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_1574395
_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         'C16 H22 N2 O'
_chemical_formula_sum            'C16 H22 N2 O'
_chemical_formula_weight         258.35
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-21
_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                79.252(2)
_cell_angle_beta                 85.493(2)
_cell_angle_gamma                83.620(2)
_cell_formula_units_Z            4
_cell_length_a                   6.6423(2)
_cell_length_b                   13.8452(3)
_cell_length_c                   16.6714(4)
_cell_measurement_reflns_used    15593
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      77.2220
_cell_measurement_theta_min      3.8350
_cell_volume                     1494.31(7)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9932
_diffrn_measured_fraction_theta_max 0.9645
_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     37.00 112.00   0.50    0.25    --   49.06  58.00 -32.00  150
  2  \w    -14.00  61.00   0.50    0.25    --   49.06 -58.00-172.00  150
  3  \w     44.00 119.00   0.50    1.00    --  106.83 -58.00-172.00  150
  4  \w     95.00 170.00   0.50    1.00    --  106.83  58.00 -32.00  150
  5  \w   -105.00 -35.00   0.50    0.25    --  -38.50 -37.00-150.00  140
  6  \w   -101.00 -27.00   0.50    0.25    --  -38.50 -58.00-172.00  148
  7  \w    -50.00  24.00   0.50    0.25    --  -38.50  57.00  30.00  148
  8  \w    -50.00  24.00   0.50    0.25    --  -38.50  58.00 -32.00  148
  9  \w      7.00  84.00   0.50    0.25    --   49.06 -99.00  60.00  154
 10  \w     44.00 112.00   0.50    1.00    --  106.83-125.00-180.00  136
 11  \w     39.00 106.00   0.50    1.00    --  106.83 -94.00  30.00  134
 12  \w     94.00 170.00   0.50    1.00    --  106.83  61.00 -90.00  152
 13  \w     99.00 175.00   0.50    1.00    --  106.83  15.00-120.00  152
 14  \w    102.00 171.00   0.50    1.00    --  106.83  45.00   0.00  138
 15  \w     42.00 111.00   0.50    1.00    --  106.83 -45.00 -30.00  138
 16  \w     39.00 106.00   0.50    1.00    --  106.83 -94.00-150.00  134
 17  \w     44.00 120.00   0.50    1.00    --  106.83 -61.00 -90.00  152
 18  \w     44.00 112.00   0.50    1.00    --  106.83-125.00 150.00  136
 19  \w     42.00 111.00   0.50    1.00    --  106.83 -45.00  60.00  138
 20  \w     39.00 106.00   0.50    1.00    --  106.83 -94.00 -30.00  134
 21  \w     94.00 170.00   0.50    1.00    --  106.83  61.00 -60.00  152
 22  \w     94.00 170.00   0.50    1.00    --  106.83  61.00-120.00  152
 23  \w     38.00 112.00   0.50    0.25    --   49.06  57.00  90.00  148
 24  \w     38.00 112.00   0.50    0.25    --   49.06  57.00 120.00  148
 25  \w     38.00 112.00   0.50    0.25    --   49.06  57.00-180.00  148
 26  \w     38.00 112.00   0.50    0.25    --   49.06  57.00-150.00  148
 27  \w     38.00 112.00   0.50    0.25    --   49.06  57.00  30.00  148
 28  \w     38.00 112.00   0.50    0.25    --   49.06  57.00   0.00  148
 29  \w     38.00 112.00   0.50    0.25    --   49.06  57.00 150.00  148
 30  \w     38.00 112.00   0.50    0.25    --   49.06  57.00 -90.00  148
 31  \w    102.00 162.00   0.50    1.00    --  106.83  45.00  90.00  120
 32  \w    104.00 175.00   0.50    1.00    --  106.83  30.00-180.00  142
 33  \w    104.00 175.00   0.50    1.00    --  106.83  30.00  60.00  142
 34  \w     99.00 175.00   0.50    1.00    --  106.83  15.00 150.00  152
;
_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      -0.2124168000
_diffrn_orient_matrix_UB_12      0.0534760000
_diffrn_orient_matrix_UB_13      0.0139345000
_diffrn_orient_matrix_UB_21      -0.0582186000
_diffrn_orient_matrix_UB_22      -0.0900158000
_diffrn_orient_matrix_UB_23      0.0634692000
_diffrn_orient_matrix_UB_31      0.0784026000
_diffrn_orient_matrix_UB_32      0.0446130000
_diffrn_orient_matrix_UB_33      0.0682314000
_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  0.0383
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            23558
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.515
_diffrn_reflns_theta_min         3.265
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.563
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77936
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.148
_exptl_crystal_description       block
_exptl_crystal_F_000             560
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'Slow evaporation'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.185
_refine_diff_density_min         -0.222
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         6131
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0473P)^2^+0.3143P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.1011
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5482
_reflns_number_total             6131
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cy00140d2.cif
_cod_data_source_block           hsd-opc-2_auto
_cod_depositor_comments
'Adding full bibliography for 1574394--1574396.cif.'
_cod_database_code               1574395
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     'colourless block'
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.867
_diffrn_oxdiff_ac3_digest_hkl    4169b07c62cc01c532a6d1fd606cdc08af8b4b
_diffrn_oxdiff_digest_frames
;
014d06ed9bb379ba92dc3c6e196442b9ce000373070
;
_diffrn_oxdiff_digest_hkl
;
01ec2b23bdf358adfbe188a105a015e2484083
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C25(H25A,H25B), C26(H26A,H26B),
 C27(H27A,H27B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C18(H18), C19(H19), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C)
;
_shelx_res_checksum              76810
_olex2_exptl_crystal_mounting_method 'Mounted on a 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 1.541
_oxdiff_exptl_absorpt_empirical_full_min 0.703