Targeted Synthesis of Regioisomerically Pure Dodecasubstituted Type I Porphyrins through the Exploitation of Peri-interactions.
Kielmann, Marc; Flanagan, Keith J.; Senge, Mathias O.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00798

data_4038419
_publ_section_title
;
 Targeted Synthesis of Regioisomerically Pure Dodecasubstituted Type I
 Porphyrins through the Exploitation of Peri-interactions.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00798
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(Cl), C64 H72 N4'
_chemical_formula_sum            'C64 H72 Cl2 N4'
_chemical_formula_weight         968.15
_chemical_name_systematic
'2,7,12,17-tetraethyl-3,8,13,18-tetraisopropyl-5,10,15,20-tetraphenylporphyrin dication chlorine salt'
_space_group_crystal_system      cubic
_space_group_IT_number           220
_space_group_name_Hall           'I -4bd 2c 3'
_space_group_name_H-M_alt        'I -4 3 d'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   27.1155(7)
_cell_length_b                   27.1155(7)
_cell_length_c                   27.1155(7)
_cell_measurement_reflns_used    9910
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      51.99
_cell_measurement_theta_min      3.99
_cell_volume                     19936.7(9)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'APEX 3 (Bruker, 2016) '
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_detector       'Bruker PHOTON 50'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1481
_diffrn_reflns_av_unetI/netI     0.0516
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            93602
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        54.206
_diffrn_reflns_theta_max         54.206
_diffrn_reflns_theta_min         3.993
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.142
_exptl_absorpt_correction_T_max  0.7507
_exptl_absorpt_correction_T_min  0.5618
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1256 before and 0.1012 after correction. The Ratio of minimum to maximum transmission is 0.7484. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    0.968
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             6216
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.310
_refine_diff_density_min         -0.332
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.10(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     163
_refine_ls_number_reflns         2041
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0786
_refine_ls_R_factor_gt           0.0718
_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^)+(0.1670P)^2^+5.7621P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2016
_refine_ls_wR_factor_ref         0.2116
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                1815
_reflns_number_total             2041
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00798_si_003.cif
_cod_data_source_block           kjf252p
_cod_original_cell_volume        19936.7(15)
_cod_database_code               4038419
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.847
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.90(7)
 0.10(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
C201 \\sim C206 \\sim C205 \\sim C204 \\sim C203 \\sim C202: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C31(H31)
4.b Secondary CH2 refined with riding coordinates:
 C21(H21B,H21A)
4.c Aromatic/amide H refined with riding coordinates:
 N21(H21), C206(H206), C202(H202), C205(H205), C203(H203), C204(H204)
4.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C22(H22A,H22B,H22C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              54054
_shelx_hkl_checksum              54429
_shelx_fab_checksum              77449
_olex2_submission_special_instructions 'No special instructions were received'