Decrypting the hydrogen evolution in alkaline water with novel magnetoactive cobalt(II) complex-driven cobalt oxide electrocatalysts.
Saha, Subhajit; Diyali, Nilankar; Diyali, Sangharaj; Panda, Subhra Jyoti; Das, Mainak; Acharya, Sobhna; Mudi, Prafullya Kumar; Singh, Monika; Ray, Partha Pratim; Purohit, Chandra Shekhar; Biswas, Bhaskar; Dalton transactions (Cambridge, England : 2003) 53 (2024) 13805–13814; doi:10.1039/d4dt01358a

data_7716732
_publ_section_title
;
 Decrypting the hydrogen evolution in alkaline water with novel
 magnetoactive cobalt(II) complex-driven cobalt oxide electrocatalysts.
;
_journal_issue                   33
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              13805
_journal_page_last               13814
_journal_paper_doi               10.1039/d4dt01358a
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         '4(C32 H30 Co N4 O6 S2), 2[H2O]'
_chemical_formula_sum            'C128 H124 Co4 N16 O25 S8'
_chemical_formula_weight         2778.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-07-21
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-21 deposited with the CCDC.	2024-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.604(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.0342(3)
_cell_length_b                   12.2099(2)
_cell_length_c                   37.0604(9)
_cell_measurement_reflns_used    11227
_cell_measurement_temperature    250.49
_cell_measurement_theta_max      77.2390
_cell_measurement_theta_min      3.8040
_cell_volume                     6294.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      250.49
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9985
_diffrn_measured_fraction_theta_max 0.9708
_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   -101.00 -21.00   0.50    2.00    --  -38.50 -68.00-122.00  160
  2  \w    -56.00  25.00   0.50    2.00    --  -38.50  68.00  11.00  162
  3  \w     32.00 112.00   0.50    2.00    --   49.06  68.00  11.00  160
  4  \w    -14.00  67.00   0.50    2.00    --   49.06 -68.00-122.00  162
  5  \w     44.00 124.00   0.50    4.00    --  106.83 -68.00-122.00  160
  6  \w     90.00 170.00   0.50    4.00    --  106.83  68.00  11.00  160
  7  \w   -105.00 -35.00   0.50    2.00    --  -38.50 -38.00  30.00  140
  8  \w    -42.00  28.00   0.50    2.00    --  -38.50  38.00-180.00  140
  9  \w     46.00 115.00   0.50    2.00    --   49.06  38.00 150.00  138
 10  \w    104.00 166.00   0.50    4.00    --  106.83  77.00-120.00  124
 11  \w     76.00 103.00   0.50    4.00    --  106.83 -15.00-120.00   54
 12  \w     45.00 106.00   0.50    4.00    --  106.83-125.00  90.00  122
 13  \w     44.00 100.00   0.50    4.00    --  106.83-125.00-120.00  112
 14  \w     41.00 105.00   0.50    4.00    --  106.83 -94.00 120.00  128
 15  \w     51.00 111.00   0.50    4.00    --  106.83-125.00 -60.00  120
 16  \w    115.00 166.00   0.50    4.00    --  106.83  45.00 120.00  102
 17  \w     94.00 170.00   0.50    4.00    --  106.83  61.00  30.00  152
 18  \w     98.00 169.00   0.50    4.00    --  106.83 125.00 -60.00  142
 19  \w     66.00  91.00   0.50    4.00    --  106.83 -94.00-150.00   50
 20  \w    141.00 168.00   0.50    4.00    --  106.83  77.00  60.00   54
 21  \w     98.00 170.00   0.50    4.00    --  106.83 125.00-150.00  144
;
_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      -0.0221247000
_diffrn_orient_matrix_UB_12      0.1118613000
_diffrn_orient_matrix_UB_13      -0.0184500000
_diffrn_orient_matrix_UB_21      -0.0724589000
_diffrn_orient_matrix_UB_22      0.0247453000
_diffrn_orient_matrix_UB_23      0.0267113000
_diffrn_orient_matrix_UB_31      0.0807860000
_diffrn_orient_matrix_UB_32      0.0528929000
_diffrn_orient_matrix_UB_33      0.0265434000
_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  0.0951
_diffrn_reflns_av_unetI/netI     0.0654
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            25376
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.103
_diffrn_reflns_theta_min         3.815
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.952
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50738
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.466
_exptl_crystal_description       plank
_exptl_crystal_F_000             2880
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'slow evaporation'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.791
_refine_diff_density_min         -0.879
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     418
_refine_ls_number_reflns         6530
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0897
_refine_ls_R_factor_gt           0.0693
_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^)+(0.1302P)^2^+6.2177P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1820
_refine_ls_wR_factor_ref         0.2035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5035
_reflns_number_total             6530
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01358a2.cif
_cod_data_source_block           sjp-co-p11-ncs
_cod_depositor_comments
'Adding full bibliography for 7716732--7716733.cif.'
_cod_database_code               7716732
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H N O Co Cl S'
_chemical_oxdiff_usercomment     'DEEP RED NEEDLE'
_shelx_estimated_absorpt_t_max   0.414
_shelx_estimated_absorpt_t_min   0.230
_diffrn_oxdiff_ac3_digest_hkl    415a637b25b077e306817d296f994796778069
_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, All O(H,H) groups
2. Others
 Fixed Sof: O7(0.25) H7A(0.5) H7B(0.5)
3.a Free rotating group:
 O7(H7A,H7B)
3.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C18(H18), C19(H19), C20(H20), C23(H23), C25(H25), C26(H26), C27(H27),
  C28(H28)
3.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              26645
_shelx_hkl_checksum              45663
_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 2.169
_oxdiff_exptl_absorpt_empirical_full_min 0.505