Regioselective C-H amination of free base porphyrins via electrogenerated pyridinium-porphyrins and stabilization of easily oxidized amino-porphyrins by protonation.
Bousfiha, Asmae; Dimé, Abdou K D; Mankou-Makaya, Amelle; Echaubard, Julie; Berthelot, Mathieu; Cattey, Hélène; Romieu, Anthony; Roger, Julien; Devillers, Charles H.; Chemical communications (Cambridge, England) 56 (2020) 884–887; doi:10.1039/c9cc07351e

data_7125650
_publ_section_title
;
 Regioselective C-H amination of free base porphyrins via electrogenerated
 pyridinium-porphyrins and stabilization of easily oxidized
 amino-porphyrins by protonation.
;
_journal_issue                   6
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              884
_journal_page_last               887
_journal_paper_doi               10.1039/c9cc07351e
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety
'C41 H50 N5 O Zn, B F4, 2(C H2 Cl2), 0.63(O H2)'
_chemical_formula_sum            'C43 H55.26 B Cl4 F4 N5 O1.63 Zn'
_chemical_formula_weight         962.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-05-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-11 deposited with the CCDC.	2019-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.255(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.0207(5)
_cell_length_b                   15.2513(8)
_cell_length_c                   27.7168(15)
_cell_measurement_reflns_used    9571
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.50
_cell_measurement_theta_min      2.98
_cell_volume                     4598.0(4)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_collection       'APEX3 (Bruker, 2015)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 CMOS
_diffrn_detector_area_resol_mean '1024 x 1024'
_diffrn_detector_type            'Photon 100'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       '\k-geometry diffractometer triump Mo'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans''
_diffrn_radiation_collimation    '0.6 mm'
_diffrn_radiation_monochromator  'TRIUMPH curved crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            92164
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.553
_diffrn_reflns_theta_min         2.899
_diffrn_source                   'X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Siemens KFF Mo 2K-90C'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.823
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0544 before and 0.0463 after correction. The Ratio of minimum to maximum transmission is 0.9293.'
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.390
_exptl_crystal_description       prism
_exptl_crystal_F_000             2001
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of heptane and DCM  by slow evaporation'
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.526
_refine_diff_density_min         -1.742
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     590
_refine_ls_number_reflns         10589
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0894
_refine_ls_R_factor_gt           0.0765
_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^)+(0.1171P)^2^+17.3008P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2048
_refine_ls_wR_factor_ref         0.2184
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8936
_reflns_number_total             10589
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07351e2.cif
_cod_data_source_block           ZnTTBPPyBF4
_cod_depositor_comments
'Adding full bibliography for 7125649--7125650.cif.'
_cod_database_code               7125650
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.853
_shelx_estimated_absorpt_t_min   0.796
_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,H) groups
2. Others
 Fixed Sof: B2(0.67) F3(0.67) F4(0.67) F5(0.67) F6(0.67) B2A(0.33) F3A(0.33)
 F4A(0.33) F5A(0.33) F6A(0.33) O2(0.63)
3.a Free rotating group:
 B2(F3,F4,F5,F6)
3.b Rotating group:
 O1(H1A,H1B)
3.c Secondary CH2 refined with riding coordinates:
 C44(H44A,H44B), C42(H42A,H42B)
3.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C8(H8), C11(H11), C13(H13), C16(H16), C18(H18), C21(H21),
 C22(H22), C23(H23), C24(H24), C25(H25)
3.e Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C),
 C41(H41A,H41B,H41C)
;
_shelx_res_checksum              6303
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'