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_7716733
_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         'C46 H46 Co2 N3 O10, Cl O4'
_chemical_formula_sum            'C46 H46 Cl Co2 N3 O14'
_chemical_formula_weight         1018.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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                 117.330(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8373(5)
_cell_length_b                   19.2808(5)
_cell_length_c                   15.9078(5)
_cell_measurement_reflns_used    23214
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      30.5220
_cell_measurement_theta_min      3.4760
_cell_volume                     4315.3(3)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.817
_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      9.00  58.00   0.50    2.00    --    3.51-131.00  63.00   98
  2  \w     13.00  38.00   0.50    2.00    --    3.51-138.00-112.00   50
  3  \w     11.00  37.00   0.50    2.00    --    3.51 -99.00  90.00   52
  4  \w    -32.00  17.00   0.50    2.00    --    3.51 -77.00-180.00   98
  5  \w    -41.00  27.00   0.50    2.00    --    3.51 -77.00   0.00  136
  6  \w    -24.00  19.00   0.50    2.00    --   -4.14  77.00 150.00   86
  7  \w      3.00  30.00   0.50    2.00    --   -4.14 -99.00 -90.00   54
  8  \w     -5.00  21.00   0.50    2.00    --   -4.14  77.00 -60.00   52
  9  \w    -36.00  19.00   0.50    2.00    --   -4.14 -77.00-150.00  110
;
_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      -0.0304653000
_diffrn_orient_matrix_UB_12      0.0054136000
_diffrn_orient_matrix_UB_13      0.0209790000
_diffrn_orient_matrix_UB_21      -0.0034551000
_diffrn_orient_matrix_UB_22      -0.0363733000
_diffrn_orient_matrix_UB_23      0.0042895000
_diffrn_orient_matrix_UB_31      0.0400238000
_diffrn_orient_matrix_UB_32      0.0009496000
_diffrn_orient_matrix_UB_33      0.0454096000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0566
_diffrn_reflns_av_unetI/netI     0.0477
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.817
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            49383
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.817
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.504
_diffrn_reflns_theta_min         3.249
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.906
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82365
_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 red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.567
_exptl_crystal_description       block
_exptl_crystal_F_000             2104
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'slow evaporation'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.365
_refine_diff_density_min         -0.669
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     624
_refine_ls_number_reflns         10768
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0365
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0332P)^2^+1.5223P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0854
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8716
_reflns_number_total             10768
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01358a2.cif
_cod_data_source_block           csp-co-p11
_cod_depositor_comments
'Adding full bibliography for 7716732--7716733.cif.'
_cod_database_code               7716733
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C184 H180 Cl4 Co8 N12 O56 '
_chemical_oxdiff_usercomment     'DARK RED BLOCKS'
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.773
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O10-H10
 0.85 with sigma of 0.01
 C46-H10
 1.89056 with sigma of 0.02
 Co2-H10
 2.660662 with sigma of 0.02
3. Others
 Sof(O13A)=1-FVAR(1)
 Sof(O13B)=FVAR(1)
 Fixed Sof: O14A(0.61) O14B(0.39)
4.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C8(H8), C10(H10A), C11(H11), C12(H12), C13(H13),
 C18(H18), C19(H19), C20(H20), C23(H23), C25(H25), C26(H26), C27(H27), C28(H28),
  C33(H33), C34(H34), C35(H35), C38(H38), C40(H40), C41(H41), C42(H42), C43(H43)
4.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              64116
_shelx_hkl_checksum              86188
_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 1.315
_oxdiff_exptl_absorpt_empirical_full_min 0.697