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_1575120
_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         'C38 H40 Co3 N2 O12, 1.5(C H4 O)'
_chemical_formula_sum            'C39.5 H46 Co3 N2 O13.5'
_chemical_formula_weight         941.57
_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
;
2025-07-16 deposited with the CCDC.	2025-07-18 downloaded from the CCDC.
;
_cell_angle_alpha                102.365(3)
_cell_angle_beta                 105.032(3)
_cell_angle_gamma                93.290(3)
_cell_formula_units_Z            2
_cell_length_a                   11.5896(4)
_cell_length_b                   13.2720(5)
_cell_length_c                   14.6041(4)
_cell_measurement_reflns_used    10119
_cell_measurement_temperature    100.00(14)
_cell_measurement_theta_max      74.8200
_cell_measurement_theta_min      3.2770
_cell_volume                     2103.93(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_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    'SHELXD  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(14)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.904
_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    -35.00  -9.00   0.50    1.05    --  -47.45  33.00  37.00   52
  2  \w    -38.00 -13.00   0.50    4.22    --  -86.25  33.00  37.00   50
  3  \w    -42.00 -14.00   0.50    4.22    --  -86.25  45.00   0.00   56
  4  \w    -49.00 -21.00   0.50    4.22    --  -86.25  45.00 -30.00   56
  5  \w    -47.00 -13.00   0.50    4.22    --  -86.25  77.00 -90.00   68
  6  \w    -67.00 -16.00   0.50    4.22    --  -86.25  61.00  30.00  102
  7  \w    -86.00 -13.00   0.50    4.22    --  -86.25 125.00  90.00  146
  8  \w    -70.00 -13.00   0.50    4.22    --  -86.25  61.00 150.00  114
  9  \w   -120.00 -95.00   0.50    1.05    --  -47.45 -57.00 150.00   50
 10  \w   -120.00 -94.00   0.50    1.05    --  -47.45 -57.00  90.00   52
 11  \w   -120.00 -94.00   0.50    1.05    --  -47.45 -57.00 120.00   52
 12  \w   -142.00-116.00   0.50    4.22    --  -86.25 -94.00  30.00   52
 13  \w   -120.00 -95.00   0.50    1.05    --  -47.45-125.00   0.00   50
 14  \w   -119.00 -94.00   0.50    1.05    --  -47.45 -57.00 -90.00   50
 15  \w   -120.00 -34.00   0.50    1.05    --  -47.45 -33.00-120.00  172
 16  \w     35.00  97.00   0.50    1.05    --   47.45  33.00  37.00  124
 17  \w     94.00 119.00   0.50    1.05    --   47.45  57.00 120.00   50
 18  \w    125.00 168.00   0.50    4.22    --  106.49  33.00  37.00   86
 19  \w     93.00 119.00   0.50    4.22    --  106.49  33.00  37.00   52
 20  \w     93.00 174.00   0.50    4.22    --  106.49  15.00 150.00  162
 21  \w     80.00 105.00   0.50    4.22    --  106.49 -94.00 -60.00   50
 22  \w     81.00 111.00   0.50    4.22    --  106.49-125.00-150.00   60
 23  \w     75.00 101.00   0.50    4.22    --  106.49 -94.00-180.00   52
 24  \w     65.00 111.00   0.50    4.22    --  106.49-125.00-180.00   92
 25  \w     50.00  76.00   0.50    4.22    --  106.49-125.00-150.00   52
 26  \w     36.00 111.00   0.50    4.22    --  106.49-125.00 -90.00  150
 27  \w     51.00  88.00   0.50    4.22    --  106.49 -94.00  30.00   74
 28  \w     82.00 111.00   0.50    4.22    --  106.49-125.00  90.00   58
 29  \w     39.00 109.00   0.50    4.22    --  106.49-114.00 -27.10  140
 30  \w     36.00  63.00   0.50    4.22    --  106.49 -61.00-180.00   54
 31  \w     35.00  60.00   0.50    4.22    --  106.49 -61.00-120.00   50
 32  \w     35.00  68.00   0.50    4.22    --  106.49 -61.00 -60.00   66
 33  \w     35.00  63.00   0.50    4.22    --  106.49 -94.00 -60.00   56
 34  \w     40.00  97.00   0.50    4.22    --  106.49-100.00 -99.82  114
 35  \w     37.00  66.00   0.50    4.22    --  106.49 -61.00  30.00   58
 36  \w     35.00 103.00   0.50    4.22    --  106.49 -94.00   0.00  136
 37  \w     35.00  61.00   0.50    4.22    --  106.49-125.00  90.00   52
 38  \w     34.00  91.00   0.50    4.22    --  106.49 -94.00  90.00  114
 39  \w     35.00  67.00   0.50    4.22    --  106.49 -61.00 150.00   64
 40  \w    -21.00  38.00   0.50    1.05    --   47.45 -37.00 120.00  118
 41  \w    -15.00  38.00   0.50    1.05    --   47.45 -33.00-120.00  106
 42  \w     96.00 122.00   0.50    4.22    --  106.49  30.00-180.00   52
 43  \w    133.00 176.00   0.50    4.22    --  106.49  30.00-180.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0892783000
_diffrn_orient_matrix_UB_12      0.0693867000
_diffrn_orient_matrix_UB_13      0.0356581000
_diffrn_orient_matrix_UB_21      0.0545168000
_diffrn_orient_matrix_UB_22      0.0908435000
_diffrn_orient_matrix_UB_23      -0.0318093000
_diffrn_orient_matrix_UB_31      -0.0909739000
_diffrn_orient_matrix_UB_32      -0.0354885000
_diffrn_orient_matrix_UB_33      -0.1017856000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0790
_diffrn_reflns_av_unetI/netI     0.0700
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.904
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24332
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.191
_diffrn_reflns_theta_min         3.226
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.718
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52276
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       block
_exptl_crystal_F_000             972
_exptl_crystal_recrystallization_method
'slow evaporation of a methanol solution'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.015
_refine_diff_density_max         1.453
_refine_diff_density_min         -1.194
_refine_diff_density_rms         0.180
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     545
_refine_ls_number_reflns         8246
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0917
_refine_ls_R_factor_gt           0.0784
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1707P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2135
_refine_ls_wR_factor_ref         0.2297
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6644
_reflns_number_total             8246
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02476e2.cif
_cod_data_source_block           Co3MeBSIPOAc3
_cod_depositor_comments
'Adding full bibliography for 1575120--1575121.cif.'
_cod_original_formula_sum        'C39.50 H46 Co3 N2 O13.50'
_cod_database_code               1575120
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.323
_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
 0.85 with sigma of 0.01
 Co3-H12
 2.654169 with sigma of 0.02
 C38-H12
 1.881259 with sigma of 0.02
3. Others
 Fixed Sof: O13(0.5) H13A(0.5) C39(0.5) H39A(0.5) H39B(0.5) H39C(0.5)
4.a Ternary CH refined with riding coordinates:
 C15(H15)
4.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C16(H16A,H16B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C7(H7), C10(H10), C11(H11), C12(H12A), C13(H13),
 C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C25(H25), C27(H27), C28(H28)
4.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C35(H35A,H35B,
 H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C)
4.e Idealised tetrahedral OH refined as rotating group:
 O13(H13A), O14(H14)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              75735
_shelx_hkl_checksum              61677
_shelx_fab_checksum              94553
_olex2_exptl_crystal_mounting_method 'on a glass fibre loop in Fomblin Y oil'
_olex2_submission_original_sample_id Co3LMeOAc3
_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 3.071
_oxdiff_exptl_absorpt_empirical_full_min 0.512