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_4038416
_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_formula_moiety         'C64 H68 N4 Ni, 2(C0.5 H Cl)'
_chemical_formula_sum            'C65 H70 Cl2 N4 Ni'
_chemical_formula_weight         1036.86
_chemical_name_systematic
'[2,7,12,17-tetraethyl-3,8,13,18-tetraisopropyl-5,10,15,20-tetraphenylporphyrinato] nickel(II) DCM solvate'
_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_Hall           '-P 4bc'
_space_group_name_H-M_alt        'P 42/n :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-15
_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            2
_cell_length_a                   14.6097(5)
_cell_length_b                   14.6097(5)
_cell_length_c                   15.4733(5)
_cell_measurement_reflns_used    9505
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.63
_cell_measurement_theta_min      3.02
_cell_volume                     3302.67(19)
_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                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.12
_diffrn_detector_type            'Bruker APEX2 area detector'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    '0.5 mm double-pinhole'
_diffrn_radiation_detector       'Bruker APEX2 area detector'
_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  0.0495
_diffrn_reflns_av_unetI/netI     0.0156
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            70820
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        66.647
_diffrn_reflns_theta_max         66.647
_diffrn_reflns_theta_min         4.162
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.443
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6453
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0861 before and 0.0720 after correction. The Ratio of minimum to maximum transmission is 0.8572. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.043
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Block
_exptl_crystal_F_000             1100
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.949
_refine_diff_density_min         -0.757
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     173
_refine_ls_number_reflns         2906
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0777
_refine_ls_R_factor_gt           0.0770
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1137P)^2^+6.5808P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2202
_refine_ls_wR_factor_ref         0.2208
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2854
_reflns_number_total             2906
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00798_si_004.cif
_cod_data_source_block           kjf255
_cod_original_cell_volume        3302.7(2)
_cod_original_sg_symbol_H-M      'P 42/n'
_cod_database_code               4038416
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.761
_shelx_estimated_absorpt_t_min   0.761
_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. Uiso/Uaniso restraints and constraints
C1S: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1S) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
3. Others
 Fixed Sof: Cl1S(0.5) C1S(0.25) H1SA(0.25) H1SB(0.25)
4.a Ternary CH refined with riding coordinates:
 C31(H31)
4.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C1S(H1SA,H1SB)
4.c Aromatic/amide H refined with riding coordinates:
 C202(H202), C206(H206), C203(H203), C205(H205), C204(H204)
4.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              85149
_shelx_hkl_checksum              48578
_shelx_fab_checksum              86410
_olex2_submission_special_instructions 'No special instructions were received'