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_7063712
_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
'C48 H42 Co N6 O6, 2(Cl O4), 0.25(H2 O), 0.5[CH2Cl2]'
_chemical_formula_sum            'C48.5 H43.5 Cl3 Co N6 O14.25'
_chemical_formula_weight         1103.67
_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                91.549(2)
_cell_angle_beta                 100.772(2)
_cell_angle_gamma                105.942(2)
_cell_formula_units_Z            2
_cell_length_a                   9.3891(2)
_cell_length_b                   12.8470(3)
_cell_length_c                   20.7104(5)
_cell_measurement_reflns_used    28725
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      30.5500
_cell_measurement_theta_min      3.5260
_cell_volume                     2351.59(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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      100.15
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -15.00  39.00   0.50    3.28    --    3.35 -99.00-118.00  108
  2  \w    -15.00  31.00   0.50    3.28    --   -4.45 -99.00-118.00   92
  3  \w     -8.00  66.00   0.50    3.28    --    3.35  57.00-150.00  148
  4  \w     -8.00  66.00   0.50    3.28    --    3.35  57.00 150.00  148
  5  \w    -16.00  58.00   0.50    3.28    --   -4.45  57.00  90.00  148
  6  \w    -28.00  21.00   0.50    3.28    --   -4.45  77.00  30.00   98
  7  \w    -28.00  21.00   0.50    3.28    --   -4.45  77.00   0.00   98
  8  \w    -42.00  19.00   0.50    3.28    --   -4.45 -77.00-120.00  122
  9  \w    -15.00  31.00   0.50    3.28    --   -4.45 -99.00 -30.00   92
 10  \w    -15.00  31.00   0.50    3.28    --   -4.45 -99.00 -90.00   92
 11  \w     -8.00  62.00   0.50    3.28    --   -4.45  37.00   0.00  140
 12  \w    -15.00  27.00   0.50    3.28    --   -4.45 -99.00-180.00   84
 13  \w     -8.00  24.00   0.50    3.28    --   -4.45 -99.00 -60.00   64
 14  \w    -23.00   4.00   0.50    3.28    --   -4.45  77.00  60.00   54
;
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            45916
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.404
_exptl_absorpt_coefficient_mu    0.613
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58195
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.559
_exptl_crystal_description       block
_exptl_crystal_F_000             1137
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.729
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     691
_refine_ls_number_reflns         8255
_refine_ls_number_restraints     170
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0452P)^2^+1.5440P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0867
_refine_ls_wR_factor_ref         0.0895
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7412
_reflns_number_total             8255
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj05517a2.cif
_cod_data_source_block           njsk-4n_autored
_cod_depositor_comments
'Adding full bibliography for 7063711--7063713.cif.'
_cod_original_cell_volume        2351.58(10)
_cod_original_formula_sum        'C48.50 H43.50 Cl3 Co N6 O14.25'
_cod_database_code               7063712
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O Co Cl'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, H01W of C01W, All O(H,H) groups
 At 1.2 times of:
  H00Y of C00Y, H00Z of C00Z, H010 of C010, H012 of C012, H015 of C015, H016
  of C016, H019 of C019, H01A of C01A, H01B of C01B, H01D of C01D, H01E of C01E,
   H01F of C01F, H01G of C01G, H01H of C01H, H01K of C01K, H01M of C01M, H01N
  of C01N, H01O of C01O, H01P of C01P, H01R of C01R, H01T of C01T, H01U of C01U,
   H01V of C01V, H01 of C01Y
2. Restrained distances
 Cl-O0 \\sim ClA-O0A
 with sigma of 0.02
 Cl-O1 \\sim ClA-O1A
 with sigma of 0.02
 Cl-O2 \\sim ClA-O2A
 with sigma of 0.02
 Cl-O3 \\sim ClA-O3A
 with sigma of 0.02
 O0-O1 \\sim O0A-O1A
 with sigma of 0.04
 O0-O2 \\sim O0A-O2A
 with sigma of 0.04
 O0-O3 \\sim O0A-O3A
 with sigma of 0.04
 O1-O2 \\sim O1A-O2A
 with sigma of 0.04
 O1-O3 \\sim O1A-O3A
 with sigma of 0.04
 O2-O3 \\sim O2A-O3A
 with sigma of 0.04
 Cl-O0 \\sim ClA-O0A \\sim Cl-O1 \\sim ClA-O1A \\sim ClA-O3A \\sim Cl-O3 \\sim
ClA-O2A \\sim Cl-O2
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl \\sim O0 \\sim O1 \\sim O2 \\sim O3 \\sim ClA \\sim O0A \\sim O2A \\sim O3A
\\sim O1A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Uanis(ClA) = Uanis(Cl)
Uanis(O3) = Uanis(O3A)
Uanis(O1A) = Uanis(O1)
4. Others
 Sof(ClA)=Sof(O0A)=Sof(O2A)=Sof(O3A)=Sof(O1A)=1-FVAR(1)
 Sof(Cl)=Sof(O0)=Sof(O1)=Sof(O2)=Sof(O3)=FVAR(1)
 Fixed Sof: O4(0.25) H4A(0.25) H4B(0.25)
5.a Riding coordinates:
 O4(H4A,H4B)
5.b Aromatic/amide H refined with riding coordinates:
 C00Y(H00Y), C00Z(H00Z), C010(H010), C012(H012), C015(H015), C016(H016),
 C019(H019), C01A(H01A), C01B(H01B), C01D(H01D), C01E(H01E), C01F(H01F),
 C01G(H01G), C01H(H01H), C01K(H01K), C01M(H01M), C01N(H01N), C01O(H01O),
 C01P(H01P), C01R(H01R), C01T(H01T), C01U(H01U), C01V(H01V), C01Y(H01)
5.c Idealised Me refined as rotating group:
 C01Q(H01C,H01I,H01J), C01S(H01L,H01Q,H01S), C01X(H01Z,H,HA), C01Z(H1,HB,HC),
 C020(H02A,H02B,H02C)
5.d Idealised tetrahedral OH refined as rotating group:
 C01W(H01W)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              9165
_shelx_hkl_checksum              58496
_shelx_fab_checksum              11719
_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 1.767
_oxdiff_exptl_absorpt_empirical_full_min 0.427