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_1558067
_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         'C22 H23 F3 I Ir N3 O, F6 P, C H4 O'
_chemical_formula_sum            'C23 H27 F9 I Ir N3 O2 P'
_chemical_formula_weight         898.54
_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
_audit_creation_date             2018-06-04
_audit_creation_method
;
Olex2 1.2
(compiled Apr  3 2018 11:26:26 for OlexSys, GUI svn.r5486)
;
_audit_update_record
;
2018-08-08 deposited with the CCDC.	2020-04-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.2450(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.85870(10)
_cell_length_b                   20.2807(2)
_cell_length_c                   15.0835(2)
_cell_measurement_reflns_used    11692
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      77.6370
_cell_measurement_theta_min      4.6180
_cell_volume                     2909.69(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      296(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1417
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.968
_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 -116.00 -17.00 1.00 10.00 -- -41.71 -38.00 60.00 99 2 \w -130.00 46.00 1.00 10.00 -- -41.71 0.00-120.00 176 3 \w 18.00 98.00 1.00 10.00 -- 41.71-125.00 90.00 80 4 \w 18.00 98.00 1.00 10.00 -- 41.71-125.00 -60.00 80 5 \w 88.00 178.00 1.00 50.00 -- 114.00 45.00 -90.00 90 6 \w 57.00 151.00 1.00 50.00 -- 114.00 178.00-180.00 94 7 \w 38.00 91.00 1.00 50.00 -- 114.00 -30.00 -90.00 53 8 \w 100.00 178.00 1.00 50.00 -- 114.00 111.00 0.00 78 9 \w 38.00 91.00 1.00 50.00 -- 114.00 -30.00 90.00 53 10 \w 38.00 91.00 1.00 50.00 -- 114.00 -30.00 120.00 53 11 \w 100.00 178.00 1.00 50.00 -- 114.00 111.00-120.00 78 12 \w 41.00 99.00 1.00 50.00 -- 114.00 -45.00 -30.00 58 13 \w 38.00 88.00 1.00 50.00 -- 114.00-111.00 -30.00 50'
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1270385000
_diffrn_orient_matrix_UB_12      0.0024116000
_diffrn_orient_matrix_UB_13      0.0414414000
_diffrn_orient_matrix_UB_21      0.0605839000
_diffrn_orient_matrix_UB_22      -0.0586786000
_diffrn_orient_matrix_UB_23      0.0628612000
_diffrn_orient_matrix_UB_31      0.0801148000
_diffrn_orient_matrix_UB_32      0.0481656000
_diffrn_orient_matrix_UB_33      0.0744439000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0469
_diffrn_reflns_av_unetI/netI     0.0438
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            16591
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.991
_diffrn_reflns_theta_min         3.738
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.514
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12127
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'metallic dark purple'
_exptl_crystal_density_diffrn    2.051
_exptl_crystal_description       block
_exptl_crystal_F_000             1712
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.915
_refine_diff_density_min         -1.713
_refine_diff_density_rms         0.185
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     390
_refine_ls_number_reflns         6029
_refine_ls_number_restraints     112
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0507
_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^)+(0.1029P)^2^+1.4618P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1375
_refine_ls_wR_factor_ref         0.1404
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5698
_reflns_number_total             6029
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc00897d2.cif
_cod_data_source_block           wz10
_cod_depositor_comments
;Adding full bibliography for 1558064--1558071.cif.

 Adding full bibliography for 1558064--1558071.cif.
;
_cod_database_code               1558067
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 Ir'
_shelx_estimated_absorpt_t_max   0.319
_shelx_estimated_absorpt_t_min   0.095
_reflns_odcompleteness_completeness 99.39
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
The OH hydrogens were placed at calculated positions.
The PF6 was modeled over two positions related by a rotation about P10. The occupancy of the two components 
was linked to a free variable which refined to 73:27. The minor component was refined isotropically.
The Cp* was modeled as disordered over two positions related by a rotation about the bond to Ir1. 
The occupancy of the two components was originally linked to a free variable but fixed at 70:30 for the refinement. 
Both Cp* rings were refined with geometric restraints (AFIX 105) to give them idealized bond lengths and angles and 
a RIGU restraint was used to give reasonable thermal parameters for the methyl group of the major component.

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. Restrained distances
 P10-F11 = P10-F12 = P10-F13 = P10-F14 = P10-F15 = P10-F16
 1.6 with sigma of 0.02
 P10-F11A = P10-F12A = P10-F13A = P10-F14A = P10-F0AA = P10-F16A
 1.6 with sigma of 0.02
 H14-H21E
 -1.9 with sigma of 0.02
 F11-F13 = F11-F14 = F11-F15 = F11-F16
 2.26 with sigma of 0.04
 F12-F13 = F12-F14 = F12-F15 = F12-F16
 2.26 with sigma of 0.04
 F13-F15 = F13-F16 = F14-F15 = F14-F16
 2.26 with sigma of 0.04
 F11A-F13A = F11A-F14A = F11A-F0AA = F11A-F16A
 2.26 with sigma of 0.04
 F12A-F13A = F12A-F14A = F12A-F0AA = F12A-F16A
 2.26 with sigma of 0.04
 F13A-F0AA = F13A-F16A = F14A-F0AA = F14A-F16A
 2.26 with sigma of 0.04
3. Rigid body (RIGU) restrains
 C23, C24, C25, C21, C22, C20, C16, C17, C18, C19
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Others
 Sof(F13A)=Sof(F16A)=Sof(F12A)=Sof(F14A)=Sof(F0AA)=Sof(F11A)=1-FVAR(1)
 Sof(F14)=Sof(F13)=Sof(F15)=Sof(F11)=Sof(F16)=Sof(F12)=FVAR(1)
 Fixed Sof: C20(0.7) C16(0.7) C17(0.7) C18(0.7) C19(0.7) C25(0.7) H25A(0.7)
 H25B(0.7) H25C(0.7) C21(0.7) H21A(0.7) H21B(0.7) H21C(0.7) C22(0.7) H22A(0.7)
 H22B(0.7) H22C(0.7) C23(0.7) H23A(0.7) H23B(0.7) H23C(0.7) C24(0.7) H24A(0.7)
 H24B(0.7) H24C(0.7) C16A(0.3) C17A(0.3) C18A(0.3) C19A(0.3) C20A(0.3)
 C21A(0.3) H21D(0.3) H21E(0.3) H21F(0.3) C22A(0.3) H22D(0.3) H22E(0.3)
 H22F(0.3) C23A(0.3) H23D(0.3) H23E(0.3) H23F(0.3) C24A(0.3) H24D(0.3)
 H24E(0.3) H24F(0.3) C25A(0.3) H25D(0.3) H25E(0.3) H25F(0.3)
5.a Me refined with riding coordinates:
 C21A(H21D,H21E,H21F)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C2(H2), C13(H13), C10(H10), C11(H11), C14(H14)
5.c Cp* refined as free rotating group:
 C20(C16,C17,C18,C19,C25,C21,C22,C23,C24), C16A(C17A,C18A,C19A,C20A,C21A,C22A,
 C23A,C24A,C25A)
5.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C27(H27A,H27B,H27C), C22A(H22D,H22E,H22F),
 C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F)
5.e Idealised tetrahedral OH refined as rotating group:
 O12(H12), O26(H26)
;
_shelx_res_checksum              34609
_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 6.020
_oxdiff_exptl_absorpt_empirical_full_min 0.516