Iridium-catalysed 3,5-bis-borylation of phthalonitrile enables access to a family of C<sub>4h</sub> octaarylphthalocyanines.
Mulholland, Katie D.; Yoon, Sangbin; Rennie, Christopher C.; Sitch, Eleanor K.; McKay, Alasdair I.; Edkins, Katharina; Edkins, Robert M.; Chemical communications (Cambridge, England) 56 (2020) 8452–8455; doi:10.1039/d0cc03161e

data_7126722
_publ_section_title
;
 Iridium-catalysed 3,5-bis-borylation of phthalonitrile enables access to
 a family of C<sub>4h</sub> octaarylphthalocyanines.
;
_journal_issue                   60
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              8452
_journal_page_last               8455
_journal_paper_doi               10.1039/d0cc03161e
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C24 H8 F12 N2, 0.5[C6H14]'
_chemical_formula_sum            'C27 H15 F12 N2'
_chemical_formula_weight         595.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-06-09
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.05.22 svn.r1d9e7f8d for OlexSys, GUI svn.r6115)
;
_audit_update_record
;
2020-06-09 deposited with the CCDC.	2020-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.7836(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.3200(12)
_cell_length_b                   8.4133(4)
_cell_length_c                   22.4036(10)
_cell_measurement_reflns_used    9927
_cell_measurement_temperature    120
_cell_measurement_theta_max      26.81
_cell_measurement_theta_min      2.32
_cell_volume                     4935.8(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEXII (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      120
_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 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    '0.3 x 1.5 Double Pinhole'
_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  0.0422
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            34315
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.794
_diffrn_reflns_theta_min         2.277
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.158
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9122
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0745 before and 0.0501 after correction. The Ratio of minimum to maximum transmission is 0.9122. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.603
_exptl_crystal_description       prism
_exptl_crystal_F_000             2392
_exptl_crystal_preparation       'Cut from a larger crystal'
_exptl_crystal_recrystallization_method
'Crystallise from hexane/dichloromethane solution by slow cooling'
_exptl_crystal_size_max          0.288
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.201
_refine_diff_density_max         0.448
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         5262
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0474
_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^)+(0.0521P)^2^+8.4179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1128
_refine_ls_wR_factor_ref         0.1225
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4178
_reflns_number_total             5262
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc03161e2.cif
_cod_data_source_block           ke060
_cod_depositor_comments
'Adding full bibliography for 7126716--7126723.cif.'
_cod_database_code               7126722
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C5-F4 = C5-F5 = C5-F6 = C5-F4A = C5-F5A = C5-F6A
 1.328 with sigma of 0.02
 F4-F5 = F4-F6 = F5-F6
 2.125 with sigma of 0.02
 F4A-F5A = F4A-F6A = F5A-F6A
 2.125 with sigma of 0.02
 C5-F5 \\sim C5-F4 \\sim C5-F6 \\sim C5-F5A \\sim C5-F4A \\sim C5-F6A
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(F6) \\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(F5A) \\sim Ueq, Uanis(F5)
\\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Sof(F3A)=Sof(C1A)=Sof(F1A)=Sof(F2A)=1-FVAR(1)
 Sof(C1)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Fixed Sof: F5(0.5) F4(0.5) F6(0.5) F4A(0.5) F5A(0.5) F6A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C6(H6), C18(H18), C22(H22), C10(H10), C20(H20), C4(H4), C8(H8)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_exptl_crystal_mounting_method
'Crystal soaked in perfluoro polyether oil and mounted on a MiTeGen sample holder directly into the pre-cooled cryostream'
_olex2_submission_special_instructions 'No special instructions were received'