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_7134145
_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         'C64 H60 Co N4 O8, 0.6[C7H16]'
_chemical_formula_sum            'C64 H60 Co N4 O8'
_chemical_formula_weight         1072.09
_chemical_name_systematic
'5,10,15,20-tetrakis(para-dipivaloyloxyphenyl)Cobalt Porphyrin'
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-06-07
_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                77.886(7)
_cell_angle_beta                 86.561(7)
_cell_angle_gamma                82.747(7)
_cell_formula_units_Z            2
_cell_length_a                   9.8827(18)
_cell_length_b                   16.038(3)
_cell_length_c                   19.204(3)
_cell_measurement_reflns_used    6647
_cell_measurement_temperature    190.00(10)
_cell_measurement_theta_max      46.612
_cell_measurement_theta_min      3.516
_cell_volume                     2950.5(9)
_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      190.00(10)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0932
_diffrn_reflns_av_unetI/netI     0.0867
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            40473
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.032
_diffrn_reflns_theta_min         2.048
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           2.86
_diffrn_source_power             0.19937059999999998
_diffrn_source_target            Mo
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.884
_exptl_absorpt_correction_T_max  0.7506
_exptl_absorpt_correction_T_min  0.5362
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1271 before and 0.0696 after correction.
The Ratio of minimum to maximum transmission is 0.7144.
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    1.207
_exptl_crystal_description       block
_exptl_crystal_F_000             1126
_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         0.635
_refine_diff_density_min         -0.586
_refine_diff_density_rms         0.072
_refine_ls_extinction_coef       0.0018(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1190
_refine_ls_number_reflns         10975
_refine_ls_number_restraints     1831
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.1841
_refine_ls_R_factor_gt           0.1003
_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^)+(0.1825P)^2^+1.5463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2677
_refine_ls_wR_factor_ref         0.3331
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5162
_reflns_number_total             10975
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc06012a2.cif
_cod_data_source_block           myh-1072
_cod_depositor_comments
'Adding full bibliography for 7134144--7134145.cif.'
_cod_original_cell_volume        2950.3(9)
_cod_database_code               7134145
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.834
_shelx_estimated_absorpt_t_min   0.704
_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
2. Restrained distances
 C28-C27 = C39-C38 = C50-C49 = C61-C60
 1.5 with sigma of 0.01
 O8-C60 = O2-C27 = O4-C38 = O6-C49
 1.23 with sigma of 0.01
 O7-C60 = O1-C27 = O3-C38 = O5-C49
 1.35 with sigma of 0.01
 O7-C57 = O5-C46 = O3-C35 = O1-C24
 1.35 with sigma of 0.01
 C63-C61 = C64-C61 = C62-C61 = C29-C28 = C30-C28 = C31-C28 = C41-C39 = C42-C39
 = C40-C39 = C51-C50 = C52-C50 = C53-C50
 1.54 with sigma of 0.01
3. Restrained planarity
 C60, C61, O7, O8
 with sigma of 0.01
 C59A, C57A, C56A, C54A, C58A, C55A, C20, O7A
 with sigma of 0.01
 C24, C22, C21, C25, C23, C26, O1, C5
 with sigma of 0.01
 C57, C55, C54, C58, C56, C59, C20, O7
 with sigma of 0.01
 C46, C44, C43, C47, C45, C48, C15, O5
 with sigma of 0.01
 C36A, C34A, C33A, C37A, C35A, C32A, O3A, C10
 with sigma of 0.01
 C26A, C24A, C23A, C21A, C25A, C22A, C5, O1A
 with sigma of 0.01
 C35, C33, C32, C36, C34, C37, C10, O3
 with sigma of 0.01
 C48A, C46A, C45A, C43A, C47A, C44A, C15, O5A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim
C51 \\sim C52 \\sim C53 \\sim O5 \\sim O6 \\sim C43A \\sim C44A \\sim C45A
\\sim C46A \\sim C47A \\sim C48A \\sim C49A \\sim C50A \\sim C51A \\sim C52A
\\sim C53A \\sim O5A \\sim O6A \\sim C15: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim
C40 \\sim C41 \\sim C42 \\sim O3 \\sim O4 \\sim C32A \\sim C33A \\sim C34A
\\sim C35A \\sim C36A \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim C41A
\\sim C42A \\sim O3A \\sim O4A \\sim C10: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim
C62 \\sim C63 \\sim C64 \\sim O7 \\sim O8 \\sim C54A \\sim C55A \\sim C56A
