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_7126723
_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         'C99 H35 F48 N8.6 O0.5 Zn, 6(C5 H5 N)'
_chemical_formula_sum            'C129 H65 F48 N14.6 O0.5 Zn'
_chemical_formula_weight         2804.72
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-06-08
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.05.22 svn.r1d9e7f8d for OlexSys, GUI svn.r6115)
;
_audit_update_record
;
2020-06-08 deposited with the CCDC.	2020-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                104.0668(18)
_cell_angle_beta                 102.2170(17)
_cell_angle_gamma                94.6532(19)
_cell_formula_units_Z            1
_cell_length_a                   9.8387(6)
_cell_length_b                   15.9659(11)
_cell_length_c                   19.7070(13)
_cell_measurement_reflns_used    9943
_cell_measurement_temperature    120
_cell_measurement_theta_max      26.61
_cell_measurement_theta_min      2.53
_cell_volume                     2906.0(3)
_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 1.3-alpha (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 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  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1095
_diffrn_reflns_av_unetI/netI     0.0665
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            83083
_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         25.998
_diffrn_reflns_theta_min         1.935
_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    0.350
_exptl_absorpt_correction_T_max  0.9689
_exptl_absorpt_correction_T_min  0.7980
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1291 before and 0.0814 after correction. The Ratio of minimum to maximum transmission is 0.8236. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.603
_exptl_crystal_description       plate
_exptl_crystal_F_000             1407
_exptl_crystal_preparation       'cut from a larger crystal'
_exptl_crystal_size_max          0.366
_exptl_crystal_size_mid          0.353
_exptl_crystal_size_min          0.185
_refine_diff_density_max         0.772
_refine_diff_density_min         -0.595
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1072
_refine_ls_number_reflns         11412
_refine_ls_number_restraints     240
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.1163
_refine_ls_R_factor_gt           0.0718
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0877P)^2^+6.4935P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1728
_refine_ls_wR_factor_ref         0.2016
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7658
_reflns_number_total             11412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc03161e2.cif
_cod_data_source_block           ke067
_cod_depositor_comments
'Adding full bibliography for 7126716--7126723.cif.'
_cod_original_formula_sum        'C129 H65 F48 N14.60 O0.50 Zn'
_cod_database_code               7126723
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Shared sites
{N3, O2}
3. Restrained distances
 F13A-C74A
 1.328 with sigma of 0.02
 C74-F80
 1.328 with sigma of 0.02
 F80A-C74A
 1.328 with sigma of 0.02
 C74-F12
 1.328 with sigma of 0.02
 F12A-C74A
 1.328 with sigma of 0.02
 C74-F13
 1.328 with sigma of 0.02
 F1-C62
 1.328 with sigma of 0.02
 F1A-C62
 1.328 with sigma of 0.02
 F0AB-C62
 1.328 with sigma of 0.02
 F1AA-C62
 1.328 with sigma of 0.02
 F0AA-C62
 1.328 with sigma of 0.02
 F1AB-C62
 1.328 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C74 \\sim C74A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
F3AB \\sim F6 \\sim F6A \\sim F2AA \\sim F2AB \\sim F3AA: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C18) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(N0AA)
\\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.002
Uanis(C5) \\sim Ueq, Uanis(C1BA) \\sim Ueq, Uanis(C0BA) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C2BA) \\sim Ueq, Uanis(N2) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.002
Uanis(C2AA) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(N2AA) \\sim Ueq, Uanis(C6)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.002
Uanis(C5A) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4AB) \\sim Ueq, Uanis(C3AA)
\\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.002
Uanis(C74A) \\sim Ueq, Uanis(C74) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.002
Uanis(N1) \\sim Ueq, Uanis(C9AA) \\sim Ueq, Uanis(C5AA) \\sim Ueq, Uanis(C8AA)
\\sim Ueq, Uanis(C6AA) \\sim Ueq, Uanis(C7AA) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.002
Uanis(N3) = Uanis(O2)
5. Others
 Fixed Sof: F12(0.5) C74(0.5) F80(0.5) Zn1(0.5) F13(0.5) N0AA(0.7) C3(0.7)
 H3(0.7) C0AA(0.7) H0AA(0.7) C16(0.7) H16(0.7) C18(0.7) H18(0.7) C1AA(0.7)
 H1AA(0.7) C4(0.7) H4(0.7) C2AA(0.7) H2AA(0.7) C8(0.7) H8(0.7) N2AA(0.7)
 C6(0.7) H6(0.7) C7(0.7) H7(0.7) N1(0.3) C8AA(0.3) H8AA(0.3) C6AA(0.3)
 H6AA(0.3) C9AA(0.3) H9AA(0.3) C5AA(0.3) H5AA(0.3) C7AA(0.3) H7AA(0.3) F1(0.5)
 F1AA(0.5) F0AA(0.5) F0AB(0.5) F1AB(0.5) F1A(0.5) F12A(0.5) C74A(0.5) F80A(0.5)
 F13A(0.5) N3(0.3) C9(0.3) H9(0.3) C3AA(0.3) H3AA(0.3) C4AB(0.3) H4AB(0.3)
 C2(0.3) H2(0.3) C5A(0.3) H5A(0.3) F3AA(0.5) F2AA(0.5) F6(0.5) F3AB(0.5)
 F2AB(0.5) F6A(0.5) C1BA(0.3) H1BA(0.3) C0BA(0.3) H0BA(0.3) C14(0.3) H14(0.3)
 C2BA(0.3) H2BA(0.3) N2(0.3) H2c(0.3) C5(0.3) O2(0.25) H2a(0.25) H2b(0.25)
 H5(0.3)
6.a Rotating group:
 O2(H2a,H2b)
6.b Ternary CH refined with riding coordinates:
 C3AA(H3AA), C4AB(H4AB)
6.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C23(H23), C28(H28), C30(H30), C39(H39), C40(H40), C44(H44),
 C46(H46), C49(H49), C53(H53), C55(H55), C57(H57), C58(H58), C59(H59), C64(H64),
  C65(H65), C72(H72), C75(H75), C76(H76), C84(H84), C87(H87), C3(H3),
 C0AA(H0AA), C16(H16), C18(H18), C1AA(H1AA), C4(H4), C2AA(H2AA), C8(H8), C6(H6),
  C7(H7), C8AA(H8AA), C6AA(H6AA), C9AA(H9AA), C5AA(H5AA), C7AA(H7AA), C9(H9),
 C2(H2), C5A(H5A), C1BA(H1BA), C0BA(H0BA), C14(H14), C2BA(H2BA), C5(H5)
6.d Fitted hexagon refined as free rotating group:
 C4(C2AA,C8,N2AA,C6,C7), N3(C9,C3AA,C4AB,C2,C5A), C1BA(C0BA,C14,C2BA,N2,C5)
;
_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'