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_7063936
_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         'C38 H22 Co F4 N10, 2(Cl O4), 3(C3 H7 N O)'
_chemical_formula_sum            'C47 H43 Cl2 Co F4 N13 O11'
_chemical_formula_weight         1171.77
_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             2025-03-20
_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                93.8930(10)
_cell_angle_beta                 92.8090(10)
_cell_angle_gamma                104.1580(10)
_cell_formula_units_Z            2
_cell_length_a                   12.8362(2)
_cell_length_b                   14.2164(2)
_cell_length_c                   14.4063(2)
_cell_measurement_reflns_used    30189
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.4800
_cell_measurement_theta_min      3.5650
_cell_volume                     2537.34(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 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.998
_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    -91.00  -9.00   0.50    0.12    --  -38.50 130.00  68.00  164
  2  \w    -97.00 -13.00   0.50    0.12    --  -38.50 139.00-117.00  168
  3  \w     31.00 102.00   0.50    0.12    --   49.06-130.00  -3.00  142
  4  \w     44.00 123.00   0.50    0.73    --  106.83-139.00-177.00  158
  5  \w     44.00 116.00   0.50    0.73    --  106.83-130.00  -3.00  144
  6  \w     95.00 170.00   0.50    0.73    --  106.83 130.00  68.00  150
  7  \w     90.00 170.00   0.50    0.73    --  106.83 139.00-117.00  160
  8  \w    -62.00  26.00   0.50    0.12    --  -38.50  77.00  90.00  176
  9  \w   -102.00 -20.00   0.50    0.12    --  -38.50 -71.00 -42.67  164
 10  \w    -50.00  24.00   0.50    0.12    --  -38.50  57.00  30.00  148
 11  \w     35.00 108.00   0.50    0.12    --   49.06-139.00-177.00  146
 12  \w     38.00 112.00   0.50    0.12    --   49.06  57.00  90.00  148
 13  \w     38.00 112.00   0.50    0.12    --   49.06  57.00-180.00  148
 14  \w     38.00 112.00   0.50    0.12    --   49.06  57.00-120.00  148
 15  \w     43.00 130.00   0.50    0.73    --  106.83 -77.00 -30.00  174
 16  \w    102.00 171.00   0.50    0.73    --  106.83  45.00  90.00  138
 17  \w     39.00 110.00   0.50    0.73    --  106.83 -30.00-180.00  142
 18  \w     39.00 115.00   0.50    0.73    --  106.83 -15.00   0.00  152
 19  \w    102.00 171.00   0.50    0.73    --  106.83  45.00 -30.00  138
 20  \w     94.00 170.00   0.50    0.73    --  106.83  61.00 -30.00  152
 21  \w     39.00 110.00   0.50    0.73    --  106.83 -30.00 -30.00  142
 22  \w     39.00 106.00   0.50    0.73    --  106.83 -94.00  90.00  134
 23  \w     44.00 112.00   0.50    0.73    --  106.83-125.00-120.00  136
 24  \w     90.00 170.00   0.50    0.73    --  106.83  68.00 141.25  160
 25  \w     39.00 110.00   0.50    0.73    --  106.83 -30.00  90.00  142
 26  \w     39.00 115.00   0.50    0.73    --  106.83 -15.00 -60.00  152
 27  \w     39.00 106.00   0.50    0.73    --  106.83 -94.00 150.00  134
 28  \w     44.00 124.00   0.50    0.73    --  106.83-140.00 -37.18  160
 29  \w     39.00 106.00   0.50    0.73    --  106.83 -94.00-150.00  134
 30  \w     39.00 106.00   0.50    0.73    --  106.83 -94.00  60.00  134
 31  \w     42.00 111.00   0.50    0.73    --  106.83 -45.00-180.00  138
 32  \w     39.00 106.00   0.50    0.73    --  106.83 -94.00 -30.00  134
 33  \w     42.00 111.00   0.50    0.73    --  106.83 -45.00 150.00  138
 34  \w    102.00 171.00   0.50    0.73    --  106.83  45.00   0.00  138
 35  \w     38.00 112.00   0.50    0.12    --   49.06  57.00 -60.00  148
 36  \w     38.00 112.00   0.50    0.12    --   49.06  57.00 120.00  148
 37  \w     38.00 112.00   0.50    0.12    --   49.06  57.00  30.00  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_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0618
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            44781
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.997
_diffrn_reflns_theta_min         3.559
_exptl_absorpt_coefficient_mu    4.392
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85471
_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            'light white'
_exptl_crystal_density_diffrn    1.534
_exptl_crystal_description       block
_exptl_crystal_F_000             1202
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.990
_refine_diff_density_min         -0.624
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     788
_refine_ls_number_reflns         10539
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0574
_refine_ls_R_factor_gt           0.0512
_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^)+(0.0540P)^2^+3.2613P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1271
_refine_ls_wR_factor_ref         0.1363
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9684
_reflns_number_total             10539
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj01975c2.cif
_cod_data_source_block           complex-3
_cod_depositor_comments
'Adding full bibliography for 7063936--7063938.cif.'
_cod_original_cell_volume        2537.33(6)
_cod_database_code               7063936
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.668
_shelx_estimated_absorpt_t_min   0.474
_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. Restrained distances
 O9-O12 \\sim O10-O13
 with sigma of 0.04
 O15-O11 \\sim O8-O14
 with sigma of 0.04
 Cl2-O11 \\sim Cl2-O14
 with sigma of 0.04
 O12-O11 \\sim O13-O14
 with sigma of 0.04
 Cl2-O15 \\sim Cl2-O8
 with sigma of 0.04
 Cl2-O9 \\sim Cl2-O10
 with sigma of 0.04
 Cl2-O12 \\sim Cl2-O13
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C22) = Uanis(C21) = Uanis(C23) = Uanis(C20) = Uanis(C14) = Uanis(C19)
4. Others
 Sof(C23)=Sof(H23)=Sof(C21)=Sof(H21)=Sof(C20)=Sof(H20)=Sof(C22)=1-FVAR(1)
 Sof(C15)=Sof(H15)=Sof(C16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=FVAR(1)
 Fixed Sof: O15(0.5) O9(0.5) O12(0.5) O11(0.5) F3(0.65) H26(0.5) H3(0.5)
 F2(0.5) H4(0.5) F8(0.5) H27(0.5) H40(0.4) F7(0.5) F6(0.6) H39(0.6) F1(0.5)
 F5(0.4) F4(0.35) O8(0.5) O10(0.5) O13(0.5) O14(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 N2(H2), N7(H7), N10(H10), N5(H5), C34(H34), C11(H11), C9(H9), C10(H10A),
 C33(H33), C32(H32), C41(H41), C49(H49), C25(H25), C2(H2A), C5(H5A), C26(H26),
 C28(H28), C3(H3), C4(H4), C46(H46), C23(H23), C27(H27), C43(H43), C40(H40),
 C21(H21), C20(H20), C38(H38), C39(H39), C15(H15), C17(H17), C18(H18)
5.b Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C47(H47A,H47B,H47C), C51(H51A,H51B,H51C), C45(H45A,H45B,
 H45C), C50(H50A,H50B,H50C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              3311
_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
;