Anion controlled selectivity in oxygen reduction catalysed by a dinuclear cobalt N,O-Schiff base complex.
James, Charles A.; Swindells, Jessica E.; Ellis, Harry; Arjariya, Richa; Jarvis, Samuel P.; Brookfield, Adam; Fielden, John; Chemical communications (Cambridge, England) 61 (2025) 13201–13204; doi:10.1039/d5cc02476e

data_1575121
_publ_section_title
;
 Anion controlled selectivity in oxygen reduction catalysed by a dinuclear
 cobalt N,O-Schiff base complex.
;
_journal_issue                   70
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              13201
_journal_page_last               13204
_journal_paper_doi               10.1039/d5cc02476e
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C64 H62 Co4 N4 O12, 2(B F4), 4(C H4 O)'
_chemical_formula_sum            'C68 H78 B2 Co4 F8 N4 O16'
_chemical_formula_weight         1616.68
_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
_audit_creation_date             2025-07-07
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-07-08 deposited with the CCDC.	2025-07-18 downloaded from the CCDC.
;
_cell_angle_alpha                97.2080(10)
_cell_angle_beta                 97.696(2)
_cell_angle_gamma                108.398(2)
_cell_formula_units_Z            2
_cell_length_a                   12.7253(2)
_cell_length_b                   13.2722(2)
_cell_length_c                   22.5229(4)
_cell_measurement_reflns_used    26202
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      31.1100
_cell_measurement_theta_min      1.9340
_cell_volume                     3519.64(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.800
_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    -28.00  18.00   0.50   10.27    --    5.03 -57.00 -60.00   92
  2  \w     -7.00  72.00   0.50   10.27    --    5.03  37.00 -60.00  158
  3  \w    -21.00  22.00   0.50   10.27    --    5.03 -77.00 -90.00   86
  4  \w     -3.00  35.00   0.50   10.27    --    5.03  57.00  60.00   76
  5  \w     -1.00  37.00   0.50   10.27    --    5.03 -99.00 120.00   76
  6  \w     -2.00  39.00   0.50   10.27    --    5.03 -99.00-180.00   82
  7  \w    -16.00  17.00   0.50   10.27    --   -5.57 -77.00  90.00   66
  8  \w    -21.00  10.00   0.50   10.27    --   -5.57 -77.00  30.00   62
  9  \w    -20.00  12.00   0.50   10.27    --   -5.57 -77.00-120.00   64
 10  \w    -17.00  52.00   0.50   10.27    --   -5.57  19.00  60.00  138
 11  \w    -28.00  -2.00   0.50   10.27    --   -5.57  77.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.800
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            57745
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.800
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.069
_diffrn_reflns_theta_min         1.855
_exptl_absorpt_coefficient_mu    1.017
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90675
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.115a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.525
_exptl_crystal_description       block
_exptl_crystal_F_000             1664
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.559
_refine_diff_density_min         -0.543
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     957
_refine_ls_number_reflns         18079
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0681
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0780P)^2^+1.3111P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1282
_refine_ls_wR_factor_ref         0.1376
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13508
_reflns_number_total             18079
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02476e2.cif
_cod_data_source_block           Co4(MeBSIP)2(BF4)2
_cod_depositor_comments
'Adding full bibliography for 1575120--1575121.cif.'
_cod_database_code               1575121
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.785
_shelx_estimated_absorpt_t_min   0.743
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O12-H12
 0.87 with sigma of 0.01
 O11-H11
 0.87 with sigma of 0.01
 C63-H11
 1.914334 with sigma of 0.02
 Co4-H12
 2.713754 with sigma of 0.02
 Co1-H11
 2.683979 with sigma of 0.02
 C64-H12
 1.920289 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F7) \\sim Ueq, Uanis(F8) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: F5(0.45) F7(0.45) F5B(0.55) F7B(0.55)
5.a Ternary CH refined with riding coordinates:
 C15(H15), C46(H46)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C16(H16A,H16B), C45(H45A,H45B), C47(H47A,H47B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C7(H7), C10(H10), C11(H11A), C12(H12A), C13(H13),
 C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C25(H25), C27(H27), C28(H28),
  C33(H33), C34(H34), C36(H36), C38(H38), C40(H40), C41(H41), C42(H42),
 C43(H43), C49(H49), C50(H50), C51(H51), C52(H52), C54(H54), C56(H56), C58(H58),
  C59(H59)
5.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C61(H61A,H61B,H61C), C62(H62A,H62B,
 H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,
 H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C)
5.e Idealised tetrahedral OH refined as rotating group:
 O13(H13A), O14(H14), O15(H15A), O16(H16)
;
_shelx_res_checksum              54531
_shelx_hkl_checksum              39409
_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
;