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_7063938
_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 H26 N10 Zn, Cl O4, 4(C2 H6 O S), Cl0.65 O1.4, Cl0.35 O2.6'
_chemical_formula_sum            'C46 H50 Cl2 N10 O12 S4 Zn'
_chemical_formula_weight         1199.47
_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                87.477(8)
_cell_angle_beta                 76.607(6)
_cell_angle_gamma                70.038(8)
_cell_formula_units_Z            2
_cell_length_a                   11.5816(8)
_cell_length_b                   14.6348(17)
_cell_length_c                   17.7481(13)
_cell_measurement_reflns_used    7740
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.7470
_cell_measurement_theta_min      3.6840
_cell_volume                     2748.6(5)
_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      293(2)
_diffrn_detector_area_resol_mean 10.4324
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.976
_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     29.00  55.00   1.00   52.50    --   10.22  38.00-150.00   26
  2  \w    -42.00  48.00   1.00   52.50    --  -10.38  77.00  60.00   90
  3  \w    -84.00  15.00   1.00   52.50    --  -10.38 -77.00 -60.00   99
  4  \w    -71.00 -45.00   1.00   52.50    --  -10.38 -57.00  30.00   26
  5  \w    -81.00   6.00   1.00   52.50    --  -10.38 -57.00 150.00   87
;
_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  0.0317
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25246
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.102
_diffrn_reflns_theta_min         3.370
_exptl_absorpt_coefficient_mu    0.763
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63459
_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            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.449
_exptl_crystal_description       block
_exptl_crystal_F_000             1240
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.384
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     738
_refine_ls_number_reflns         11829
_refine_ls_number_restraints     96
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0924
_refine_ls_R_factor_gt           0.0716
_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^)+(0.1442P)^2^+1.1064P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2047
_refine_ls_wR_factor_ref         0.2321
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8776
_reflns_number_total             11829
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj01975c2.cif
_cod_data_source_block           complex-4
_cod_depositor_comments
'Adding full bibliography for 7063936--7063938.cif.'
_cod_original_cell_volume        2748.6(4)
_cod_database_code               7063938
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.862
_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
 Cl2-O17 \\sim Cl3-O16
 with sigma of 0.02
 Cl2-O11 \\sim Cl3-O12
 with sigma of 0.02
 Cl2-O13 \\sim Cl3-O10
 with sigma of 0.02
 Cl2-O14 \\sim Cl3-O15
 with sigma of 0.02
 O17-O11 \\sim O16-O12
 with sigma of 0.04
 O17-O13 \\sim O16-O10
 with sigma of 0.04
 O17-O14 \\sim O16-O15
 with sigma of 0.04
 O11-O13 \\sim O12-O10
 with sigma of 0.04
 O11-O14 \\sim O12-O15
 with sigma of 0.04
 O13-O14 \\sim O10-O15
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O12) \\sim Ueq, Uanis(O14) \\sim Ueq, Uanis(O15) \\sim Ueq, Uanis(O17)
\\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(O10) \\sim Ueq,
Uanis(Cl3) \\sim Ueq, Uanis(O13) \\sim Ueq, Uanis(Cl2) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 O15, O17, O11, O16, O13, O10, O12, O14, Cl2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Sof: Cl2(0.65) O17(0.65) O11(0.65) O13(0.65) O14(0.65) O3(0.5) O4(0.5)
 O12(0.35) O16(0.35) O10(0.35) O15(0.35) Cl3(0.35)
6.a Aromatic/amide H refined with riding coordinates:
 N5(H5), N2(H2), N10(H10), N7(H7), C18(H18), C2(H2A), C9(H9), C17(H17),
 C10(H10A), C11(H11), C3(H3), C15(H15), C4(H4), C16(H16), C28(H28), C30(H30),
 C5(H5A), C21(H21), C37(H37), C29(H29), C24(H24), C34(H34), C22(H22), C36(H36),
 C35(H35), C23(H23)
6.b Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C44(H44A,H44B,
 H44C), C39(H39A,H39B,H39C), C46(H46A,H46B,H46C), C45(H45A,H45B,H45C), C41(H41A,
 H41B,H41C)
;
_shelx_res_checksum              64467
_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
;