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_4032496
_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_formula_moiety         '0.8(C76 H70 N4 S4), 0.2(C66 H64 N4 S4)'
_chemical_formula_sum            'C74 H68.8 N4 S4'
_chemical_formula_weight         1142.37
_chemical_name_systematic
;
2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetrakis(naphthyl-2-ylthio)porphyrin
and 2,3,7,8,12,13,17,18-octaethyl-10,15,20-tri(naphthyl-2-ylthio)- 
5-thiolporphyrin
;
_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'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_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                 97.683(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4050(5)
_cell_length_b                   29.2714(9)
_cell_length_c                   15.8470(5)
_cell_measurement_reflns_used    9283
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.07
_cell_measurement_theta_min      3.10
_cell_volume                     6622.0(4)
_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      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1082
_diffrn_reflns_av_unetI/netI     0.0860
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            69543
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.42
_diffrn_reflns_theta_min         1.51
_diffrn_source                   'sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.647
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6689
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1094 before and 0.0772 after correction.
The Ratio of minimum to maximum transmission is 0.8882.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.146
_exptl_crystal_description       Needle
_exptl_crystal_F_000             2419
_exptl_crystal_recrystallization_method
;
The material was recrystallised from a mixture of DCM and 
methanol by solvent layering'
;
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.846
_refine_diff_density_min         -0.450
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     802
_refine_ls_number_reflns         12120
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0944
_refine_ls_R_factor_gt           0.0678
_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^)+(0.1082P)^2^+3.4336P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1843
_refine_ls_wR_factor_ref         0.2054
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8598
_reflns_number_total             12120
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b00328_si_002.cif
_cod_data_source_block           kjf109b_a
_cod_depositor_comments
'Adding full bibliography for 4032493--4032500.cif.'
_cod_original_formula_sum        'C74 H68.80 N4 S4'
_cod_database_code               4032496
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.827
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All S(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C212) \\sim Ueq, Uanis(C213) \\sim Ueq, Uanis(C214) \\sim Ueq,
Uanis(C207) \\sim Ueq, Uanis(C206) \\sim Ueq, Uanis(C205) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
3. Others
 Fixed Sof: C152(0.8) C153(0.8) H153(0.8) C154(0.8) C155(0.8) H155(0.8)
 C156(0.8) H156(0.8) C157(0.8) H157(0.8) C158(0.8) H158(0.8) C159(0.8)
 C160(0.8) H160(0.8) C161(0.8) H161(0.8) H210(0.61) H208(0.61) H20A(0.39)
 C207(0.61) H207(0.61) C206(0.61) H206(0.61) C205(0.61) H205(0.61) H204(0.39)
 C212(0.39) H212(0.39) C213(0.39) H213(0.39) C214(0.39) H214(0.39) S151(0.8)
 S1(0.2) H1(0.2)
4.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)
4.b Aromatic/amide H refined with riding coordinates:
 C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59), C61(H61),
 C111(H111), C110(H110), C108(H108), C107(H107), C106(H106), C105(H105),
 C103(H103), C153(H153), C155(H155), C156(H156), C157(H157), C158(H158),
 C160(H160), C161(H161), C211(H211), C210(H210), C208(H208), C208(H20A),
 C207(H207), C206(H206), C205(H205), C204(H204), C203(H203), C212(H212),
 C213(H213), C214(H214), N21(H21), N23(H23)
4.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)
4.d Idealised tetrahedral OH refined as rotating group:
 S1(H1)
;
_shelx_res_checksum              52886
_shelx_hkl_checksum              54188
_shelx_fab_checksum              42324
_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'