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_4032493
_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         'C60 H58 Br4 N4 S4'
_chemical_formula_sum            'C60 H58 Br4 N4 S4'
_chemical_formula_weight         1282.98
_chemical_name_systematic
5,10,15,20-tetrakis((4-bromophenyl)thio)-2,3,7,8,12,13,17,18-octaethylporphyrin
_space_group_crystal_system      tetragonal
_space_group_IT_number           114
_space_group_name_Hall           'P -4 2n'
_space_group_name_H-M_alt        'P -4 21 c'
_symmetry_space_group_name_Hall  'P -4 2n'
_symmetry_space_group_name_H-M   'P -4 21 c'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-08-02
_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            2
_cell_length_a                   19.0974(9)
_cell_length_b                   19.0974(9)
_cell_length_c                   8.3204(4)
_cell_measurement_reflns_used    8855
_cell_measurement_temperature    100.02
_cell_measurement_theta_max      27.26
_cell_measurement_theta_min      2.38
_cell_volume                     3034.5(2)
_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      100.02
_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 1.000
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0281
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            27514
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.488
_diffrn_reflns_theta_min         1.508
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.830
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6088
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0765 before and 0.0563 after correction.
The Ratio of minimum to maximum transmission is 0.8165.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dark black'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       Block
_exptl_crystal_F_000             1300
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of acetone and water by slow evaporation'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.055
_refine_diff_density_min         -0.483
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.015(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     166
_refine_ls_number_reflns         3487
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0258P)^2^+3.0378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0700
_refine_ls_wR_factor_ref         0.0713
_reflns_Friedel_coverage         0.773
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3215
_reflns_number_total             3487
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b00328_si_002.cif
_cod_data_source_block           kjf096
_cod_depositor_comments
'Adding full bibliography for 4032493--4032500.cif.'
_cod_original_cell_volume        3034.5(3)
_cod_database_code               4032493
_shelx_estimated_absorpt_t_max   0.660
_shelx_estimated_absorpt_t_min   0.484
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.985(14) 0.015(14)
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. Others
 Fixed Sof: H21(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C81(H81A,H81B), C71(H71A,H71B)
4.b Aromatic/amide H refined with riding coordinates:
 C53(H53), C54(H54), C56(H56), C57(H57), N21(H21)
4.c Idealised Me refined as rotating group:
 C82(H82A,H82B,H82C), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              98099
_shelx_hkl_checksum              86896
_shelx_fab_checksum              23820
_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 in oil'
_olex2_submission_special_instructions 'No special instructions were received'