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_7125649
_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         'C44 H31 N5'
_chemical_formula_sum            'C44 H31 N5'
_chemical_formula_weight         629.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-09-09 deposited with the CCDC.	2019-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.209(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.7683(9)
_cell_length_b                   9.6009(5)
_cell_length_c                   12.4544(7)
_cell_measurement_reflns_used    9858
_cell_measurement_temperature    100.01
_cell_measurement_theta_max      27.44
_cell_measurement_theta_min      3.02
_cell_volume                     1610.60(16)
_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      100.01
_diffrn_detector                 CMOS
_diffrn_detector_area_resol_mean '1024 x 1024'
_diffrn_detector_type            'Photon 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       '\k-geometry diffractometer triump Mo'
_diffrn_measurement_device_type  'Bruker D8 Venture triumph Mo'
_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  0.0520
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            39621
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.603
_diffrn_reflns_theta_min         3.025
_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    0.077
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6253
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0756 before and 0.0645 after correction. The Ratio of minimum to maximum transmission is 0.8387.'
_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    1.299
_exptl_crystal_description       prism
_exptl_crystal_F_000             660
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and ether  by slow evaporation'
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.641
_refine_diff_density_min         -0.279
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3712
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0517
_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^)+(0.0560P)^2^+1.4297P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1215
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2840
_reflns_number_total             3712
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07351e2.cif
_cod_data_source_block           H2TPP-NH2
_cod_depositor_comments
'Adding full bibliography for 7125649--7125650.cif.'
_cod_database_code               7125649
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.974
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
2. Others
 Fixed Sof: H2(0.5) N3(0.5) H3A(0.5) H3B(0.5)
3.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
3.b X=CH2 refined with riding coordinates:
 N3(H3A,H3B)
;
_shelx_res_checksum              58881
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop with oil'
_olex2_submission_special_instructions 'No special instructions were received'