corners with two equivalent S(10)Tm5 trigonal bipyramids, corners with two equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(6)Tm4 trigonal pyramids, edges with two equivalent S(11)Tm5 square pyramids,  an edgeedge with one S(1)Tm5 trigonal bipyramid,  an edgeedge with one S(5)Tm5 trigonal bipyramid, edges with two equivalent S(9)Tm5 trigonal bipyramids, and  an edgeedge with one S(6)Tm4 trigonal pyramid. In the tenth S site, S(10) is bonded to one Tm(5), two equivalent Tm(3), and two equivalent Tm(6) atoms to form distorted STm5 trigonal bipyramids that share corners with two equivalent S(11)Tm5 square pyramids, corners with two equivalent S(3)Tm5 square pyramids, corners with two equivalent S(9)Tm5 trigonal bipyramids, corners with four equivalent S(8)Tm4 trigonal pyramids,  an edgeedge with one S(11)Tm5 square pyramid,  an edgeedge with one S(3)Tm5 square pyramid, edges with two equivalent S(1)Tm5 trigonal bipyramids, edges with two equivalent S(10)Tm5 trigonal bipyramids, edges with two equivalent S(5)Tm5 trigonal bipyramids,  an edgeedge with one S(8)Tm4 trigonal pyramid, and edges with two equivalent S(6)Tm4 trigonal pyramids. In the eleventh S site, S(11) is bonded to one Tm(7), two equivalent Tm(2), and two equivalent Tm(3) atoms to form STm5 square pyramids that share corners with two equivalent S(3)Tm5 square pyramids, corners with two equivalent S(1)Tm5 trigonal bipyramids, corners with two equivalent S(10)Tm5 trigonal bipyramids,  an edgeedge with one S(3)Tm5 square pyramid, edges with two equivalent S(11)Tm5 square pyramids,  an edgeedge with one S(10)Tm5 trigonal bipyramid, edges with two equivalent S(9)Tm5 trigonal bipyramids, and edges with two equivalent S(6)Tm4 trigonal pyramids. is represented by the Crystallographic Information File (CIF) [CIF]
data_Tm15S22
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   19.372
_cell_length_b   19.372
_cell_length_c   11.198
_cell_angle_alpha   89.081
_cell_angle_beta   89.081
_cell_angle_gamma   11.408
_symmetry_Int_Tables_number   1
_cell_volume   831.110
_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
  Tm  Tm0  1  0.234  0.234  0.353  1.0
  Tm  Tm1  1  0.431  0.431  0.357  1.0
  Tm  Tm2  1  0.569  0.569  0.643  1.0
  Tm  Tm3  1  0.766  0.766  0.647  1.0
  Tm  Tm4  1  0.395  0.395  0.011  1.0
  Tm  Tm5  1  0.605  0.605  0.989  1.0
  Tm  Tm6  1  0.040  0.040  0.272  1.0
  Tm  Tm7  1  0.867  0.867  0.658  1.0
  Tm  Tm8  1  0.133  0.133  0.342  1.0
  Tm  Tm9  1  0.701  0.701  0.057  1.0
  Tm  Tm10  1  0.157  0.157  0.694  1.0
  Tm  Tm11  1  0.960  0.960  0.728  1.0
  Tm  Tm12  1  0.500  0.500  0.000  1.0
  Tm  Tm13  1  0.843  0.843  0.306  1.0
  Tm  Tm14  1  0.299  0.299  0.943  1.0
  S  S15  1  0.410  0.410  0.752  1.0
  S  S16  1  0.053  0.053  0.498  1.0
  S  S17  1  0.947  0.947  0.502  1.0
  S  S18  1  0.951  0.951  0.968  1.0
  S  S19  1  0.220  0.220  0.592  1.0
  S  S20  1  0.780  0.780  0.408  1.0
  S  S21  1  0.686  0.686  0.307  1.0
  S  S22  1  0.667  0.667  0.851  1.0
  S  S23  1  0.333  0.333  0.149  1.0
  S  S24  1  0.314  0.314  0.693  1.0
  S  S25  1  0.493  0.493  0.238  1.0
  S  S26  1  0.755  0.755  0.880  1.0
  S  S27  1  0.507  0.507  0.762  1.0
  S  S28  1  0.049  0.049  0.032  1.0
  S  S29  1  0.634  0.634  0.539  1.0
  S  S30  1  0.853  0.853  0.907  1.0
  S  S31  1  0.093  0.093  0.794  1.0
  S  S32  1  0.245  0.245  0.120  1.0
  S  S33  1  0.907  0.907  0.206  1.0
  S  S34  1  0.147  0.147  0.093  1.0
  S  S35  1  0.590  0.590  0.248  1.0
  S  S36  1  0.366  0.366  0.461  1.0
[/CIF]
.
