C2/C4 Regioselective Heteroarylation of Indoles by Tuning C‒H Metalation Modes
Chen, Shuyou; Zhang, Min; Su, Rongchuan; Chen, Xingyu; Feng, Boya; Yang, Yudong; You, Jingsong; ACS Catalysis 9 (2019) 6372–; doi:10.1021/acscatal.9b01273

data_4514793
_publ_section_title
;
 C2/C4 Regioselective Heteroarylation of Indoles by Tuning C--H Metalation
 Modes
;
_journal_issue                   7
_journal_name_full               'ACS Catalysis'
_journal_page_first              6372
_journal_paper_doi               10.1021/acscatal.9b01273
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C24 H31 Cl Ir N O'
_chemical_formula_sum            'C24 H31 Cl Ir N O'
_chemical_formula_weight         577.15
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-02-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.7814(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.81332(15)
_cell_length_b                   15.7101(3)
_cell_length_c                   17.1127(2)
_cell_measurement_reflns_used    5439
_cell_measurement_temperature    292(1)
_cell_measurement_theta_max      72.7600
_cell_measurement_theta_min      5.2070
_cell_volume                     2310.68(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      292(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.981
_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    -55.00  33.00   1.00    1.00    --  -36.29  38.00 -60.00   88
  2  \w   -105.00 -17.00   1.00    1.00    --  -36.29 -38.00 -30.00   88
  3  \w     20.00 104.00   1.00    1.00    --   36.29  57.00 -60.00   84
  4  \w      1.00  75.00   1.00    1.00    --   36.29 -99.00  90.00   74
  5  \w     20.00 104.00   1.00    1.00    --   36.29  57.00   0.00   84
  6  \w      1.00  75.00   1.00    1.00    --   36.29 -99.00-150.00   74
  7  \w    100.00 178.00   1.00    1.89    --  108.71 111.00 -30.00   78
  8  \w     39.00 115.00   1.00    1.89    --  108.71-111.00  90.00   76
  9  \w     57.00 151.00   1.00    1.89    --  108.71 178.00   0.00   94
 10  \w     42.00 127.00   1.00    1.89    --  108.71 -61.00 -90.00   85
 11  \w     40.00 126.00   1.00    1.89    --  108.71 -45.00-180.00   86
 12  \w     39.00 109.00   1.00    1.89    --  108.71 -94.00 -90.00   70
 13  \w     39.00 109.00   1.00    1.89    --  108.71 -94.00-180.00   70
 14  \w     39.00 103.00   1.00    1.89    --  108.71 -94.00  30.00   64
 15  \w     37.00 142.00   1.00    1.89    --  108.71 -15.00-120.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1527294000
_diffrn_orient_matrix_UB_12      -0.0508439000
_diffrn_orient_matrix_UB_13      0.0108703000
_diffrn_orient_matrix_UB_21      0.0931017000
_diffrn_orient_matrix_UB_22      0.0837725000
_diffrn_orient_matrix_UB_23      0.0097789000
_diffrn_orient_matrix_UB_31      0.0120079000
_diffrn_orient_matrix_UB_32      -0.0029212000
_diffrn_orient_matrix_UB_33      0.0911579000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0474
_diffrn_reflns_av_unetI/netI     0.0448
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            13230
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.893
_diffrn_reflns_theta_min         3.864
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.342
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.22035
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.659
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.180
_refine_diff_density_min         -2.180
_refine_diff_density_rms         0.292
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         4521
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0549
_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^)+(0.1050P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1414
_refine_ls_wR_factor_ref         0.1483
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3999
_reflns_number_total             4521
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01273_si_004.cif
_cod_data_source_block           yjs-csy-3
_cod_database_code               4514793
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00H(H00H), C00L(H00L), C00M(H00M)
2.b Idealised Me refined as rotating group:
 C00F(H00A,H00C,H00D), C00I(H00E,H00F,H00G), C00J(H00I,H00J,H00K), C00N(H00N,
 H00O,H00P), C00O(H00Q,H00R,H00S), C00P(H00T,H00U,H00V), C00Q(H00W,H00X,H00Y),
 C00R(H00Z,H,HA), C00S(H00,HB,HC)
;
_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 2.833
_oxdiff_exptl_absorpt_empirical_full_min 0.572