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_7063713
_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         'C42 H28 Co F2 N6, 1(Cl1 O4), Cl, H2 O'
_chemical_formula_sum            'C42 H30 Cl2 Co F2 N6 O5'
_chemical_formula_weight         866.55
_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                85.981(6)
_cell_angle_beta                 78.249(6)
_cell_angle_gamma                74.246(7)
_cell_formula_units_Z            2
_cell_length_a                   8.9320(7)
_cell_length_b                   10.3376(8)
_cell_length_c                   21.3919(16)
_cell_measurement_reflns_used    4732
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      25.5290
_cell_measurement_theta_min      3.5930
_cell_volume                     1861.0(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    -36.00  59.00   1.00  100.07    --  -10.22  57.00   0.00   95
  2  \w    -75.00  14.00   1.00  100.07    --  -10.22 -77.00  90.00   89
  3  \w    -79.00  13.00   1.00  100.07    --  -10.22 -57.00-150.00   92
;
_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  0.0349
_diffrn_reflns_av_unetI/netI     0.0576
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            13213
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         3.380
_exptl_absorpt_coefficient_mu    0.672
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98865
_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 reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_description       block
_exptl_crystal_F_000             886
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.337
_refine_diff_density_min         -0.279
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     598
_refine_ls_number_reflns         6549
_refine_ls_number_restraints     187
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0494
_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^)+(0.0418P)^2^+0.8102P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1010
_refine_ls_wR_factor_ref         0.1130
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4975
_reflns_number_total             6549
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj05517a2.cif
_cod_data_source_block           4fc0
_cod_depositor_comments
'Adding full bibliography for 7063711--7063713.cif.'
_cod_database_code               7063713
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C21H14 N3 FBr O1 '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 O0AC-O0 = O0AC-O3 = O3-O0 = O0-O01M = O01M-O0AC = O01M-O3 = O01K-O0AA = O0AA-
 O1 = O1-O01K = O00Y-O0AA = O00Y-O01K = O00Y-O1 = O0AB-O2 = O2-O00Z = O00Z-O0AB
 = O0AB-O01L = O01L-O2 = O01L-O00Z
 2.4 with sigma of 0.02
 Cl-O01L \\sim Cl00-O00Y \\sim ClA-O01M \\sim Cl-O2 \\sim ClA-O3 \\sim Cl00-O1
\\sim ClA-O0 \\sim Cl-O00Z
 \\sim Cl00-O0AA \\sim Cl-O0AB \\sim ClA-O0AC \\sim Cl00-O01K
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O0AA \\sim O01K \\sim O0AB \\sim O0AC \\sim O2 \\sim O3 \\sim O1 \\sim O0 \\sim
O00Z: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
Uanis(O2A) = Uanis(Cl2)
Uanis(Cl1) = Uanis(O1A)
Uanis(Cl) = Uanis(Cl00) = Uanis(ClA)
Uanis(O01L) = Uanis(O00Y) = Uanis(O01M)
Uanis(O01K) = Uanis(O2)
4. Others
 1*[Sof(Cl00)+Sof(O00Y)+Sof(O01K)+Sof(O1)+Sof(O0AA)]+1*[Sof(O0AB)+Sof(O01L)+
 Sof(O2)+Sof(O00Z)+Sof(Cl)]+1*[Sof(ClA)+Sof(O0AC)+Sof(O0)+Sof(O3)+Sof(O01M)]=1
 with esd of 0
 Sof(Cl00)=Sof(O00Y)=Sof(O01K)=Sof(O1)=Sof(O0AA)=FVAR(1)
 Sof(O0AB)=Sof(O01L)=Sof(O2)=Sof(O00Z)=Sof(Cl)=FVAR(2)
 Sof(ClA)=Sof(O0AC)=Sof(O0)=Sof(O3)=Sof(O01M)=FVAR(3)
 Fixed Sof: Cl1(0.5) Cl2(0.5) O2A(0.5) H2AA(0.5) H2AB(0.5) O1A(0.5) H1AA(0.5)
 H1AB(0.5)
5.a Free rotating group:
 O2A(H2AA,H2AB), O1A(H1AA,H1AB)
5.b Aromatic/amide H refined with riding coordinates:
 C36(H36), C42(H42), C7(H7), C15(H15), C28(H28), C21(H21), C18(H18), C22(H22),
 C39(H39), C4(H4), C1(H1), C41(H41), C25(H25), C11(H11), C10(H10), C40(H40),
 C23(H23), C19(H19), C20(H20), C24(H24), C14(H14), C2(H2), C13(H13), C3(H3),
 C35(H35), C34(H34), C31(H31), C32(H32)
;
_shelx_res_checksum              28502
_shelx_hkl_checksum              9883
_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 1.089
_oxdiff_exptl_absorpt_empirical_full_min 0.927