The compound described by Tm15S22 crystallizes in the monoclinic C2/m space group. There are eight inequivalent Tm sites. In the first Tm site, Tm(1) is bonded to one S(8), two equivalent S(5), and three equivalent S(4) atoms to form TmS6 octahedra that share corners with three equivalent Tm(7)S6 octahedra,  a cornercorner with one Tm(6)S7 pentagonal bipyramid, edges with four equivalent Tm(1)S6 octahedra, and edges with two equivalent Tm(6)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 54-60°. In the second Tm site, Tm(2) is bonded to one S(7), one S(9), two equivalent S(11), and two equivalent S(2) atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. In the third Tm site, Tm(3) is bonded in a 8-coordinate geometry to one S(1), one S(6), two equivalent S(10), two equivalent S(11), and two equivalent S(3) atoms. In the fourth Tm site, Tm(4) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(7) atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. In the fifth Tm site, Tm(5) is bonded in a 7-coordinate geometry to one S(10), two equivalent S(1), two equivalent S(5), and two equivalent S(9) atoms. In the sixth Tm site, Tm(6) is bonded to one S(5), one S(6), two equivalent S(10), and three equivalent S(8) atoms to form distorted TmS7 pentagonal bipyramids that share  a cornercorner with one Tm(1)S6 octahedra, corners with two equivalent Tm(7)S6 octahedra, edges with two equivalent Tm(1)S6 octahedra, and edges with four equivalent Tm(6)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 38-50°. In the seventh Tm site, Tm(7) is bonded to one S(11), one S(4), two equivalent S(6), and two equivalent S(9) atoms to form TmS6 octahedra that share corners with three equivalent Tm(1)S6 octahedra, corners with two equivalent Tm(6)S7 pentagonal bipyramids, edges with two equivalent Tm(2)S6 octahedra, and edges with two equivalent Tm(7)S6 octahedra. The corner-sharing octahedral tilt angles range from 54-60°. In the eighth Tm site, Tm(8) is bonded to two equivalent S(7) and four equivalent S(3) atoms to form a mixture of edge and corner-sharing TmS6 octahedra. The corner-sharing octahedral tilt angles are 56°. There are eleven inequivalent S sites. In the first S site, S(1) is bonded to one Tm(3), two equivalent Tm(4), and two equivalent Tm(5) atoms to form distorted STm5 trigonal bipyramids that share corners with two equivalent S(11)Tm5 square pyramids, corners with two equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(9)Tm5 trigonal bipyramids,  a cornercorner with one S(6)Tm4 trigonal pyramid, edges with two equivalent S(3)Tm5 square pyramids,  an edgeedge with one S(5)Tm5 trigonal bipyramid,  an edgeedge with one S(9)Tm5 trigonal bipyramid, edges with two equivalent S(1)Tm5 trigonal bipyramids, and edges with two equivalent S(10)Tm5 trigonal bipyramids. