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_1558070
_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 H23.5 Cl Ir N3 O, C H4 O, 0.5(Cl)'
_chemical_formula_sum            'C22 H27.5 Cl1.5 Ir N3 O2'
_chemical_formula_weight         611.34
_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     direct
_audit_creation_date             2015-06-03
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2019-06-08 deposited with the CCDC.	2020-04-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.0660(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.93939(15)
_cell_length_b                   18.6768(3)
_cell_length_c                   13.4520(2)
_cell_measurement_reflns_used    18491
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      32.5290
_cell_measurement_theta_min      3.0350
_cell_volume                     2240.28(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_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 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.936
_diffrn_measurement_details
;
  1 omega  -10.00   91.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       18.2951   57.0000   60.0000 101

  2 omega  -56.00   43.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       18.2951  -38.0000  -90.0000 99

  3 omega   -6.00   93.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       18.2951   38.0000  150.0000 99

  4 omega  -25.00   22.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.2326  -99.0000   60.0000 47

  5 omega   -6.00   81.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       18.2951   38.0000  -90.0000 87

  6 omega  -25.00   59.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       18.2951  -99.0000  120.0000 84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0434787000
_diffrn_orient_matrix_UB_12      -0.0302119000
_diffrn_orient_matrix_UB_13      0.0158484000
_diffrn_orient_matrix_UB_21      -0.0566151000
_diffrn_orient_matrix_UB_22      -0.0230046000
_diffrn_orient_matrix_UB_23      -0.0214026000
_diffrn_orient_matrix_UB_31      0.0350953000
_diffrn_orient_matrix_UB_32      0.0002983000
_diffrn_orient_matrix_UB_33      -0.0456684000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            36123
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.691
_diffrn_reflns_theta_min         2.531
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.162
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46391
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.813
_exptl_crystal_description       block
_exptl_crystal_F_000             1196
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.28
_refine_diff_density_max         1.581
_refine_diff_density_min         -2.963
_refine_diff_density_rms         0.685
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.297
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     276
_refine_ls_number_reflns         7716
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.297
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0245
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0509P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0684
_refine_ls_wR_factor_ref         0.0991
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6752
_reflns_number_total             7716
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc00897d2.cif
_cod_data_source_block           gh2
_cod_depositor_comments
;Adding full bibliography for 1558064--1558071.cif.

 Adding full bibliography for 1558064--1558071.cif.
;
_cod_original_formula_sum        'C22 H27.50 Cl1.50 Ir N3 O2'
_cod_database_code               1558070
_chemical_oxdiff_formula         'C20 H20 N2 O2 F6 P Ir'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
The asymmetric unit contains the Ir complex and a molecule of methanol and a chloride counter ion. 
The chloride counter ion sits on an inversion centre (so is at half occupancy)
Four times all this in the unit cell.
The OHs on the methanol and the phenol were not located but placed at calculated positions.
The problem is that there is only half a chloride counter ion per Ir complex and the phenol 
OH forms a hydrogen bond to a symmetry related phenol, so there is a clash of the OH hydrogens
This is because there is only one proton shared between the two phenol oxygens. 
In reality the hydrogen shuttles between the phenol oxygen O12 and the symmetry related O12 
but this situation cant be resolved by this Xray experiment. 
This was modelled by simply having H12 at 50% occupancy giving a total of one fully occupied
hydrogen (2 x half occupied H12) lying between O12 and its symmetry equivalent.

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
 Fixed Sof: H12(0.5)
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), 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), C26(H26A,H26B,H26C)
3.c Idealised tetrahedral OH refined as rotating group:
 O12(H12), O25(H25)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'