Electrocatalytic proton reduction by mononuclear cobalt complexes of bis(benzimidazolyl)pyridine ligands: experimental and theoretical study
Khan, Sahanwaj; Sengupta, Swaraj; Khan, Md. Adnan; Jana, Narayan Ch.; Bagh, Bidraha; Naskar, Subhendu; New Journal of Chemistry 49 (2025) 16134–16144; doi:10.1039/D5NJ01975C

data_7063937
_publ_section_title
;
 Electrocatalytic proton reduction by mononuclear cobalt complexes of
 bis(benzimidazolyl)pyridine ligands: experimental and theoretical study
;
_journal_issue                   37
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              16134
_journal_page_last               16144
_journal_paper_doi               10.1039/D5NJ01975C
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         '3(C23 H21 Co0.5 N5), 4.5(Cl)'
_chemical_formula_sum            'C69 H63 Cl4.5 Co1.5 N15'
_chemical_formula_weight         1350.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-05-03 deposited with the CCDC.	2025-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.994(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   34.4966(14)
_cell_length_b                   18.9116(8)
_cell_length_c                   21.5652(7)
_cell_measurement_reflns_used    9091
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      26.1530
_cell_measurement_theta_min      3.5530
_cell_volume                     13761.7(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      298.00
_diffrn_detector_area_resol_mean 10.4324
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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    -22.00  22.00   1.00  150.10    --   10.07 -57.00 -90.00   44
  2  \w    -41.00  63.00   1.00  150.10    --  -10.22  77.00-180.00  104
  3  \w    -25.00  14.00   1.00  150.10    --  -10.22 -99.00   0.00   39
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            31931
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         3.403
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84497
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light brown'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_description       plate
_exptl_crystal_F_000             5592
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.907
_refine_diff_density_min         -0.937
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     848
_refine_ls_number_reflns         11975
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1266
_refine_ls_R_factor_gt           0.0821
_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^)+(0.1485P)^2^+25.2837P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2155
_refine_ls_wR_factor_ref         0.2574
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7779
_reflns_number_total             11975
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj01975c2.cif
_cod_data_source_block           complex-2
_cod_depositor_comments
'Adding full bibliography for 7063936--7063938.cif.'
_cod_original_formula_sum        'C69 H63 Cl4.50 Co1.50 N15'
_cod_database_code               7063937
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.866
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: Cl7(0.5) Cl5(0.5) Cl6(0.25) Cl4(0.25)
3.a Aromatic/amide H refined with riding coordinates:
 N5(H5), N2(H2), N7(H7), N10(H10), N5'(H5'), C17(H17), C22(H22), C2(H2A),
 C7(H7A), C11(H11), C45(H45), C34(H34), C36(H36), N2'(H2'), C12(H12), C25(H25),
 C35(H35), C13(H13), C30(H30), C2'(H2'A), C14'(H14'), C24'(H24'), C40(H40),
 C19'(H19'), C7'(H7'), C11'(H11'), C25'(H25'), C12'(H12')
3.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C4(H4A,H4B,H4C), C21(H21A,H21B,H21C), C6(H6A,H6B,H6C),
 C27(H27A,H27B,H27C), C44(H44A,H44B,H44C), C4'(H4'A,H4'B,H4'C), C29(H29A,H29B,
 H29C), C18'(H18A,H18B,H18C), C6'(H6'A,H6'B,H6'C), C42(H42A,H42B,H42C),
 C16'(H16A,H16B,H16C)
;
_shelx_res_checksum              27436
_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
;