Highly efficient phenalenyl–copper bifunctional photoredox catalyst for direct C–H bond arylation of arenes and heteroarenes
Paramanik, Krishnendu; Bandopadhyay, Nilaj; Agrawalla, Suraj Kumar; Purohit, Chandra Shekhar; Biswas, Bhaskar; Das, Hari Sankar; Catalysis Science & Technology 15 (2025) 3325–3331; doi:10.1039/D5CY00140D

data_1574394
_publ_section_title
;
 Highly efficient phenalenyl--copper bifunctional photoredox catalyst for
 direct C--H bond arylation of arenes and heteroarenes
;
_journal_issue                   11
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              3325
_journal_page_last               3331
_journal_paper_doi               10.1039/D5CY00140D
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C14 H13 N O2'
_chemical_formula_sum            'C14 H13 N O2'
_chemical_formula_weight         227.25
_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             2023-08-02
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-11-30 deposited with the CCDC.	2025-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.462(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.6579(2)
_cell_length_b                   22.1300(5)
_cell_length_c                   7.8468(2)
_cell_measurement_reflns_used    7758
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.7140
_cell_measurement_theta_min      3.9780
_cell_volume                     1133.08(5)
_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 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9995
_diffrn_measured_fraction_theta_max 0.9725
_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   -101.00 -27.00   0.50    0.12    --  -38.50 -58.00-157.00  148
  2  \w    -50.00  24.00   0.50    0.12    --  -38.50  58.00 -17.00  148
  3  \w    -13.00  61.00   0.50    0.12    --   49.56 -58.00-157.00  148
  4  \w     38.00 112.00   0.50    0.12    --   49.56  58.00 -17.00  148
  5  \w     45.00 119.00   0.50    0.29    --  107.46 -58.00-157.00  148
  6  \w     96.00 170.00   0.50    0.29    --  107.46  58.00 -17.00  148
  7  \w   -101.00 -27.00   0.50    0.12    --  -38.50 -57.00 120.00  148
  8  \w     46.00 116.00   0.50    0.12    --   49.56  37.00  90.00  140
  9  \w     95.00 170.00   0.50    0.29    --  107.46  61.00  90.00  150
 10  \w     45.00 113.00   0.50    0.29    --  107.46-125.00 -90.00  136
 11  \w     43.00 112.00   0.50    0.29    --  107.46 -45.00  30.00  138
 12  \w    103.00 172.00   0.50    0.29    --  107.46  77.00  90.00  138
 13  \w     97.00 170.00   0.50    0.29    --  107.46 125.00-180.00  146
 14  \w    103.00 172.00   0.50    0.29    --  107.46  45.00  30.00  138
 15  \w     97.00 170.00   0.50    0.29    --  107.46 125.00 -90.00  146
 16  \w     39.00 107.00   0.50    0.29    --  107.46 -94.00   0.00  136
 17  \w    103.00 172.00   0.50    0.29    --  107.46  77.00-120.00  138
 18  \w     46.00 109.00   0.50    0.12    --   49.56  37.00 -90.00  126
;
_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      0.0847283000
_diffrn_orient_matrix_UB_12      0.0019504000
_diffrn_orient_matrix_UB_13      -0.1688860000
_diffrn_orient_matrix_UB_21      0.1607348000
_diffrn_orient_matrix_UB_22      -0.0481537000
_diffrn_orient_matrix_UB_23      0.0744192000
_diffrn_orient_matrix_UB_31      -0.1507479000
_diffrn_orient_matrix_UB_32      -0.0502291000
_diffrn_orient_matrix_UB_33      -0.0779532000
_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  0.0258
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            9298
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.094
_diffrn_reflns_theta_min         3.995
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.723
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75717
_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_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.332
_exptl_crystal_description       block
_exptl_crystal_F_000             480
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'Slow evaporation'
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.332
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     156
_refine_ls_number_reflns         2355
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0559P)^2^+0.5284P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1062
_refine_ls_wR_factor_ref         0.1077
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2248
_reflns_number_total             2355
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00140d2.cif
_cod_data_source_block           sjp-cp60_auto
_cod_depositor_comments
'Adding full bibliography for 1574394--1574396.cif.'
_cod_database_code               1574394
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'O C H N'
_chemical_oxdiff_usercomment     'COLOURLESS BLOCK'
_shelx_estimated_absorpt_t_max   0.840
_shelx_estimated_absorpt_t_min   0.807
_diffrn_oxdiff_digest_frames
;
016dc8156f56a9d3907b7fb1abccdb93b500060eee0
;
_diffrn_oxdiff_digest_hkl
;
01a44ca43d29c1cb99657fa322b17038469c2e
;
_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:
 C5(H5), C2(H2), C12(H12), C9(H9), C3(H3), C6(H6), C10(H10)
2.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              72998
_olex2_exptl_crystal_mounting_method 'Mounted on the nylon loop'
_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 1.180
_oxdiff_exptl_absorpt_empirical_full_min 0.830