Cobalt-catalyzed direct carbonylative 3-acylation of (N-H)Indoles with alkyl halides.
Xu, Chao; Bao, Zhi-Peng; Shao, Sufang; Wu, Xiao-Feng; Chemical science 16 (2025) 18838–18843; doi:10.1039/d5sc05810d

data_1575621
_publ_section_title
;
 Cobalt-catalyzed direct carbonylative 3-acylation of (N-H)Indoles with
 alkyl halides.
;
_journal_issue                   40
_journal_name_full               'Chemical science'
_journal_page_first              18838
_journal_page_last               18843
_journal_paper_doi               10.1039/d5sc05810d
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C30 H24 Br0.5 Co0.5 P2, 0.5(Br), C H4 O, 0.5(H2 O)'
_chemical_formula_sum            'C31 H29 Br Co0.5 O1.5 P2'
_chemical_formula_weight         596.86
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-24
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-26 deposited with the CCDC.	2025-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.433(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.5390(4)
_cell_length_b                   9.5032(2)
_cell_length_c                   18.1818(4)
_cell_measurement_reflns_used    11501
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.5710
_cell_measurement_theta_min      2.8710
_cell_volume                     2662.35(11)
_computing_cell_refinement       'CrysAlisPro 1.171.44.91a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.91a (Rigaku OD, 2025)'
_computing_data_reduction        'CrysAlisPro 1.171.44.91a (Rigaku OD, 2025)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.952
_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  72.00   0.50    0.05    --   46.85-151.00 175.00   50
  2  \w     33.00 128.00   0.50    0.05    --  104.58-151.00 175.00  190
  3  \w     54.00  87.00   0.50    0.05    --   46.85-122.00 -22.00   66
  4  \w     35.00 110.00   0.50    0.05    --  104.58-125.00 -60.00  150
  5  \w     48.00  73.00   0.50    0.05    --  104.58-122.00 -22.00   50
  6  \w     84.00 146.00   0.50    0.05    --  104.58 122.00  58.00  124
  7  \w     62.00  93.00   0.50    0.05    --   46.85 151.00-140.00   62
  8  \w     89.00 114.00   0.50    0.05    --  104.58 151.00-140.00   50
  9  \w     81.00 106.00   0.50    0.05    --  104.58 125.00 -90.00   50
 10  \w    119.00 174.00   0.50    0.05    --  104.58 125.00 -90.00  110
 11  \w    103.00 129.00   0.50    0.05    --  104.58  45.00-150.00   52
 12  \w    151.00 176.00   0.50    0.05    --  104.58  45.00-150.00   50
 13  \w     83.00 177.00   0.50    0.05    --  104.58  77.00 120.00  188
 14  \w     89.00 176.00   0.50    0.05    --  104.58  61.00 150.00  174
 15  \w     34.00 119.00   0.50    0.05    --   46.85  57.00  60.00  170
 16  \w   -105.00 -80.00   0.50    0.05    -- -104.50 151.00-140.00   50
 17  \w   -121.00 -62.00   0.50    0.05    -- -104.50 138.00 -62.40  118
 18  \w    -88.00 -62.00   0.50    0.05    -- -104.50 141.00 -30.47   52
 19  \w   -123.00 -90.00   0.50    0.05    -- -104.50 141.00 -30.47   66
 20  \w    -93.00 -49.00   0.50    0.05    -- -104.50  77.00  60.00   88
 21  \w    -18.00  24.00   0.50    0.05    --  -46.85  19.00 150.00   84
 22  \w    -22.00   5.00   0.50    0.05    --  -46.85  19.00 -90.00   54
 23  \w    -23.00  29.00   0.50    0.05    --  -46.85  19.00-150.00  104
 24  \w    -62.00 -32.00   0.50    0.05    -- -104.50  61.00-150.00   60
 25  \w   -149.00-124.00   0.50    0.05    -- -104.50-122.00 -22.00   50
 26  \w   -119.00 -57.00   0.50    0.05    --  -46.85-151.00 175.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0247085000
_diffrn_orient_matrix_UB_12      0.1541934000
_diffrn_orient_matrix_UB_13      -0.0133486000
_diffrn_orient_matrix_UB_21      -0.0553910000
_diffrn_orient_matrix_UB_22      0.0483834000
_diffrn_orient_matrix_UB_23      0.0596310000
_diffrn_orient_matrix_UB_31      0.0794549000
_diffrn_orient_matrix_UB_32      -0.0139280000
_diffrn_orient_matrix_UB_33      0.0596971000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0807
_diffrn_reflns_av_unetI/netI     0.0448
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            19195
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.260
_diffrn_reflns_theta_min         4.008
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.788
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31819
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.91a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear brownish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_description       block
_exptl_crystal_F_000             1222
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: CH3OH'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.990
_refine_diff_density_min         -1.602
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     329
_refine_ls_number_reflns         5295
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0794
_refine_ls_R_factor_gt           0.0735
_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^)+(0.1290P)^2^+9.6785P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1979
_refine_ls_wR_factor_ref         0.2035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4730
_reflns_number_total             5295
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05810d2.cif
_cod_data_source_block           xc-1_auto
_cod_depositor_comments          'Adding full bibliography for 1575621.cif.'
_cod_original_formula_sum        'C31 H29 Br Co0.50 O1.50 P2'
_cod_database_code               1575621
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O P Co'
_chemical_oxdiff_usercomment     'CSD: GEVDUI'
_cell_oxdiff_angle_alpha         89.965(3)
_cell_oxdiff_angle_beta          97.480(2)
_cell_oxdiff_angle_gamma         90.062(3)
_cell_oxdiff_length_a            15.5454(6)
_cell_oxdiff_length_b            9.4969(4)
_cell_oxdiff_length_c            18.1883(4)
_cell_oxdiff_measurement_reflns_used 11518
_cell_oxdiff_volume              2662.34(16)
_shelx_estimated_absorpt_t_max   0.595
_shelx_estimated_absorpt_t_min   0.543
_diffrn_oxdiff_digest_hkl
;
4340f4b5c04e524b61f356698a5984acf17865
;
_diffrn_oxdiff_digest_od_ed
;

;
_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, All O(H,H) groups
2. Others
 Fixed Sof: H2A(0.5) H2B(0.5)
3.a Riding coordinates:
 O2(H2A,H2B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C31(H31), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30)
3.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C)
3.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              14927
_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 2.816
_oxdiff_exptl_absorpt_empirical_full_min 0.320