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_7063883
_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         'C24 H16'
_chemical_formula_sum            'C24 H16'
_chemical_formula_weight         304.37
_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             2024-09-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-16 deposited with the CCDC.	2025-04-14 downloaded from the CCDC.
;
_cell_angle_alpha                98.8610(10)
_cell_angle_beta                 90.6750(10)
_cell_angle_gamma                115.378(2)
_cell_formula_units_Z            4
_cell_length_a                   10.3285(2)
_cell_length_b                   11.4386(2)
_cell_length_c                   15.1218(2)
_cell_measurement_reflns_used    15290
_cell_measurement_temperature    99.91(19)
_cell_measurement_theta_max      77.5590
_cell_measurement_theta_min      4.3450
_cell_volume                     1588.81(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      99.91(19)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.972
_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 -13.00   0.50    0.30    --  -38.50 139.00  58.00  168
  2  \w    -91.00  -9.00   0.50    0.30    --  -38.50 131.00-115.00  164
  3  \w     95.00 170.00   0.50    1.20    --  106.83 131.00-115.00  150
  4  \w     90.00 170.00   0.50    1.20    --  106.83 139.00  58.00  160
  5  \w     44.00 117.00   0.50    1.20    --  106.83-131.00 172.00  146
  6  \w     44.00 123.00   0.50    1.20    --  106.83-139.00  -1.00  158
  7  \w   -101.00 -23.00   0.50    0.30    --  -38.50 -65.00   1.74  156
  8  \w    -44.00  31.00   0.50    0.30    --  -38.50  19.00-180.00  150
  9  \w     46.00 116.00   0.50    0.30    --   49.06  37.00  60.00  140
 10  \w     35.00 108.00   0.50    0.30    --   49.06-139.00  -1.00  146
 11  \w    -17.00  52.00   0.50    0.30    --   49.06 -37.00 150.00  138
 12  \w     31.00 103.00   0.50    0.30    --   49.06-131.00 172.00  144
 13  \w     38.00 112.00   0.50    0.30    --   49.06  57.00 120.00  148
 14  \w     39.00 115.00   0.50    1.20    --  106.83 -15.00-180.00  152
 15  \w     39.00 110.00   0.50    1.20    --  106.83 -30.00   0.00  142
 16  \w     42.00 111.00   0.50    1.20    --  106.83 -45.00 -30.00  138
 17  \w     39.00 110.00   0.50    1.20    --  106.83 -30.00 -90.00  142
 18  \w    103.00 171.00   0.50    1.20    --  106.83  77.00-180.00  136
 19  \w     99.00 175.00   0.50    1.20    --  106.83  15.00-150.00  152
 20  \w     42.00 111.00   0.50    1.20    --  106.83 -45.00 150.00  138
 21  \w     44.00 112.00   0.50    1.20    --  106.83-125.00 120.00  136
 22  \w     44.00 120.00   0.50    1.20    --  106.83 -61.00 120.00  152
 23  \w     44.00 112.00   0.50    1.20    --  106.83-125.00 -60.00  136
 24  \w     39.00 115.00   0.50    1.20    --  106.83 -15.00 -90.00  152
 25  \w     94.00 170.00   0.50    1.20    --  106.83  61.00 -60.00  152
 26  \w     39.00 106.00   0.50    1.20    --  106.83 -94.00 150.00  134
 27  \w     44.00 112.00   0.50    1.20    --  106.83-125.00  90.00  136
 28  \w     42.00 111.00   0.50    1.20    --  106.83 -45.00-180.00  138
 29  \w     44.00 120.00   0.50    1.20    --  106.83 -61.00 150.00  152
 30  \w     39.00 106.00   0.50    1.20    --  106.83 -94.00 -30.00  134
 31  \w     39.00 106.00   0.50    1.20    --  106.83 -94.00-180.00  134
 32  \w     98.00 170.00   0.50    1.20    --  106.83  54.00 143.63  144
 33  \w     38.00 112.00   0.50    0.30    --   49.06  57.00-150.00  148
;
_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      0.0301462000
_diffrn_orient_matrix_UB_12      -0.0614083000
_diffrn_orient_matrix_UB_13      -0.0907293000
_diffrn_orient_matrix_UB_21      -0.0911081000
_diffrn_orient_matrix_UB_22      0.0506938000
_diffrn_orient_matrix_UB_23      -0.0497566000
_diffrn_orient_matrix_UB_31      0.1351043000
_diffrn_orient_matrix_UB_32      0.1288060000
_diffrn_orient_matrix_UB_33      -0.0022456000
_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  0.0386
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            25029
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.785
_diffrn_reflns_theta_min         4.346
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.546
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75815
_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    1.272
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'Sloe evaporation'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.529
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     433
_refine_ls_number_reflns         6585
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0503
_refine_ls_R_factor_gt           0.0451
_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^)+(0.0651P)^2^+0.4487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1226
_refine_ls_wR_factor_ref         0.1271
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5744
_reflns_number_total             6585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00906e2.cif
_cod_data_source_block           hsd-gs-1_auto
_cod_database_code               7063883
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H'
_chemical_oxdiff_usercomment     'colourless block'
_shelx_estimated_absorpt_t_max   0.889
_shelx_estimated_absorpt_t_min   0.871
_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), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C14(H14), C15(H15),
 C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26),
  C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C38(H38),
 C39(H39), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48)
;
_shelx_res_checksum              31212
_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 1.413
_oxdiff_exptl_absorpt_empirical_full_min 0.721