Electrocatalytic water oxidation by molecular cobalt-terpyridine complexes in alkaline medium: experimental and theoretical study
Khan, Md. Adnan; Khan, Sahanwaj; Sengupta, Swaraj; Naskar, Subhendu; New Journal of Chemistry 49 (2025) 6963–6974; doi:10.1039/D4NJ05517A

data_7063711
_publ_section_title
;
 Electrocatalytic water oxidation by molecular cobalt-terpyridine
 complexes in alkaline medium: experimental and theoretical study
;
_journal_issue                   17
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              6963
_journal_page_last               6974
_journal_paper_doi               10.1039/D4NJ05517A
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety
'C46 H38 Co N6 O4, 2.562(H2 O), 2(Cl), 1.5[CH3OH], 1.5[H2O]'
_chemical_formula_sum            'C47.5 H52.12 Cl2 Co N6 O9.56'
_chemical_formula_weight         989.89
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-17
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-03-17 deposited with the CCDC.	2025-03-19 downloaded from the CCDC.
;
_cell_angle_alpha                84.750(6)
_cell_angle_beta                 89.913(6)
_cell_angle_gamma                83.450(7)
_cell_formula_units_Z            2
_cell_length_a                   10.5223(8)
_cell_length_b                   10.9270(10)
_cell_length_c                   19.7925(12)
_cell_measurement_reflns_used    5269
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      28.9640
_cell_measurement_theta_min      3.9980
_cell_volume                     2251.3(3)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL n/a (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      298.15
_diffrn_detector_area_resol_mean 10.4324
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -13.00  76.00   1.00   75.03    --   10.22  77.00-120.00   89
  2  \w    -37.00  60.00   1.00   75.03    --  -10.38  57.00 120.00   97
  3  \w    -81.00  16.00   1.00   75.03    --  -10.38 -57.00 -30.00   97
;
_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  0.0311
_diffrn_reflns_av_unetI/netI     0.0534
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            15464
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.380
_exptl_absorpt_coefficient_mu    0.566
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75014
_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            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.460
_exptl_crystal_description       block
_exptl_crystal_F_000             1033
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.504
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     576
_refine_ls_number_reflns         7897
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0844
_refine_ls_R_factor_gt           0.0572
_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^)+(0.0554P)^2^+2.8522P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1313
_refine_ls_wR_factor_ref         0.1490
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5680
_reflns_number_total             7897
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj05517a2.cif
_cod_data_source_block           34_diome_sn
_cod_depositor_comments
'Adding full bibliography for 7063711--7063713.cif.'
_cod_original_formula_sum        'C47.50 H52.12 Cl2 Co N6 O9.56'
_cod_database_code               7063711
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C46 H26Co N6 O4'
_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,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O1) = Uanis(Cl2)
3. Others
 1*[Sof(Cl0A)]+1*[Sof(Cl2A)]+1*[Sof(Cl2)]=2 with esd of 0
 Sof(O1)=Sof(H1A)=Sof(H1B)=FVAR(4)
4.a Riding coordinates:
 O3(H3A,H3B)
4.b Free rotating group:
 O01O(H01X,H01Y), O1(H1A,H1B)
4.c Aromatic/amide H refined with riding coordinates:
 C00G(H00G), C00M(H00M), C00S(H00S), C00U(H00U), C00Y(H00Y), C00Z(H00Z),
 C010(H010), C011(H011), C012(H012), C013(H013), C014(H014), C015(H015),
 C016(H016), C017(H017), C019(H019), C01A(H01A), C01B(H01B), C01D(H01D),
 C01E(H01E), C01F(H01F), C01G(H01G), C01H(H01H), C01I(H01I), C01J(H01J),
 C01K(H01K), C01M(H01N)
4.d Idealised Me refined as rotating group:
 C01L(H01C,H01L,H01M), C01N(H01O,H01P,H01Q), C01Q(H01R,H01S,H01T), C01R(H01U,
 H01V,H01W)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              7514
_shelx_hkl_checksum              22190
_shelx_fab_checksum              29311
_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 1.633
_oxdiff_exptl_absorpt_empirical_full_min 0.565