Copper(ii) phenalenyl complexes: structures, redox properties and catalytic activity towards Sonogashira coupling reactions
Sarkar, Gayetri; Paramanik, Krishnendu; Bandopadhyay, Nilaj; Chatterjee, Souvik; Saha, Subhajit; Panda, Subhra Jyoti; Purohit, Chandra Shekhar; Biswas, Bhaskar; Das, Hari Sankar; New Journal of Chemistry 49 (2025) 8232–8238; doi:10.1039/D5NJ00906E

data_7063882
_publ_section_title
;
 Copper(ii) phenalenyl complexes: structures, redox properties and
 catalytic activity towards Sonogashira coupling reactions
;
_journal_issue                   20
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              8232
_journal_page_last               8238
_journal_paper_doi               10.1039/D5NJ00906E
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C38 H24 Cu N2 O2'
_chemical_formula_sum            'C38 H24 Cu N2 O2'
_chemical_formula_weight         604.13
_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             2023-08-02
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2024-12-16 deposited with the CCDC.	2025-04-14 downloaded from the CCDC.
;
_cell_angle_alpha                114.720(2)
_cell_angle_beta                 110.413(2)
_cell_angle_gamma                95.321(2)
_cell_formula_units_Z            2
_cell_length_a                   10.7531(3)
_cell_length_b                   11.6550(3)
_cell_length_c                   13.0553(3)
_cell_measurement_reflns_used    15829
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      77.8010
_cell_measurement_theta_min      4.1030
_cell_volume                     1337.10(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 2014/5 (Sheldrick, 2014)'
_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 0.9986
_diffrn_measured_fraction_theta_max 0.9770
_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    -93.00 -11.00   0.50    0.10    --  -38.50 134.00 157.00  164
  2  \w    -94.00 -11.00   0.50    0.10    --  -38.50 135.00 -22.00  166
  3  \w     33.00 105.00   0.50    0.10    --   49.56-134.00  91.00  144
  4  \w     45.00 119.00   0.50    0.20    --  107.46-134.00  91.00  148
  5  \w     93.00 170.00   0.50    0.20    --  107.46 134.00 157.00  154
  6  \w     44.00 120.00   0.50    0.20    --  107.46-135.00 -88.00  152
  7  \w     93.00 171.00   0.50    0.20    --  107.46 135.00 -22.00  156
  8  \w    -42.00  28.00   0.50    0.10    --  -38.50  37.00  60.00  140
  9  \w   -101.00 -21.00   0.50    0.10    --  -38.50 -68.00  99.78  160
 10  \w   -102.00 -20.00   0.50    0.10    --  -38.50 -71.00 -90.96  164
 11  \w     46.00 116.00   0.50    0.10    --   49.56  37.00 -90.00  140
 12  \w     46.00 116.00   0.50    0.10    --   49.56  37.00 150.00  140
 13  \w     32.00 106.00   0.50    0.10    --   49.56-135.00 -88.00  148
 14  \w    -17.00  53.00   0.50    0.10    --   49.56 -37.00-150.00  140
 15  \w     43.00 112.00   0.50    0.20    --  107.46 -45.00 -90.00  138
 16  \w    104.00 176.00   0.50    0.20    --  107.46  30.00-150.00  144
 17  \w    104.00 176.00   0.50    0.20    --  107.46  30.00 -30.00  144
 18  \w    103.00 172.00   0.50    0.20    --  107.46  77.00-120.00  138
 19  \w     45.00 113.00   0.50    0.20    --  107.46-125.00  30.00  136
 20  \w    104.00 174.00   0.50    0.20    --  107.46  36.00 103.69  140
 21  \w     43.00 131.00   0.50    0.20    --  107.46 -77.00  90.00  176
 22  \w     97.00 170.00   0.50    0.20    --  107.46 125.00  30.00  146
 23  \w     39.00 107.00   0.50    0.20    --  107.46 -94.00  90.00  136
 24  \w     45.00 121.00   0.50    0.20    --  107.46 -61.00-150.00  152
 25  \w     43.00 112.00   0.50    0.20    --  107.46 -45.00  60.00  138
 26  \w    103.00 172.00   0.50    0.20    --  107.46  77.00 120.00  138
 27  \w     43.00 112.00   0.50    0.20    --  107.46 -45.00 150.00  138
 28  \w     46.00 112.00   0.50    0.20    --  107.46-125.00  60.00  132
 29  \w     39.00 107.00   0.50    0.20    --  107.46 -94.00 -60.00  136
 30  \w    106.00 168.00   0.50    0.20    --  107.46  77.00-180.00  124
 31  \w     44.00 111.00   0.50    0.20    --  107.46 -45.00  90.00  134
 32  \w     74.00 108.00   0.50    0.20    --  107.46-103.00 155.12   68
 33  \w    111.00 143.00   0.50    0.20    --  107.46  77.00 -30.00   64
 34  \w     46.00  89.00   0.50    0.20    --  107.46 -61.00  30.00   86
 35  \w    104.00 171.00   0.50    0.20    --  107.46  30.00  90.00  134
;
_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      -0.0098733000
_diffrn_orient_matrix_UB_12      -0.1447466000
_diffrn_orient_matrix_UB_13      -0.0811651000
_diffrn_orient_matrix_UB_21      0.0733424000
_diffrn_orient_matrix_UB_22      -0.0111321000
_diffrn_orient_matrix_UB_23      0.1186559000
_diffrn_orient_matrix_UB_31      -0.1410094000
_diffrn_orient_matrix_UB_32      -0.0436361000
_diffrn_orient_matrix_UB_33      -0.0021804000
_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  0.0532
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21179
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.074
_diffrn_reflns_theta_min         4.126
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.474
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46115
_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 reddish pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.501
_exptl_crystal_description       needle
_exptl_crystal_F_000             622
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'Slow evaporation'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.681
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     388
_refine_ls_number_reflns         5587
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0405
_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^)+(0.0598P)^2^+0.7793P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1113
_refine_ls_wR_factor_ref         0.1141
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5089
_reflns_number_total             5587
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00906e2.cif
_cod_data_source_block           sjp-kcu11_auto
_cod_original_cell_volume        1337.09(6)
_cod_database_code               7063882
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'O C H N Cl Cu'
_chemical_oxdiff_usercomment     'PINKISH RED'
_shelx_estimated_absorpt_t_max   0.757
_shelx_estimated_absorpt_t_min   0.683
_diffrn_oxdiff_digest_frames
;
01d0180bbd46526036f0d09dadc9ec0c7f00051104b
;
_diffrn_oxdiff_digest_hkl
;
013e493eb2824f2c1fd0487fd5d5ca5d3c3147
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13), C15(H15),
 C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C27(H27), C28(H28),
  C30(H30), C31(H31), C32(H32), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38)
;
_shelx_res_checksum              86613
_olex2_exptl_crystal_mounting_method 'Mounted on the 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 1.525
_oxdiff_exptl_absorpt_empirical_full_min 0.605