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_7126718
_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         'C96 H34 F48 Mg N8 O, 2.5[C3H6O], 2.5[C6H14]'
_chemical_formula_sum            'C118.5 H84 F48 Mg N8 O3.5'
_chemical_formula_weight         2612.24
_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   mixed
_audit_creation_date             2020-06-15
_audit_creation_method
;
Olex2 1.3-dev
(compiled 2020.05.13 svn.r35546bd3 for OlexSys, GUI svn.r5830)
;
_audit_update_record
;
2020-06-16 deposited with the CCDC.	2020-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                104.367(8)
_cell_angle_beta                 101.254(8)
_cell_angle_gamma                97.571(10)
_cell_formula_units_Z            1
_cell_length_a                   9.3959(12)
_cell_length_b                   15.9579(18)
_cell_length_c                   19.8503(14)
_cell_measurement_reflns_used    1665
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      52.4200
_cell_measurement_theta_min      6.3580
_cell_volume                     2776.5(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.896
_diffrn_measured_fraction_theta_max 0.896
_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    -83.00 -34.00   1.00   10.00    --    0.00 178.00 150.00   49
  2  \w    -24.00  40.00   1.00   10.00    --    0.00  45.00  47.00   64
  3  \w     17.00  70.00   1.00   10.00    --    0.00  37.00  90.00   53
  4  \w     68.00 118.00   1.00   50.00    --   66.68  57.00 -90.00   50
  5  \w     30.00  92.00   1.00   50.00    --   66.68 -57.00   0.00   62
  6  \w     32.00 145.00   1.00   50.00    --   66.68  19.00-120.00  113
  7  \w     63.00 140.00   1.00   50.00    --   66.68  37.00 120.00   77
  8  \w     31.00  68.00   1.00   50.00    --   66.68-125.00   0.00   37
  9  \w     20.00  96.00   1.00   50.00    --   66.68 -77.00-150.00   76
 10  \w     56.00 122.00   1.00   50.00    --   66.68-125.00  30.00   66
 11  \w     -2.00  29.00   1.00   50.00    --   66.68 -37.00 -60.00   31
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1599365000
_diffrn_orient_matrix_UB_12      0.0062723000
_diffrn_orient_matrix_UB_13      0.0410054000
_diffrn_orient_matrix_UB_21      -0.0219194000
_diffrn_orient_matrix_UB_22      -0.1012990000
_diffrn_orient_matrix_UB_23      -0.0214035000
_diffrn_orient_matrix_UB_31      0.0541294000
_diffrn_orient_matrix_UB_32      0.0009909000
_diffrn_orient_matrix_UB_33      -0.0682765000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0646
_diffrn_reflns_av_unetI/netI     0.1172
_diffrn_reflns_Laue_measured_fraction_full 0.896
_diffrn_reflns_Laue_measured_fraction_max 0.896
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            10196
_diffrn_reflns_point_group_measured_fraction_full 0.896
_diffrn_reflns_point_group_measured_fraction_max 0.896
_diffrn_reflns_theta_full        54.312
_diffrn_reflns_theta_max         54.312
_diffrn_reflns_theta_min         4.734
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.393
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42814
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_description       plate
_exptl_crystal_F_000             1442
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.843
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.962
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     867
_refine_ls_number_reflns         6083
_refine_ls_number_restraints     389
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.1428
_refine_ls_R_factor_gt           0.0852
_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^)+(0.1598P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2260
_refine_ls_wR_factor_ref         0.2732
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3156
_reflns_number_total             6083
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc03161e2.cif
_cod_data_source_block           159aim17
_cod_depositor_comments
'Adding full bibliography for 7126716--7126723.cif.'
