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_7126717
_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         '0.5(C28 H30 B2 N4 O4), 2(H0.5 O0.13)'
_chemical_formula_sum            'C14 H16 B N2 O2.25'
_chemical_formula_weight         259.10
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-05
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2020-03-11 deposited with the CCDC.	2020-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.6432(10)
_cell_length_b                   6.8628(5)
_cell_length_c                   7.9989(3)
_cell_measurement_reflns_used    2541
_cell_measurement_temperature    120
_cell_measurement_theta_max      22.4360
_cell_measurement_theta_min      2.9510
_cell_volume                     1462.57(13)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7c (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7c (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7c (Rigaku OD, 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    'ShelXS (Sheldrick, 2008)'
_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 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -15.57 158.83   0.80    8.00    --    7.38  73.77  -0.09  218
  2  \w    -15.57 158.83   0.80    8.00    --    7.38  73.77 -63.06  218
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0219111000
_diffrn_orient_matrix_UB_12      -0.0354954000
_diffrn_orient_matrix_UB_13      0.0400967000
_diffrn_orient_matrix_UB_21      0.0134502000
_diffrn_orient_matrix_UB_22      -0.0079126000
_diffrn_orient_matrix_UB_23      0.0762142000
_diffrn_orient_matrix_UB_31      -0.0069271000
_diffrn_orient_matrix_UB_32      0.0967257000
_diffrn_orient_matrix_UB_33      0.0211443000
_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  0.0420
_diffrn_reflns_av_unetI/netI     0.0169
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            15027
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.659
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62411
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7c (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_description       plate
_exptl_crystal_F_000             548
_exptl_crystal_preparation       'Cut from a larger crystal'
_exptl_crystal_recrystallization_method 'Crystallised from methanol solution'
_exptl_crystal_size_max          0.391
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.164
_refine_diff_density_max         0.505
_refine_diff_density_min         -0.419
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     145
_refine_ls_number_reflns         1406
_refine_ls_number_restraints     177
_refine_ls_restrained_S_all      1.138
_refine_ls_R_factor_all          0.0968
_refine_ls_R_factor_gt           0.0749
_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^)+(0.0933P)^2^+1.8580P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1924
_refine_ls_wR_factor_ref         0.2123
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1056
_reflns_number_total             1406
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc03161e2.cif
_cod_data_source_block           mo_ke043
_cod_depositor_comments
'Adding full bibliography for 7126716--7126723.cif.'
_cod_database_code               7126717
_reflns_odcompleteness_completeness 92.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.58
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C13-C12 \\sim C12-C14 \\sim C11-C9 \\sim C10-C9
 with sigma of 0.01
 C13-C14 \\sim C10-C11
 with sigma of 0.01
3. Restrained planarity
 O2, B1, O1, C9, C12
 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C4, C3, C5, C2, H3, C6, H5, C8, C1, H6, N2, C7, N1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, O1, C9, C12, B1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O2, O1, C9, C12, C13, C11, B1, C14, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Fixed Sof: O2(0.5) O1(0.5) C9(0.5) C12(0.5) C13(0.5) H13A(0.5) H13B(0.5)
 H13C(0.5) C11(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C14(0.5) H14A(0.5) H14B(0.5)
 H14C(0.5) C10(0.5) H10A(0.5) H10B(0.5) H10C(0.5) O3(0.125) H3A(0.25) H3B(0.25)
7.a Riding coordinates:
 C13(H13A,H13B,H13C), C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C10(H10A,H10B,
 H10C), O3(H3A,H3B)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C5(H5)
;
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method
'crystal soaked in perfluoro polyether oil and mounted on MiTeGen sample holder directly into the pre-cooled cryostream'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.481
_oxdiff_exptl_absorpt_empirical_full_min 0.656