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_4032500
_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         'C36 H43 N7 O6'
_chemical_formula_sum            'C36 H43 N7 O6'
_chemical_formula_weight         669.77
_chemical_name_systematic
2,3,7,8,12,13,17,18-octaethyl-5,10,15-trinitroporphyrin
_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             2017-01-03
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6656(11)
_cell_length_b                   13.9561(17)
_cell_length_c                   27.365(3)
_cell_measurement_reflns_used    9010
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.18
_cell_measurement_theta_min      2.47
_cell_volume                     3309.5(7)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device       'Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0572
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            45306
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.240
_diffrn_reflns_theta_min         1.488
_diffrn_source                   'sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.093
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5508
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0997 before and 0.0653 after correction.
The Ratio of minimum to maximum transmission is 0.7388.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       Block
_exptl_crystal_F_000             1424
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and methanol by slow evaporation'
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.243
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 2588 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     458
_refine_ls_number_reflns         7236
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0458P)^2^+1.3167P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0966
_refine_ls_wR_factor_ref         0.1000
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                6536
_reflns_number_total             7236
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b00328_si_002.cif
_cod_data_source_block           kjf030_a1
_cod_depositor_comments
'Adding full bibliography for 4032493--4032500.cif.'
_cod_database_code               4032500
_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:
 C21(H21A,H21B), C31(H31A,H31B), C71(H71A,H71B), C81(H81A,H81B), C121(H12A,
 H12B), C131(H13A,H13B), C171(H17A,H17B), C181(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C20(H20)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C32(H32A,H32B,H32C), C72(H72A,H72B,H72C), C82(H82A,H82B,
 H82C), C122(H12C,H12D,H12E), C132(H13C,H13D,H13E), C172(H17C,H17D,H17E),
 C182(H18C,H18D,H18E)
;
_shelx_res_checksum              17742
_shelx_hkl_checksum              74987
_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 with oil'
_olex2_submission_special_instructions 'No special instructions were received'