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Tm(4) and two equivalent Tm(2) atoms. In the third S site, S(3) is bonded to one Tm(4), two equivalent Tm(3), and two equivalent Tm(8) atoms to form STm5 square pyramids that share corners with two equivalent S(11)Tm5 square pyramids, corners with two equivalent S(3)Tm5 square pyramids, corners with two equivalent S(10)Tm5 trigonal bipyramids, corners with two equivalent S(6)Tm4 trigonal pyramids,  an edgeedge with one S(11)Tm5 square pyramid, edges with three equivalent S(3)Tm5 square pyramids,  an edgeedge with one S(10)Tm5 trigonal bipyramid, and edges with two equivalent S(1)Tm5 trigonal bipyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Tm(7) and three equivalent Tm(1) atoms. In the fifth S site, S(5) is bonded to one Tm(6), two equivalent Tm(1), and two equivalent Tm(5) atoms to form STm5 trigonal bipyramids that share corners with two equivalent S(1)Tm5 trigonal bipyramids, corners with two equivalent S(9)Tm5 trigonal bipyramids,  a cornercorner with one S(6)Tm4 trigonal pyramid,  a cornercorner with one S(8)Tm4 trigonal pyramid,  an edgeedge with one S(1)Tm5 trigonal bipyramid,  an edgeedge with one S(9)Tm5 trigonal bipyramid, edges with two equivalent S(10)Tm5 trigonal bipyramids, edges with two equivalent S(5)Tm5 trigonal bipyramids, and edges with two equivalent S(8)Tm4 trigonal pyramids. In the sixth S site, S(6) is bonded to one Tm(3), one Tm(6), and two equivalent Tm(7) atoms to form distorted STm4 trigonal pyramids that share corners with two equivalent S(3)Tm5 square pyramids,  a cornercorner with one S(1)Tm5 trigonal bipyramid,  a cornercorner with one S(5)Tm5 trigonal bipyramid, corners with two equivalent S(9)Tm5 trigonal bipyramids, corners with two equivalent S(6)Tm4 trigonal pyramids, corners with three equivalent S(8)Tm4 trigonal pyramids, edges with two equivalent S(11)Tm5 square pyramids,  an edgeedge with one S(9)Tm5 trigonal bipyramid, and edges with two equivalent S(10)Tm5 trigonal bipyramids. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to one Tm(2), one Tm(8), and two equivalent Tm(4) atoms. In the eighth S site, S(8) is bonded to one Tm(1) and three equivalent Tm(6) atoms to form distorted STm4 trigonal pyramids that share  a cornercorner with one S(5)Tm5 trigonal bipyramid, corners with four equivalent S(10)Tm5 trigonal bipyramids, corners with two equivalent S(8)Tm4 trigonal pyramids, corners with three equivalent S(6)Tm4 trigonal pyramids,  an edgeedge with one S(10)Tm5 trigonal bipyramid, edges with two equivalent S(5)Tm5 trigonal bipyramids, and edges with two equivalent S(8)Tm4 trigonal pyramids. In the ninth S site, S(9) is bonded to one Tm(2), two equivalent Tm(5), and two equivalent Tm(7) atoms to form STm5 trigonal bipyramids that share corners with two equivalent S(1)Tm5 trigonal bipyramids, corners with two equivalent S(10)Tm5 trigonal bipyramids, corners with two equivalent S(5)Tm5 trigonal bipyramids, corners with two equivalent S(6)Tm4 trigonal pyramids, edges with two equivalent S(11)Tm5 square pyramids,  an edgeedge with one S(1)Tm5 trigonal bipyramid,  an edgeedge with one S(5)Tm5 trigonal bipyramid, edges with two equivalent S(9)Tm5 trigonal bipyramids, and  an edgeedge with one S(6)Tm4 trigonal pyramid. In the tenth S site, S(10) is bonded to one Tm(5), two