Importance of steric bulkiness of iridium photocatalysts with PNNP tetradentate ligands for CO2 reduction
Kamada, Kenji; Jung, Jieun; Kametani, Yohei; Wakabayashi, Taku; Shiota, Yoshihito; Yoshizawa, Kazunari; Bae, Seong Hee; Muraki, Manami; Naruto, Masayuki; Sekizawa, Keita; Sato, Shunsuke; Morikawa, Takeshi; Saito, Susumu; Chemical Communications  (2022) –; doi:10.1039/D2CC01701F

data_7130436
_publ_section_title
;
 Importance of steric bulkiness of iridium photocatalysts with PNNP
 tetradentate ligands for CO2 reduction
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01701F
_journal_year                    2022
_chemical_formula_moiety         'C24 H39 Cl Ir N2 P2, C24 H20 B, C H2 Cl2'
_chemical_formula_sum            'C49 H61 B Cl3 Ir N2 P2'
_chemical_formula_weight         1049.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2022-06-01 deposited with the CCDC.	2022-07-27 downloaded from the CCDC.
;
_cell_angle_alpha                81.1450(10)
_cell_angle_beta                 79.3760(10)
_cell_angle_gamma                76.0240(10)
_cell_formula_units_Z            2
_cell_length_a                   12.7305(2)
_cell_length_b                   13.2336(2)
_cell_length_c                   14.6639(2)
_cell_measurement_reflns_used    30644
_cell_measurement_temperature    123.15
_cell_measurement_theta_max      31.4430
_cell_measurement_theta_min      2.8350
_cell_volume                     2340.65(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123.15
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.852
_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    -70.00 -29.00   0.50    2.12    --    1.30  45.00 150.00   82
  2  \w    -20.00   9.00   0.50    2.12    --    1.30  45.00 150.00   58
  3  \w     13.00  89.00   0.50    2.12    --    1.30  45.00 150.00  152
  4  \w    -62.00  90.00   0.50    2.12    --    1.30  45.00  30.00  304
  5  \w     46.00  78.00   0.50    2.12    --    1.30  45.00  90.00   64
  6  \w    -80.00 -34.00   0.50    2.12    --    1.30  45.00  60.00   92
  7  \w    -36.00  -9.00   0.50    2.12    --    1.30  45.00   0.00   54
  8  \w      9.00  44.00   0.50    2.12    --    1.30  45.00   0.00   70
  9  \w     -6.00  21.00   0.50    2.12    --    1.30  45.00 120.00   54
 10  \w    -85.00  52.00   0.50    2.12    --    2.70  45.00  90.00  274
;
_diffrn_measurement_device       'fixed Chi diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0426402000
_diffrn_orient_matrix_UB_12      -0.0413804000
_diffrn_orient_matrix_UB_13      -0.0166858000
_diffrn_orient_matrix_UB_21      -0.0230447000
_diffrn_orient_matrix_UB_22      0.0053103000
_diffrn_orient_matrix_UB_23      -0.0414511000
_diffrn_orient_matrix_UB_31      0.0320460000
_diffrn_orient_matrix_UB_32      0.0367545000
_diffrn_orient_matrix_UB_33      -0.0213943000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0279
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.852
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            62197
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.852
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.791
_diffrn_reflns_theta_min         2.550
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    3.127
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86835
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'fluorescent light yellow'
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_description       block
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.127
_refine_diff_density_max         1.872
_refine_diff_density_min         -1.090
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     535
_refine_ls_number_reflns         13598
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0243
_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^)+(0.0320P)^2^+0.9060P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0553
_refine_ls_wR_factor_ref         0.0564
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12512
_reflns_number_total             13598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01701f2.cif
_cod_data_source_block           irpip2
_cod_database_code               7130436
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C56H59IrBClN2P2
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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.a Ternary CH refined with riding coordinates:
 C7(H7), C22(H22), C10(H10), C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C6(H6A,H6B), C49(H49A,H49B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C14(H14), C15(H15), C36(H36), C16(H16), C45(H45),
 C41(H41), C40(H40), C44(H44), C48(H48), C32(H32), C26(H26), C30(H30), C47(H47),
  C46(H46), C33(H33), C42(H42), C38(H38), C39(H39), C35(H35), C27(H27),
 C29(H29), C34(H34), C28(H28)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C8(H8A,H8B,H8C), C11(H11A,H11B,H11C), C24(H24A,H24B,H24C),
 C23(H23A,H23B,H23C), C12(H12A,H12B,H12C), C21(H21A,H21B,H21C), C20(H20A,H20B,
 H20C)
;
_shelx_res_checksum              32771
_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 1.233
_oxdiff_exptl_absorpt_empirical_full_min 0.840