Reversible P–P bond cleavage at an iridium(iii) metal centre
Coles, Simon J.; Horton, Peter N.; Kimber, Patrick; Klooster, Wim T.; Liu, Pingchuan; Plasser, Felix; Smith, Martin B.; Tizzard, Graham J.; Chemical Communications  (2022) –; doi:10.1039/D2CC00706A

data_7129989
_publ_section_title
;
 Reversible P--P bond cleavage at an iridium(iii) metal centre
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00706A
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C56 H74 Au2 Cl6 Ir2 N4 O4 P4, C Cl3 D'
_chemical_formula_sum            'C57 H74 Au2 Cl9 D Ir2 N4 O4 P4'
_chemical_formula_weight         2102.47
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-10
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-04-04 deposited with the CCDC.	2022-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.06100(10)
_cell_length_b                   20.28880(10)
_cell_length_c                   25.7121(2)
_cell_measurement_reflns_used    118571
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.4450
_cell_measurement_theta_min      1.9630
_cell_volume                     6813.50(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'hybrid pixel array detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000HE'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -47.00  78.00   0.25    2.00    --  -11.20  57.00 -90.00  500
  2  \w   -101.00  24.00   0.25    2.00    --  -11.20 -60.00-180.00  500
  3  \w    -47.00  78.00   0.25    2.00    --  -11.20  60.00   0.00  500
  4  \w   -101.00  78.00   0.25    2.00    --  -11.20 -19.00 120.00  716
  5  \w   -101.00  24.00   0.25    2.00    --  -11.20 -60.00  60.00  500
  6  \w    -47.00  78.00   0.25    2.00    --  -11.20  60.00-180.00  500
  7  \w   -101.00  20.00   0.25    2.00    --  -11.20 -60.00 -60.00  484
  8  \w    -53.00  77.00   0.25    2.00    --  -11.20  45.00 139.95  520
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, AFC12 \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ diffractometer with Arc)Sec VHF Varimax confocal mirrors, an AFC12 goniometer and HyPix 6000HE detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0143229000
_diffrn_orient_matrix_UB_12      0.0334316000
_diffrn_orient_matrix_UB_13      0.0035721000
_diffrn_orient_matrix_UB_21      -0.0265895000
_diffrn_orient_matrix_UB_22      0.0086648000
_diffrn_orient_matrix_UB_23      -0.0230571000
_diffrn_orient_matrix_UB_31      -0.0451204000
_diffrn_orient_matrix_UB_32      0.0054844000
_diffrn_orient_matrix_UB_33      0.0147146000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, Arc)Sec VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            193070
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.158
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    8.680
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.537
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.050
_exptl_crystal_description       block
_exptl_crystal_F_000             4008
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.868
_refine_diff_density_min         -1.088
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details
;
 Flack x determined using 6944 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0118(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     753
_refine_ls_number_reflns         15614
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0167
_refine_ls_R_factor_gt           0.0164
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0208P)^2^+13.2620P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0427
_refine_ls_wR_factor_ref         0.0428
_reflns_Friedel_coverage         0.832
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                15494
_reflns_number_total             15614
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00706a2.cif
_cod_data_source_block           2-CDCl3
_cod_database_code               7129989
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C28 H37 N2 O2 P2 Au Ir Cl3 CHCl3'
_chemical_oxdiff_usercomment     ms2732
_shelx_estimated_absorpt_t_max   0.671
_shelx_estimated_absorpt_t_min   0.304
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O2) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
3.a Ternary CH refined with riding coordinates:
 C57(D57)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C1(H1A,H1B), C10(H10A,H10B), C38(H38A,H38B), C39(H39A,H39B),
 C30(H30A,H30B), C29(H29A,H29B), C11(H11A,H11B)
3.c Aromatic/amide H refined with riding coordinates:
 C36(H36), C33(H33), C42(H42), C41(H41), C45(H45), C4(H4), C8(H8), C7(H7),
 C14(H14), C44(H44), C35(H35), C32(H32), C17(H17), C13(H13), C5(H5), C16(H16)
3.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C24(H24A,H24B,H24C), C27(H27A,H27B,H27C), C25(H25A,H25B,
 H25C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C37(H37A,H37B,H37C), C46(H46A,
 H46B,H46C), C9(H9A,H9B,H9C), C26(H26A,H26B,H26C), C54(H54A,H54B,H54C),
 C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              43280
_shelx_hkl_checksum              90127
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.956
_oxdiff_exptl_absorpt_empirical_full_min 0.430