The steric hindrance effect of Co porphyrins promoting two-electron oxygen reduction reaction selectivity.
Mou, Yonghong; Zhang, Jieling; Qin, Haonan; Li, Xinyue; Zeng, Zequan; Zhang, Rong; Liang, Zuozhong; Cao, Rui; Chemical communications (Cambridge, England) 61 (2025) 1878–1881; doi:10.1039/d4cc06012a

data_7134144
_publ_section_title
;
 The steric hindrance effect of Co porphyrins promoting two-electron
 oxygen reduction reaction selectivity.
;
_journal_issue                   9
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1878
_journal_page_last               1881
_journal_paper_doi               10.1039/d4cc06012a
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C84 H94 Co N4 O17'
_chemical_formula_sum            'C84 H94 Co N4 O17'
_chemical_formula_weight         1490.56
_chemical_name_systematic
'5,10,15,20-tetrakis(2',6'-dipivaloyloxyphenyl)Cobalt porphyrin'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           63
_space_group_name_Hall           '-C 2c 2'
_space_group_name_H-M_alt        'C m c m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-01-31
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-09-15 deposited with the CCDC.	2024-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.907(3)
_cell_length_b                   23.347(4)
_cell_length_c                   25.011(4)
_cell_measurement_reflns_used    6567
_cell_measurement_temperature    153.00(10)
_cell_measurement_theta_max      20.478
_cell_measurement_theta_min      2.357
_cell_volume                     8121(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      153.00(10)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture 296K'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1324
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            67886
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.095
_diffrn_reflns_theta_max         25.095
_diffrn_reflns_theta_min         1.889
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.279
_exptl_absorpt_correction_T_max  0.7289
_exptl_absorpt_correction_T_min  0.6329
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1857 before and 0.1023 after correction.
The Ratio of minimum to maximum transmission is 0.8683.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.219
_exptl_crystal_description       block
_exptl_crystal_F_000             3156
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.538
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         3854
_refine_ls_number_restraints     254
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.1542
_refine_ls_R_factor_gt           0.1167
_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^)+(0.1179P)^2^+46.4180P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2773
_refine_ls_wR_factor_ref         0.3106
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2773
_reflns_number_total             3854
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc06012a2.cif
_cod_data_source_block           1472-ocotbu
_cod_depositor_comments
'Adding full bibliography for 7134144--7134145.cif.'
_cod_original_cell_volume        8121(2)
_cod_database_code               7134144
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.946
_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. Restrained distances
 C19-C16 = C18-C16 = C17-C16
 1.54 with sigma of 0.01
 O3-C21 = O5-C25
 1.45 with sigma of 0.01
 C17-C18 = C17-C19 = C18-C19
 2.515 with sigma of 0.02
3. Restrained planarity
 O3, C20, C21, C22, C23, C24, C25, O5, C8
 with sigma of 0.1
4. Rigid bond restraints
 Co1, O7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Uiso/Uaniso restraints and constraints
C12 \\sim O1 \\sim O2 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim
O1A \\sim O2A \\sim C15A \\sim C16A \\sim C17A \\sim C18A \\sim C19A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C8 \\sim O3 \\sim O5 \\sim O6 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24
\\sim C25 \\sim C26 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim O4
\\sim C27 \\sim C28 \\sim C29 \\sim C30: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
6. Same fragment restrains
{C12, O1A, O2A, C15A, C16A, C17A, C18A, C19A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C12, O1, O2, C15, C16, C17, C18, C19}
7. Others
 Sof(O1A)=Sof(O2A)=Sof(C15A)=Sof(C16A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=
 Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=1-FVAR(1)
 Sof(O1)=Sof(O2)=Sof(C15)=Sof(C16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 FVAR(1)
 Fixed Sof: C5(0.5) H5(0.5) C6(0.5) H6(0.5) C7(0.5) C8(0.5) O3(0.5) O4(0.5)
 O5(0.5) O6(0.5) C21(0.5) C20(0.5) C25(0.5) C24(0.5) H24(0.5) C23(0.5) H23(0.5)
 C22(0.5) H22(0.5) C26(0.5) C27(0.5) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5)
 C29(0.5) H29A(0.5) H29B(0.5) H29C(0.5) C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5)
 C31(0.5) C32(0.5) C33(0.5) H33A(0.5) H33B(0.5) H33C(0.5) C34(0.5) H34A(0.5)
 H34B(0.5) H34C(0.5) C35(0.5) H35A(0.5) H35B(0.5) H35C(0.5) O7(0.25) H7A(0.25)
 H7B(0.25)
8.a Riding coordinates:
 O7(H7A,H7B)
8.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C6(H6), C10(H10), C13(H13), C14(H14), C24(H24), C23(H23),
 C22(H22)
8.c Fitted hexagon refined as free rotating group:
 C21(C20,C25,C24,C23,C22)
8.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C17A(H17D,H17E,
 H17F), C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F), C28(H28A,H28B,H28C),
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              97718
_olex2_submission_special_instructions 'No special instructions were received'