Ligand-centred redox activation of inert organoiridium anticancer catalysts
Zhang, Wen-Ying; Banerjee, Samya; Hughes, George M.; Bridgewater, Hannah E.; Song, Ji-Inn; Breeze, Ben G.; Clarkson, Guy J.; Coverdale, James P. C.; Sanchez-Cano, Carlos; Ponte, Fortuna; Sicilia, Emilia; Sadler, Peter J.; Chemical Science 11 (2020) 5466–5480; doi:10.1039/D0SC00897D

data_1558066
_publ_section_title
;
 Ligand-centred redox activation of inert organoiridium anticancer
 catalysts
;
_journal_issue                   21
_journal_name_full               'Chemical Science'
_journal_page_first              5466
_journal_page_last               5480
_journal_paper_doi               10.1039/D0SC00897D
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C21 H23 Br I Ir N3 O, C H4 O, F6 P'
_chemical_formula_sum            'C22 H27 Br F6 I Ir N3 O2 P'
_chemical_formula_weight         909.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-08-08 deposited with the CCDC.	2020-04-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.4265(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.61097(8)
_cell_length_b                   20.10144(16)
_cell_length_c                   14.45419(15)
_cell_measurement_reflns_used    39529
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.3490
_cell_measurement_theta_min      4.3620
_cell_volume                     2716.15(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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    -65.00  31.00   1.00    1.00    --  -42.36  37.00  90.00   96
  2  \w   -129.00  44.00   1.00    1.00    --  -42.36   0.00  30.00  173
  3  \w     20.00 115.00   1.00    1.00    --   42.36  37.00  30.00   95
  4  \w     97.00 178.00   1.00    4.00    --  106.00  83.00  65.00   81
  5  \w     25.00 109.00   1.00    4.00    --  106.00 -94.00 -90.00   84
  6  \w     35.00 130.00   1.00    4.00    --  106.00 -45.00 -90.00   95
  7  \w     82.00 178.00   1.00    4.00    --  106.00  30.00-150.00   96
  8  \w     82.00 177.00   1.00    4.00    --  106.00  45.00  30.00   95
  9  \w     25.00 109.00   1.00    4.00    --  106.00 -94.00  90.00   84
 10  \w     31.00 130.00   1.00    4.00    --  106.00 -30.00  60.00   99
 11  \w     82.00 178.00   1.00    4.00    --  106.00  30.00 150.00   96
 12  \w     34.00 121.00   1.00    4.00    --  106.00-125.00  90.00   87
 13  \w     25.00 109.00   1.00    4.00    --  106.00 -94.00-150.00   84
 14  \w     23.00  97.00   1.00    1.00    --   42.36-125.00-120.00   74
 15  \w     11.00 116.00   1.00    1.00    --   42.36  77.00  60.00  105
 16  \w     11.00 116.00   1.00    1.00    --   42.36  77.00 -90.00  105
 17  \w     11.00 116.00   1.00    1.00    --   42.36  77.00 150.00  105
 18  \w     78.00 176.00   1.00    4.00    --  106.00  61.00-150.00   98
 19  \w     78.00 176.00   1.00    4.00    --  106.00  61.00-120.00   98
 20  \w     78.00 176.00   1.00    4.00    --  106.00  61.00 -30.00   98
 21  \w     78.00 176.00   1.00    4.00    --  106.00  61.00 150.00   98
 22  \w     82.00 178.00   1.00    4.00    --  106.00  30.00 -60.00   96
 23  \w     78.00 176.00   1.00    4.00    --  106.00  61.00 -60.00   98
 24  \w     78.00 176.00   1.00    4.00    --  106.00  61.00  90.00   98
 25  \w     78.00 176.00   1.00    4.00    --  106.00  61.00  60.00   98
 26  \w   -116.00 -11.00   1.00    1.00    --  -42.36 -77.00 -30.00  105
 27  \w     23.00  97.00   1.00    1.00    --   42.36-125.00 -30.00   74
 28  \w     16.00 113.00   1.00    1.00    --   42.36  57.00-120.00   97
 29  \w      1.00  82.00   1.00    1.00    --   42.36 -99.00-180.00   81
 30  \w     78.00 176.00   1.00    4.00    --  106.00  61.00  30.00   98
 31  \w     25.00 109.00   1.00    4.00    --  106.00 -94.00 150.00   84
 32  \w     78.00 176.00   1.00    4.00    --  106.00  61.00   0.00   98
 33  \w     78.00 117.00   1.00    4.00    --  106.00  61.00 120.00   39
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0448326000
_diffrn_orient_matrix_UB_12      0.0663629000
_diffrn_orient_matrix_UB_13      0.0517883000
_diffrn_orient_matrix_UB_21      -0.1492917000
_diffrn_orient_matrix_UB_22      0.0062506000
_diffrn_orient_matrix_UB_23      0.0213475000
_diffrn_orient_matrix_UB_31      0.0537155000
_diffrn_orient_matrix_UB_32      -0.0378477000
_diffrn_orient_matrix_UB_33      0.0940911000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0555
_diffrn_reflns_av_unetI/netI     0.0296
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            29026
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.330
_diffrn_reflns_theta_min         3.837
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    21.338
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35438
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    2.224
_exptl_crystal_description       block
_exptl_crystal_F_000             1720
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.000
_refine_diff_density_min         -1.808
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     379
_refine_ls_number_reflns         5384
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.0295
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0452P)^2^+4.5103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0770
_refine_ls_wR_factor_ref         0.0772
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5341
_reflns_number_total             5384
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc00897d2.cif
_cod_data_source_block           wz6
_cod_depositor_comments
;Adding full bibliography for 1558064--1558071.cif.

 Adding full bibliography for 1558064--1558071.cif.
;
_cod_original_cell_volume        2716.14(4)
_cod_database_code               1558066
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C20 H20 N2 O2 Cl Rh'
_shelx_estimated_absorpt_t_max   0.361
_shelx_estimated_absorpt_t_min   0.131
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
The OHs were located in a difference map but placed at calculated positions for the refinement.
The PF6 counter ion was modeled as disordered over two positions related by a rotation about the 
F11-P1-F12 axis. The occupancy of the two components was linked to a free variable which refined to 61:39

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Others
 Sof(F13A)=Sof(F15A)=Sof(F14A)=Sof(F16A)=1-FVAR(1)
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=FVAR(1)
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C10(H10), C11(H11), C13(H13), C14(H14)
3.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C02(H02A,H02B,H02C)
3.c Idealised tetrahedral OH refined as rotating group:
 O12(H12), O01(H01)
;
_shelx_res_checksum              14123
_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 3.977
_oxdiff_exptl_absorpt_empirical_full_min 0.465