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_1574396
_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         'C29 H19 Cl Cu N2 O2, 5/3(H2 O)'
_chemical_formula_sum            'C29 H22.33333 Cl Cu N2 O3.66667'
_chemical_formula_weight         556.48
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-05 deposited with the CCDC.	2025-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                84.990(2)
_cell_angle_beta                 84.5840(10)
_cell_angle_gamma                82.3890(10)
_cell_formula_units_Z            6
_cell_length_a                   11.9198(2)
_cell_length_b                   13.4831(2)
_cell_length_c                   22.5889(4)
_cell_measurement_reflns_used    25105
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.1170
_cell_measurement_theta_min      3.7360
_cell_volume                     3572.03(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.89a 64-bit (release 24-03-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (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    'SHELXD  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.970
_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   -102.00 -21.00   0.50    0.70    --  -38.50 -70.00 -59.00  162
  2  \w    -14.00  67.00   0.50    0.70    --   49.06 -70.00 -59.00  162
  3  \w     31.00 112.00   0.50    0.70    --   49.06  70.00  71.00  162
  4  \w     39.00 120.00   0.50    2.80    --  102.00 -70.00 -59.00  162
  5  \w     84.00 165.00   0.50    2.80    --  102.00  70.00  71.00  162
  6  \w   -101.00 -27.00   0.50    0.70    --  -38.50 -57.00-180.00  148
  7  \w   -105.00 -35.00   0.50    0.70    --  -38.50 -37.00 -30.00  140
  8  \w    -42.00  28.00   0.50    0.70    --  -38.50  37.00  30.00  140
  9  \w    -56.00  25.00   0.50    0.70    --  -38.50  70.00  71.00  162
 10  \w    -50.00  24.00   0.50    0.70    --  -38.50  57.00 150.00  148
 11  \w    -17.00  52.00   0.50    0.70    --   49.06 -37.00-180.00  138
 12  \w     39.00 112.00   0.50    2.80    --  102.00-125.00 150.00  146
 13  \w    103.00 167.00   0.50    2.80    --  102.00  77.00-180.00  128
 14  \w     34.00 106.00   0.50    2.80    --  102.00 -94.00 150.00  144
 15  \w     38.00 107.00   0.50    2.80    --  102.00 -45.00 -30.00  138
 16  \w     39.00 115.00   0.50    2.80    --  102.00 -61.00   0.00  152
 17  \w     34.00 105.00   0.50    2.80    --  102.00 -30.00 120.00  142
 18  \w     39.00 112.00   0.50    2.80    --  102.00-125.00  30.00  146
 19  \w     34.00 106.00   0.50    2.80    --  102.00 -94.00 -90.00  144
 20  \w     94.00 171.00   0.50    2.80    --  102.00  15.00 -60.00  154
 21  \w    103.00 167.00   0.50    2.80    --  102.00  77.00 -60.00  128
 22  \w     39.00 112.00   0.50    2.80    --  102.00-125.00 -30.00  146
 23  \w     94.00 171.00   0.50    2.80    --  102.00  15.00-120.00  154
 24  \w     39.00 112.00   0.50    2.80    --  102.00-125.00 -60.00  146
 25  \w     38.00 105.00   0.50    2.80    --  102.00 -94.00-180.00  134
 26  \w     96.00 149.00   0.50    2.80    --  102.00  61.00 -30.00  106
 27  \w    101.00 164.00   0.50    2.80    --  102.00 125.00 -90.00  126
 28  \w     35.00 106.00   0.50    2.80    --  102.00 -15.00 120.00  142
 29  \w    108.00 149.00   0.50    2.80    --  102.00 125.00 150.00   82
 30  \w    103.00 129.00   0.50    2.80    --  102.00 125.00-120.00   52
 31  \w    137.00 165.00   0.50    2.80    --  102.00 125.00-120.00   56
 32  \w     78.00 104.00   0.50    2.80    --  102.00-125.00 120.00   52
 33  \w     39.00  88.00   0.50    2.80    --  102.00 -45.00-120.00   98
 34  \w     98.00 162.00   0.50    2.80    --  102.00 125.00   0.00  128
 35  \w     80.00 106.00   0.50    2.80    --  102.00 -94.00  30.00   52
 36  \w     76.00 111.00   0.50    2.80    --  102.00 -77.00 120.00   70
 37  \w     80.00 106.00   0.50    2.80    --  102.00 -94.00 -60.00   52
;
_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      -0.0714432000
_diffrn_orient_matrix_UB_12      0.0102378000
_diffrn_orient_matrix_UB_13      -0.0540966000
_diffrn_orient_matrix_UB_21      0.0250771000
_diffrn_orient_matrix_UB_22      -0.1140504000
_diffrn_orient_matrix_UB_23      -0.0054305000
_diffrn_orient_matrix_UB_31      -0.1067230000
_diffrn_orient_matrix_UB_32      -0.0158989000
_diffrn_orient_matrix_UB_33      0.0420032000
_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  0.0748
_diffrn_reflns_av_unetI/netI     0.0543
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            55333
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.630
_diffrn_reflns_theta_min         3.317
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.653
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57321
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_description       block
_exptl_crystal_F_000             1714
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'Slow evaporation'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.580
_refine_diff_density_min         -0.536
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1006
_refine_ls_number_reflns         14375
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0517
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0577P)^2^+2.0386P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1176
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11934
_reflns_number_total             14375
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00140d2.cif
_cod_data_source_block           ska-k12-cu
_cod_depositor_comments
;

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel

 Adding full bibliography for 1574394--1574396.cif.
;
_cod_original_formula_moiety     '3(C29 H19 Cl Cu N2 O2), 5[H2O]'
_cod_original_formula_sum        'C87 H67 Cl3 Cu3 N6 O11'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     1669.43
_cod_database_code               1574396
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H N O Cu Cl'
_chemical_oxdiff_usercomment     'light green block'
_shelx_estimated_absorpt_t_max   0.606
_shelx_estimated_absorpt_t_min   0.569
_reflns_odcompleteness_completeness 99.89
_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 O(H,H) groups
2.a Free rotating group:
 O7(H7A,H7B), O8(H8A,H8B), O9(H9A,H9B), O10(H10A,H10B), O11(H11A,H11B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C7(H7), C9(H9), C10(H10), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C26(H26),
  C27(H27), C28(H28), C29(H29), C31(H31), C32(H32), C34(H34), C36(H36),
 C38(H38), C39(H39), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49),
  C50(H50), C51(H51), C52(H52), C55(H55), C56(H56), C57(H57), C58(H58),
 C60(H60), C61(H61), C63(H63), C65(H65), C67(H67), C68(H68), C73(H73), C74(H74),
  C75(H75), C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C81(H81),
 C84(H84), C85(H85), C86(H86), C87(H87)
;
_shelx_res_checksum              12977
_olex2_exptl_crystal_mounting_method 'Mounted on a 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 2.051
_oxdiff_exptl_absorpt_empirical_full_min 0.279