_cod_original_formula_sum        'C118.50 H84 F48 Mg N8 O3.50'
_cod_database_code               7126718
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.722
_reflns_odcompleteness_completeness 91.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     52.57
_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. Restrained distances
 C01J-F2
 1.328 with sigma of 0.02
 F01W-C01J
 1.328 with sigma of 0.02
 C023-F01Y
 1.328 with sigma of 0.02
 F3-C01J
 1.328 with sigma of 0.02
 C023-F024
 1.328 with sigma of 0.02
 C023-F01X
 1.328 with sigma of 0.02
 C023-F0
 1.328 with sigma of 0.02
 C023-F025
 1.328 with sigma of 0.02
 C023-F1
 1.328 with sigma of 0.02
 F01V-C01J
 1.328 with sigma of 0.02
 F01U-C01J
 1.328 with sigma of 0.02
 F007-C01J
 1.328 with sigma of 0.02
 Mg00-O1
 2 with sigma of 0.001
 C01R-F6 \\sim C01R-F5 \\sim C01R-F4
 with sigma of 0.02
3. Rigid bond restraints
 Mg00
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Mg00, O1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
F4 \\sim F5 \\sim F6 \\sim C01R: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
F013 \\sim C01R \\sim F00F \\sim F00B: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Mg00: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
Mg00 \\sim O1: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(F3A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F01W) \\sim Ueq, Uanis(F2A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F025) \\sim Ueq, Uanis(F0) \\sim Ueq, Uanis(F01X) \\sim Ueq, Uanis(F01Y)
\\sim Ueq, Uanis(F024) \\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F4) \\sim Ueq, Uanis(F6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 F00G, F01P, C01W, F021
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1A, F3A, F2A, C01S, F1B, F2B, F3B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5, F00B, F00F, F013, C01R, F4, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F01V, F2, F01W, F007, C01J, F01U, F3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C00N, C00J, C00Q, C00K, C00U, C011
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Mg00
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F01X, C023, F024, F025, F0, F01Y, F1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F002, F00I, F015, C022, F8, F00J, F9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F0)=Sof(F01Y)=Sof(F1)=1-FVAR(1)
 Sof(F01X)=Sof(F024)=Sof(F025)=FVAR(1)
 Sof(F2)=Sof(F01W)=Sof(F3)=1-FVAR(2)
 Sof(F007)=Sof(F01U)=Sof(F01V)=FVAR(2)
 Fixed Sof: F002(0.5) Mg00(0.5) F00B(0.70745) F1A(0.14319) F00F(0.70745)
 F00G(0.57209) F00I(0.5) F3A(0.14319) F013(0.70745) F015(0.5) F2A(0.14319)
 F01P(0.57209) F021(0.57209) F1B(0.85681) F2B(0.85681) F3B(0.85681) F4(0.29255)
 F5(0.29255) F6(0.29255) F7(0.42791) F01Q(0.42791) F00H(0.42791) F8(0.5)
 F00J(0.5) F9(0.5) O1(0.5) H1A(0.5) H1B(0.5)
7.a Riding coordinates:
 O1(H1A,H1B)
7.b Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C00M(H00M), C00T(H00T), C00V(H00V), C00X(H00X), C00Y(H00Y),
 C010(H010), C011(H011), C018(H018), C01F(H01F), C01G(H01G), C01K(H01K),
 C01N(H01N), C01O(H01O), C01Q(H01Q), C01Z(H01Z)
;
_smtbx_masks_special_details
'A solvent mask was calculated and 185 electrons were found in a volume of 736\%A^3^ in 2 voids per unit cell. This is consistent with the presence of 2.5[C3H6O], 2.5[C6H14] per Formula Unit which account for 205 electrons per unit cell. The electron count is short because the ligand water molecule is only present in one side of the disordered complex, and when it is *not* present, the acetone/hexane solvent fills the void. In order to mask this, the mask was first calculated *including* the bound water molecule and the electron count pointed towards an equal amount of acetone and hexane (plus the water). The final R1 of that masked structure was 7.77%. Since we do not want to lose the information that there *is* a water molecule, we re-calcuated the mask with the ligand in position. This makes it impossible for the mask to evaluate the residual density nearby that bound water molecule, leading to a lower electron count than expected. '
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              19865
_shelx_fab_checksum              84312
_olex2_submission_special_instructions 'No special instructions were received'