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_1558065
_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         'C26 H25.5 I Ir N3 O, F3 P0.5'
_chemical_formula_sum            'C26 H25.5 F3 I Ir N3 O P0.5'
_chemical_formula_weight         787.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yc'
_space_group_name_H-M_alt        'P 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-03-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2018-08-08 deposited with the CCDC.	2020-04-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.2675(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.1650(4)
_cell_length_b                   7.44609(9)
_cell_length_c                   15.7060(2)
_cell_measurement_reflns_used    34647
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      32.7940
_cell_measurement_theta_min      2.8820
_cell_volume                     2587.01(7)
_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    'ShelXS (Sheldrick, 2008)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.951
_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    -53.00  48.00   1.00    6.26    --   20.12 -57.00 -60.00  101
  2  \w     -4.00  95.00   1.00    6.26    --   20.12  37.00-180.00   99
  3  \w     34.00 107.00   1.00    6.26    --   20.12-178.00 120.00   73
  4  \w     -8.00  93.00   1.00    6.26    --   20.12  57.00-150.00  101
  5  \w    -56.00  53.00   1.00    6.26    --   20.12 -77.00  90.00  109
  6  \w     -8.00  93.00   1.00    6.26    --   20.12  57.00-120.00  101
  7  \w   -108.00 -57.00   1.00    6.26    --  -19.19-178.00  90.00   51
  8  \w    -12.00  96.00   1.00    6.26    --   20.12  77.00 -60.00  108
  9  \w    -20.00  61.00   1.00    6.26    --   20.12 -99.00-120.00   81
 10  \w     -8.00  93.00   1.00    6.26    --   20.12  57.00  90.00  101
 11  \w     -4.00  95.00   1.00    6.26    --   20.12  37.00  60.00   99
 12  \w    -20.00  61.00   1.00    6.26    --   20.12 -99.00 -30.00   81
 13  \w    -17.00  32.00   1.00    6.26    --   20.12-104.00  72.00   49
 14  \w    -20.00  61.00   1.00    6.26    --   20.12 -99.00-180.00   81
;
_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      -0.0454527000
_diffrn_orient_matrix_UB_12      -0.0103806000
_diffrn_orient_matrix_UB_13      -0.0169135000
_diffrn_orient_matrix_UB_21      -0.0129325000
_diffrn_orient_matrix_UB_22      0.0234607000
_diffrn_orient_matrix_UB_23      0.0258687000
_diffrn_orient_matrix_UB_31      -0.0018476000
_diffrn_orient_matrix_UB_32      0.0917351000
_diffrn_orient_matrix_UB_33      -0.0085378000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0514
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            97034
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.100
_diffrn_reflns_theta_min         2.596
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.431
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58172
_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            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    2.022
_exptl_crystal_description       block
_exptl_crystal_F_000             1500
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.805
_refine_diff_density_min         -0.962
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         9366
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0231
_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^)+(0.0119P)^2^+2.4792P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0416
_refine_ls_wR_factor_ref         0.0439
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8195
_reflns_number_total             9366
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc00897d2.cif
_cod_data_source_block           wz1
_cod_depositor_comments
;Adding full bibliography for 1558064--1558071.cif.

 Adding full bibliography for 1558064--1558071.cif.
;
_cod_original_cell_volume        2587.00(7)
_cod_original_formula_sum        'C26 H25.50 F3 I Ir N3 O P0.50'
_cod_database_code               1558065
_shelx_shelxl_version_number     2014/7
_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 PF6 counter ion that sits on a two fold axis. The PF6 is disordered across the two fold axis 
about the meridian of the PF6. F11 is at full occupancy but F12 and F13 were modeled at 75% occupancy. 
The other component of the disorder lies with two of the fluorides (F12A F14A) on the 2 fold axis 
and F13A (at 25% occupancy) on a general position.

This is balanced by the phenol which is partially ionized.
The phenol is partially ionized as two phenoxides share a proton and are related by an inversion centre 
so also contributes half a minus charge. 
The partially occupied proton was located in a difference map but refined at a calculated position at 50% occupancy. 
This works out at one proton (H12) shared between two phenolic oxygens (O12 and a symmetry related O12) related by an 
inversion centre.

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) F12(0.75) F13(0.75) F12A(0.125) F14A(0.125) F13A(0.25)
3.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C4(H4), C2(H2), C5(H5), C19(H19), C11(H11), C15(H15), C16(H16),
 C18(H18), C14(H14), C3(H3), C13(H13), C17(H17)
3.b Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C)
3.c Idealised tetrahedral OH refined as rotating group:
 O12(H12)
;
_shelx_res_checksum              60551
_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 2.115
_oxdiff_exptl_absorpt_empirical_full_min 0.691