The coordination chemistry and anticancer activity of organo-ruthenium(II), -iridium(III) and -rhodium(III) complexes with sulfonyl-substituted thiourea ligands.
Risi, Matthew C.; Stjärnhage, Julia; Henderson, William; Lane, Joseph R.; Hartinger, Christian G.; Saunders, Graham C.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 539–549; doi:10.1039/d4dt02733g

data_7717548
_publ_section_title
;
 The coordination chemistry and anticancer activity of
 organo-ruthenium(II), -iridium(III) and -rhodium(III) complexes with
 sulfonyl-substituted thiourea ligands.
;
_journal_issue                   2
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              539
_journal_page_last               549
_journal_paper_doi               10.1039/d4dt02733g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C44 H53 Ir N7 O4 P S4, 3[H2O], 2[CH4O]'
_chemical_formula_sum            'C46 H67 Ir N7 O9 P S4'
_chemical_formula_weight         1213.541
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-11-06
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-11-06 deposited with the CCDC.	2024-11-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.392(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9061(2)
_cell_length_b                   16.4040(2)
_cell_length_c                   26.5797(3)
_cell_measurement_reflns_used    31840
_cell_measurement_temperature    99.9(5)
_cell_measurement_theta_max      74.0050
_cell_measurement_theta_min      3.1390
_cell_volume                     5189.69(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 0.9877
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -37.00  33.00   0.50    0.20    --  -46.98  38.00 -90.00  140
  2  \w    -13.00  13.00   0.50    0.20    --  -46.98  19.00-120.00   52
  3  \w    -39.00   3.00   0.50    0.20    --  -46.98  38.00-150.00   84
  4  \w    -47.00 -22.00   0.50    1.00    --  -90.25 112.00-133.00   50
  5  \w    -67.00 -42.00   0.50    0.20    --  -46.98 112.00-133.00   50
  6  \w    -44.00 -18.00   0.50    1.00    --  -90.25  45.00-180.00   52
  7  \w    -77.00 -15.00   0.50    1.00    --  -90.25  77.00-120.00  124
  8  \w    -48.00 -16.00   0.50    1.00    --  -90.25  45.00 -60.00   64
  9  \w    -64.00  -7.00   0.50    0.20    --  -46.98  57.00 -30.00  114
 10  \w    -51.00 -13.00   0.50    1.00    --  -90.25  45.00  60.00   76
 11  \w    -44.00 -12.00   0.50    1.00    --  -90.25  45.00  90.00   64
 12  \w   -120.00 -26.00   0.50    0.20    --  -46.98 -57.00 120.00  188
 13  \w     29.00  90.00   0.50    0.20    --   46.98-112.00 134.00  122
 14  \w     66.00 109.00   0.50    1.00    --  100.91-112.00 134.00   86
 15  \w     63.00 103.00   0.50    1.00    --  100.91 -95.00  60.00   80
 16  \w     82.00 108.00   0.50    1.00    --  100.91-111.00  30.00   52
 17  \w     76.00 102.00   0.50    1.00    --  100.91 -95.00 -30.00   52
 18  \w     82.00 108.00   0.50    1.00    --  100.91-111.00 -90.00   52
 19  \w     76.00 103.00   0.50    1.00    --  100.91-111.00-120.00   54
 20  \w     58.00 101.00   0.50    1.00    --  100.91 -77.00-120.00   86
 21  \w     62.00 106.00   0.50    1.00    --  100.91-111.00 -30.00   88
 22  \w     43.00 100.00   0.50    1.00    --  100.91 -95.00-120.00  114
 23  \w     34.00  66.00   0.50    1.00    --  100.91-111.00 -90.00   64
 24  \w     28.00  58.00   0.50    1.00    --  100.91 -61.00 -90.00   60
 25  \w     31.00  72.00   0.50    1.00    --  100.91 -95.00 -30.00   82
 26  \w     29.00  58.00   0.50    1.00    --  100.91 -61.00  30.00   58
 27  \w     30.00  71.00   0.50    1.00    --  100.91 -61.00  60.00   82
 28  \w     28.00 108.00   0.50    1.00    --  100.91-111.00  60.00  160
 29  \w     43.00  97.00   0.50    1.00    --  100.91-111.00 150.00  108
 30  \w     28.00  53.00   0.50    1.00    --  100.91 -61.00  90.00   50
 31  \w     24.00  51.00   0.50    1.00    --  100.91 -45.00  60.00   54
 32  \w     23.00  51.00   0.50    1.00    --  100.91 -45.00  90.00   56
 33  \w     23.00  48.00   0.50    1.00    --  100.91 -45.00  30.00   50
 34  \w     26.00  97.00   0.50    1.00    --  100.91 -77.00 -30.00  142
 35  \w     28.00  61.00   0.50    1.00    --  100.91-111.00-120.00   66
 36  \w     23.00  92.00   0.50    1.00    --  100.91 -95.00-180.00  138
 37  \w     24.00  51.00   0.50    1.00    --  100.91 -45.00 -90.00   54
 38  \w     23.00  48.00   0.50    1.00    --  100.91 -45.00-120.00   50
 39  \w     29.00  60.00   0.50    1.00    --  100.91 -61.00-180.00   62
 40  \w     26.00 108.00   0.50    1.00    --  100.91-111.00-180.00  164
