Synthesis of a Family of Highly Substituted Porphyrin Thioethers via Nitro Displacement in 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetranitroporphyrin.
Kielmann, Marc; Flanagan, Keith J.; Norvaiša, Karolis; Intrieri, Daniela; Senge, Mathias O.; The Journal of organic chemistry 82 (2017) 5122–5134; doi:10.1021/acs.joc.7b00328

data_4032495
_publ_section_title
;
 Synthesis of a Family of Highly Substituted Porphyrin Thioethers via
 Nitro Displacement in
 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetranitroporphyrin.
;
_journal_issue                   10
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5122
_journal_page_last               5134
_journal_paper_doi               10.1021/acs.joc.7b00328
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C56 H58 N8 S4'
_chemical_formula_sum            'C56 H58 N8 S4'
_chemical_formula_weight         971.34
_chemical_name_systematic
2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(pyridin-2-ylthio)porphyrin
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2016-07-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.7585(5)
_cell_length_b                   23.2617(14)
_cell_length_c                   24.6838(14)
_cell_measurement_reflns_used    8258
_cell_measurement_temperature    100.01
_cell_measurement_theta_max      68.118
_cell_measurement_theta_min      3.581
_cell_volume                     5029.0(5)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker, 2014)'
_computing_data_collection       'APEX2 Ver. v.7-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker, 2014)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.258
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1181
_diffrn_reflns_av_unetI/netI     0.0694
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            60358
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.585
_diffrn_reflns_theta_min         3.581
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.095
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.2715
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1484 before and 0.1175 after correction.
The Ratio of minimum to maximum transmission is 0.3605.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       needle
_exptl_crystal_F_000             2056
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of acetone and water by slow evaporation'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.664
_refine_diff_density_min         -0.653
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Flack x determined using 3112 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     629
_refine_ls_number_reflns         9224
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0736
_refine_ls_R_factor_gt           0.0656
_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^)+(0.1231P)^2^+0.5589P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1695
_refine_ls_wR_factor_ref         0.1773
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                8107
_reflns_number_total             9224
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b00328_si_002.cif
_cod_data_source_block           kjf106a_a
_cod_depositor_comments
'Adding full bibliography for 4032493--4032500.cif.'
_cod_database_code               4032495
_shelx_estimated_absorpt_t_max   0.818
_shelx_estimated_absorpt_t_min   0.421
_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
2.a Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C33(H33A,H33B), C37(H37A,H37B), C29(H29A,H29B), C31(H31A,
 H31B), C27(H27A,H27B), C25(H25A,H25B), C35(H35A,H35B)
2.b Aromatic/amide H refined with riding coordinates:
 C152(H152), C52(H52), C102(H102), C202(H202), C55(H55), C105(H105), C53(H53),
 C204(H204), C54(H54), C203(H203), C103(H103), C104(H104), C205(H205),
 C155(H155), C153(H153), C154(H154)
2.c Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C30(H30A,H30B,H30C), C40(H40A,H40B,H40C), C34(H34A,H34B,
 H34C), C26(H26A,H26B,H26C), C36(H36A,H36B,H36C), C32(H32A,H32B,H32C), C28(H28A,
 H28B,H28C)
;
_shelx_res_checksum              10271
_shelx_hkl_checksum              51025
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN micromount oil'
_olex2_submission_special_instructions 'No special instructions were received'