Cobalt(III)-catalysed annulation of indoles with phenylethynyl ether for the synthesis of the ABC ring system of ergot alkaloids.
Ghosh, Abhipsa; Panda, Asutosh; Mahulkar, Pranav Shridhar; Ravikumar, Ponneri C.; Chemical communications (Cambridge, England)  (2025) –; doi:10.1039/d5cc05860k

data_7135238
_publ_section_title
;
 Cobalt(III)-catalysed annulation of indoles with phenylethynyl ether for
 the synthesis of the ABC ring system of ergot alkaloids.
;
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_paper_doi               10.1039/d5cc05860k
_journal_year                    2025
_chemical_formula_moiety         'C22 H20 N O2'
_chemical_formula_sum            'C22 H20 N O2'
_chemical_formula_weight         330.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-30
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-08-06 deposited with the CCDC.	2025-11-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.298(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.7902(2)
_cell_length_b                   31.2988(5)
_cell_length_c                   7.03520(10)
_cell_measurement_reflns_used    8220
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      77.4750
_cell_measurement_theta_min      5.3560
_cell_volume                     1815.35(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.976
_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    -97.00 -14.00   0.50    3.24    --  -38.50 140.00-104.00  166
  2  \w    -91.00  -9.00   0.50    3.24    --  -38.50 130.00  81.00  164
  3  \w     31.00 103.00   0.50    3.24    --   49.56-130.00   9.00  144
  4  \w     45.00 116.00   0.50    7.16    --  107.46-130.00   9.00  142
  5  \w     45.00 123.00   0.50    7.16    --  107.46-140.00-164.00  156
  6  \w     95.00 170.00   0.50    7.16    --  107.46 130.00  81.00  150
  7  \w     88.00 170.00   0.50    7.16    --  107.46 140.00-104.00  164
  8  \w    -43.00  31.00   0.50    3.24    --  -38.50  19.00-120.00  148
  9  \w    -98.00 -28.00   0.50    3.24    --  -38.50 -57.00  60.00  140
 10  \w     48.00  73.00   0.50    3.24    --   49.56-140.00-164.00   50
 11  \w    -16.00  36.00   0.50    3.24    --   49.56 -37.00 -90.00  104
 12  \w     39.00 107.00   0.50    7.16    --  107.46 -94.00  30.00  136
 13  \w    104.00 129.00   0.50    7.16    --  107.46  30.00   0.00   50
 14  \w     42.00 115.00   0.50    7.16    --  107.46 -15.00   0.00  146
 15  \w     50.00 110.00   0.50    7.16    --  107.46 -30.00   0.00  120
 16  \w    135.00 161.00   0.50    7.16    --  107.46  30.00   0.00   52
 17  \w     46.00  71.00   0.50    7.16    --  107.46-125.00  60.00   50
 18  \w     86.00 112.00   0.50    7.16    --  107.46-125.00  60.00   52
 19  \w     54.00 119.00   0.50    7.16    --  107.46 -61.00 150.00  130
 20  \w    125.00 151.00   0.50    7.16    --  107.46  77.00   0.00   52
 21  \w     58.00 107.00   0.50    7.16    --  107.46 -94.00 -60.00   98
 22  \w     48.00 110.00   0.50    7.16    --  107.46 -30.00 -60.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1391560000
_diffrn_orient_matrix_UB_12      -0.0323443000
_diffrn_orient_matrix_UB_13      -0.0859181000
_diffrn_orient_matrix_UB_21      0.1199145000
_diffrn_orient_matrix_UB_22      -0.0370542000
_diffrn_orient_matrix_UB_23      0.0840466000
_diffrn_orient_matrix_UB_31      -0.0344151000
_diffrn_orient_matrix_UB_32      0.0016867000
_diffrn_orient_matrix_UB_33      0.2001828000
_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  0.0465
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            14614
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.183
_diffrn_reflns_theta_min         5.366
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.611
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76570
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.209
_exptl_crystal_description       block
_exptl_crystal_F_000             700
_refine_diff_density_max         0.458
_refine_diff_density_min         -0.351
_refine_diff_density_rms         0.057
_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     229
_refine_ls_number_reflns         3795
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0814
_refine_ls_R_factor_gt           0.0753
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1467P)^2^+0.5198P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2299
_refine_ls_wR_factor_ref         0.2377
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3227
_reflns_number_total             3795
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05860k2.cif
_cod_data_source_block           pcrpsm-369
_cod_database_code               7135238
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N O'
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Restrained distances
 C14-C15
 1.7 with sigma of 0.02
2.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C7(H7), C8(H8), C13(H13), C18(H18), C22(H22), C21(H21), C20(H20),
 C19(H19)
2.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              72275
_shelx_hkl_checksum              34948
_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 1.922
_oxdiff_exptl_absorpt_empirical_full_min 0.471