 41  \w     29.00  71.00   0.50    1.00    --  100.91 -61.00 -30.00   84
 42  \w     23.00  56.00   0.50    1.00    --  100.91-111.00 -30.00   66
 43  \w     25.00  51.00   0.50    1.00    --  100.91-111.00  30.00   52
 44  \w     31.00  56.00   0.50    1.00    --  100.91 -95.00  60.00   50
 45  \w     24.00  50.00   0.50    1.00    --  100.91 -45.00 150.00   52
 46  \w     82.00 176.00   0.50    1.00    --  100.91  30.00  60.00  188
 47  \w     82.00 177.00   0.50    1.00    --  100.91  30.00  30.00  190
 48  \w    114.00 153.00   0.50    1.00    --  100.91 112.00-133.00   78
 49  \w    -31.00  26.00   0.50    0.20    --   46.98 -19.00 120.00  114
 50  \w   -100.00 -29.00   0.50    0.20    --  -46.98 -57.00-120.00  142
 51  \w   -123.00 -78.00   0.50    0.20    --  -46.98-125.00-150.00   90
 52  \w   -119.00 -83.00   0.50    0.20    --  -46.98-125.00 -60.00   72
 53  \w   -120.00 -94.00   0.50    0.20    --  -46.98-125.00 -30.00   52
 54  \w   -145.00-105.00   0.50    1.00    --  -90.25 -77.00  60.00   80
 55  \w   -123.00 -89.00   0.50    0.20    --  -46.98-112.00 134.00   68
 56  \w   -125.00-100.00   0.50    1.00    --  -90.25-112.00 134.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0000914000
_diffrn_orient_matrix_UB_12      -0.0922122000
_diffrn_orient_matrix_UB_13      0.0109876000
_diffrn_orient_matrix_UB_21      -0.1292665000
_diffrn_orient_matrix_UB_22      -0.0005657000
_diffrn_orient_matrix_UB_23      -0.0041781000
_diffrn_orient_matrix_UB_31      0.0062607000
_diffrn_orient_matrix_UB_32      -0.0177839000
_diffrn_orient_matrix_UB_33      -0.0567798000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0699
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.9877
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            77729
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.9877
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         74.30
_diffrn_reflns_theta_min         3.17
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.268
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69946
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_description       needle
_exptl_crystal_F_000             2476.778
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.6116
_refine_diff_density_min         -1.3007
_refine_diff_density_rms         0.1318
_refine_ls_d_res_high            0.8008
_refine_ls_d_res_low             13.9584
_refine_ls_extinction_coef       0.00022(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   0.7073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    86
_refine_ls_number_parameters     558
_refine_ls_number_reflns         10450
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.7073
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0437
_refine_ls_shift/su_max          0.0006
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0929P)^2^+53.4582P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1249
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              14
_reflns_limit_h_min              -14
_reflns_limit_k_max              20
_reflns_limit_k_min              0
_reflns_limit_l_max              32
_reflns_limit_l_min              0
_reflns_number_gt                9567
_reflns_number_total             10450
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4dt02733g2.cif
_cod_data_source_block           MCR_12
_cod_depositor_comments
'Adding full bibliography for 7717543--7717550.cif.'
_cod_original_formula_sum        'C46 H67 Ir1 N7 O9 P1 S4'
_cod_database_code               7717548
_chemical_oxdiff_formula         C30H39IrN5O2PS2
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C6aa(H6aa,H6ab), C30(H30a,H30b), C3aa(H3aa,H3ab), C5aa(H5aa,H5ab), C28(H28a,
 H28b), C4aa(H4aa,H4ab)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N1a(H1a), C22a(H22a), C16a(H16a), C12a(H12a), C13a(H13a), C26(H26),
 C26a(H26a), C23a(H23a), C22(H22), C25a(H25a), C25(H25), C15a(H15a), C12(H12),
 C14a(H14a), C23(H23), C16(H16), C13(H13), C15(H15), C14(H14)
2.c Idealised Me refined as rotating group:
 C37(H37a,H37b,H37c), C36(H36a,H36b,H36c), C39(H39a,H39b,H39c), C38(H38a,H38b,
 H38c), C40(H40a,H40b,H40c), C27a(H27a,H27b,H27c), C27(H27d,H27e,H27f)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 282 electrons were 
found in a volume of 1074\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[H2O], 2[CH4O] per Formula Unit 
which account for 264 electrons 
per unit cell.
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.708
_oxdiff_exptl_absorpt_empirical_full_min 0.564