\\sim C57A \\sim C58A \\sim C59A \\sim C60A \\sim C61A \\sim C62A \\sim C63A
\\sim C64A \\sim O7A \\sim O8A \\sim C20: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim
C29 \\sim C30 \\sim C31 \\sim O1 \\sim O2 \\sim C21A \\sim C22A \\sim C23A
\\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A \\sim C29A \\sim C30A
\\sim C31A \\sim O1A \\sim O2A \\sim C5: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
5. Same fragment restrains
{C5, C21A, C22A, C23A, C24A, C25A, C26A, C27A, C28A, C29A, C30A, C31A, O1A,
O2A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C5, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, O1, O2}
{C10, C32A, C33A, C34A, C35A, C36A, C37A, C38A, C39A, C40A, C41A, C42A, O3A,
O4A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C10, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, O3, O4}
{C15, C43A, C44A, C45A, C46A, C47A, C48A, C49A, C50A, C51A, C52A, C53A, O5A,
O6A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C15, C43, C44, C45, C46, C47, C48, C49, C50, C51, C52, C53, O5, O6}
{C20, C54A, C55A, C56A, C57A, C58A, C59A, C60A, C61A, C62A, C63A, C64A, O7A,
O8A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C20, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, O7, O8}
6. Others
 Sof(C54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(C58A)=
 Sof(H58A)=Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(C61A)=Sof(C62A)=Sof(H62D)=
 Sof(H62E)=Sof(H62F)=Sof(C63A)=Sof(H63D)=Sof(H63E)=Sof(H63F)=Sof(C64A)=
 Sof(H64D)=Sof(H64E)=Sof(H64F)=Sof(O7A)=Sof(O8A)=1-FVAR(1)
 Sof(C54)=Sof(C55)=Sof(H55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(C58)=Sof(H58)=
 Sof(C59)=Sof(H59)=Sof(C60)=Sof(C61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=
 Sof(O7)=Sof(O8)=FVAR(1)
 Sof(C21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(C25A)=
 Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(C28A)=Sof(C29A)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=
 Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(O1A)=Sof(O2A)=1-FVAR(2)
 Sof(C21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(C25)=Sof(H25)=
 Sof(C26)=Sof(H26)=Sof(C27)=Sof(C28)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=
 Sof(O1)=Sof(O2)=FVAR(2)
 Sof(C32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(C36A)=
 Sof(H36A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(C39A)=Sof(C40A)=Sof(H40D)=
 Sof(H40E)=Sof(H40F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C42A)=
 Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(O3A)=Sof(O4A)=1-FVAR(3)
 Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(C36)=Sof(H36)=
 Sof(C37)=Sof(H37)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 Sof(O3)=Sof(O4)=FVAR(3)
 Sof(C43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(C47A)=
 Sof(H47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(C50A)=Sof(C51A)=Sof(H51D)=
 Sof(H51E)=Sof(H51F)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53A)=
 Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(O5A)=Sof(O6A)=1-FVAR(4)
 Sof(C43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(C47)=Sof(H47)=
 Sof(C48)=Sof(H48)=Sof(C49)=Sof(C50)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 Sof(O5)=Sof(O6)=FVAR(4)
7.a Riding coordinates:
 C53A(H53D,H53E,H53F)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C22(H22), C23(H23), C25(H25), C26(H26), C7(H7), C8(H8),
 C33(H33), C34(H34), C36(H36), C37(H37), C12(H12), C13(H13), C44(H44), C45(H45),
  C47(H47), C48(H48), C17(H17), C18(H18), C55(H55), C56(H56), C58(H58),
 C59(H59), C22A(H22A), C23A(H23A), C25A(H25A), C26A(H26A), C33A(H33A),
 C34A(H34A), C36A(H36A), C37A(H37A), C44A(H44A), C45A(H45A), C47A(H47A),
 C48A(H48A), C55A(H55A), C56A(H56A), C58A(H58A), C59A(H59A)
7.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C40(H40A,H40B,
 H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C51(H51A,H51B,H51C), C52(H52A,
 H52B,H52C), C53(H53A,H53B,H53C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C), C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F), C31A(H31D,
 H31E,H31F), C40A(H40D,H40E,H40F), C41A(H41D,H41E,H41F), C42A(H42D,H42E,H42F),
 C51A(H51D,H51E,H51F), C52A(H52D,H52E,H52F), C62A(H62D,H62E,H62F), C63A(H63D,
 H63E,H63F), C64A(H64D,H64E,H64F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 69 electrons were 
found in a volume of 315\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.6[C7H16] per Asymmetric Unit 
which account for 70 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              33149
_shelx_fab_checksum              32055
_olex2_submission_special_instructions 'No special instructions were received'