equivalent Tm(3), and two equivalent Tm(6) atoms to form distorted STm5 trigonal bipyramids that share corners with two equivalent S(11)Tm5 square pyramids, corners with two equivalent S(3)Tm5 square pyramids, corners with two equivalent S(9)Tm5 trigonal bipyramids, corners with four equivalent S(8)Tm4 trigonal pyramids,  an edgeedge with one S(11)Tm5 square pyramid,  an edgeedge with one S(3)Tm5 square pyramid, edges with two equivalent S(1)Tm5 trigonal bipyramids, edges with two equivalent S(10)Tm5 trigonal bipyramids, edges with two equivalent S(5)Tm5 trigonal bipyramids,  an edgeedge with one S(8)Tm4 trigonal pyramid, and edges with two equivalent S(6)Tm4 trigonal pyramids. In the eleventh S site, S(11) is bonded to one Tm(7), two equivalent Tm(2), and two equivalent Tm(3) atoms to form STm5 square pyramids that share corners with two equivalent S(3)Tm5 square pyramids, corners with two equivalent S(1)Tm5 trigonal bipyramids, corners with two equivalent S(10)Tm5 trigonal bipyramids,  an edgeedge with one S(3)Tm5 square pyramid, edges with two equivalent S(11)Tm5 square pyramids,  an edgeedge with one S(10)Tm5 trigonal bipyramid, edges with two equivalent S(9)Tm5 trigonal bipyramids, and edges with two equivalent S(6)Tm4 trigonal pyramids. is represented by the Crystallographic Information File (CIF) [CIF]
data_Tm15S22
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   19.372
_cell_length_b   19.372
_cell_length_c   11.198
_cell_angle_alpha   89.081
_cell_angle_beta   89.081
_cell_angle_gamma   11.408
_symmetry_Int_Tables_number   1
_cell_volume   831.110
_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
  Tm  Tm0  1  0.234  0.234  0.353  1.0
  Tm  Tm1  1  0.431  0.431  0.357  1.0
  Tm  Tm2  1  0.569  0.569  0.643  1.0
  Tm  Tm3  1  0.766  0.766  0.647  1.0
  Tm  Tm4  1  0.395  0.395  0.011  1.0
  Tm  Tm5  1  0.605  0.605  0.989  1.0
  Tm  Tm6  1  0.040  0.040  0.272  1.0
  Tm  Tm7  1  0.867  0.867  0.658  1.0
  Tm  Tm8  1  0.133  0.133  0.342  1.0
  Tm  Tm9  1  0.701  0.701  0.057  1.0
  Tm  Tm10  1  0.157  0.157  0.694  1.0
  Tm  Tm11  1  0.960  0.960  0.728  1.0
  Tm  Tm12  1  0.500  0.500  0.000  1.0
  Tm  Tm13  1  0.843  0.843  0.306  1.0
  Tm  Tm14  1  0.299  0.299  0.943  1.0
  S  S15  1  0.410  0.410  0.752  1.0
  S  S16  1  0.053  0.053  0.498  1.0
  S  S17  1  0.947  0.947  0.502  1.0
  S  S18  1  0.951  0.951  0.968  1.0
  S  S19  1  0.220  0.220  0.592  1.0
  S  S20  1  0.780  0.780  0.408  1.0
  S  S21  1  0.686  0.686  0.307  1.0
  S  S22  1  0.667  0.667  0.851  1.0
  S  S23  1  0.333  0.333  0.149  1.0
  S  S24  1  0.314  0.314  0.693  1.0
  S  S25  1  0.493  0.493  0.238  1.0
  S  S26  1  0.755  0.755  0.880  1.0
  S  S27  1  0.507  0.507  0.762  1.0
  S  S28  1  0.049  0.049  0.032  1.0
  S  S29  1  0.634  0.634  0.539  1.0
  S  S30  1  0.853  0.853  0.907  1.0
  S  S31  1  0.093  0.093  0.794  1.0
  S  S32  1  0.245  0.245  0.120  1.0
  S  S33  1  0.907  0.907  0.206  1.0
  S  S34  1  0.147  0.147  0.093  1.0
  S  S35  1  0.590  0.590  0.248  1.0
  S  S36  1  0.366  0.366  0.461  1.0
[/CIF]
.