Rhodium(III)-catalyzed direct C-H activation of 2-aryl-3<i>H</i>-indoles: a strategy for 4-heteroaryl pyrazole synthesis.
Yang, Zi; Luo, Ji; Zhang, Wenbo; Lei, Jieni; Liu, Chaoshui; Li, Yaqian; Organic & biomolecular chemistry 23 (2025) 323–327; doi:10.1039/d4ob01655f

data_7160247
_publ_section_title
;
 Rhodium(III)-catalyzed direct C-H activation of 2-aryl-3<i>H</i>-indoles:
 a strategy for 4-heteroaryl pyrazole synthesis.
;
_journal_issue                   2
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              323
_journal_page_last               327
_journal_paper_doi               10.1039/d4ob01655f
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C26 H22 Cl N3 O'
_chemical_formula_sum            'C26 H22 Cl N3 O'
_chemical_formula_weight         427.91
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-14
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-08-21 deposited with the CCDC.	2024-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.735(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4744(9)
_cell_length_b                   16.0747(14)
_cell_length_c                   14.7594(11)
_cell_measurement_reflns_used    2742
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      26.3990
_cell_measurement_theta_min      2.8910
_cell_volume                     2215.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0606
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.850
_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     -1.00  74.00   1.00    4.00    --   16.96  19.00 150.00   75
  2  \w     27.00  77.00   1.00    4.00    --   16.96  37.00  60.00   50
  3  \w    -46.00  16.00   1.00    4.00    --  -17.43  77.00 -60.00   62
  4  \w    -20.00  10.00   1.00    4.00    --  -17.43 -77.00-180.00   30
  5  \w    -26.00   9.00   1.00    4.00    --  -17.43 -77.00  90.00   35
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0316993000
_diffrn_orient_matrix_UB_12      0.0394563000
_diffrn_orient_matrix_UB_13      0.0040630000
_diffrn_orient_matrix_UB_21      0.0558456000
_diffrn_orient_matrix_UB_22      0.0191352000
_diffrn_orient_matrix_UB_23      -0.0190207000
_diffrn_orient_matrix_UB_31      -0.0406975000
_diffrn_orient_matrix_UB_32      -0.0045706000
_diffrn_orient_matrix_UB_33      -0.0447138000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.850
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            11487
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.850
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.311
_diffrn_reflns_theta_min         2.384
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.195
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90309
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.99a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.177
_refine_diff_density_min         -0.226
_refine_diff_density_rms         0.035
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         5140
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0873
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0433P)^2^+0.5179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1094
_refine_ls_wR_factor_ref         0.1247
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3530
_reflns_number_total             5140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01655f2.cif
_cod_data_source_block           exp_13844
_cod_depositor_comments          'Adding full bibliography for 7160247.cif.'
_cod_database_code               7160247
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.973
_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, All O(H) groups
2.a Riding coordinates:
 O1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C21(H21), C22(H22), C24(H24)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C17(H17A,H17B,H17C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              52010
_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 1.121
_oxdiff_exptl_absorpt_empirical_full_min 0.889