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_7126720
_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         'C144 H176 N8 Zn, C144 H178 N8 O Zn'
_chemical_formula_sum            'C288 H354 N16 O Zn2'
_chemical_formula_weight         4186.59
_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             2020-06-17
_audit_creation_method
;
Olex2 1.3-dev
(compiled 2020.05.13 svn.r35546bd3 for OlexSys, GUI svn.r5830)
;
_audit_update_record
;
2020-06-17 deposited with the CCDC.	2020-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                99.467(3)
_cell_angle_beta                 111.596(2)
_cell_angle_gamma                95.906(2)
_cell_formula_units_Z            1
_cell_length_a                   19.5182(8)
_cell_length_b                   19.5876(9)
_cell_length_c                   22.5521(9)
_cell_measurement_reflns_used    4660
_cell_measurement_temperature    120
_cell_measurement_theta_max      48.89
_cell_measurement_theta_min      2.32
_cell_volume                     7781.0(6)
_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-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    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      120.0
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.2699
_diffrn_reflns_av_unetI/netI     0.2307
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            101564
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         76.104
_diffrn_reflns_theta_min         2.159
_exptl_absorpt_coefficient_mu    0.537
_exptl_absorpt_correction_T_max  0.9825
_exptl_absorpt_correction_T_min  0.8168
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0816 before and 0.0646 after correction.
The Ratio of minimum to maximum transmission is 0.8313.
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    0.893
_exptl_crystal_description       plate
_exptl_crystal_F_000             2262
_exptl_crystal_recrystallization_method
'Crystallised by slow evaporation from acetone'
_exptl_crystal_size_max          0.241
_exptl_crystal_size_mid          0.221
_exptl_crystal_size_min          0.144
_refine_diff_density_max         0.645
_refine_diff_density_min         -0.362
_refine_diff_density_rms         0.073
_refine_ls_extinction_coef       0.00074(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.993
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1438
_refine_ls_number_reflns         31289
_refine_ls_number_restraints     1354
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.2863
_refine_ls_R_factor_gt           0.1402
_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^)+(0.1842P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3666
_refine_ls_wR_factor_ref         0.4498
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8419
_reflns_number_total             31289
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc03161e2.cif
_cod_data_source_block           ke070
_cod_depositor_comments
'Adding full bibliography for 7126716--7126723.cif.'
_cod_database_code               7126720
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.882
_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. Uiso/Uaniso restraints and constraints
Uanis(C03Y) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C1AA) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C2AA) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Fixed Sof: Zn02(0.5) O046(0.5) H04D(0.5) H04E(0.5)
5.a Riding coordinates:
 C045(H04S,H04R,H04T), C3(H3A,H3B,H3C), C1AA(H1AA,H1AB,H1AC), C2AA(H2AA,H2AB,
 H2AC), C9(H9A,H9B,H9C)
5.b Rotating group:
 O046(H04D,H04E)
5.c Aromatic/amide H refined with riding coordinates:
 C00D(H00D), C00H(H00H), C00I(H00I), C00L(H00L), C00N(H00N), C00P(H00P),
 C00S(H00S), C00V(H00V), C00X(H00X), C00Y(H00Y), C010(H010), C017(H017),
 C01C(H01C), C01G(H01G), C01H(H01H), C01I(H01I), C01J(H01J), C01L(H01L),
 C01O(H01O), C01P(H01P), C01T(H01T), C01Y(H01Y), C023(H023), C026(H026),
 C027(H027), C029(H029), C02D(H02T), C02G(H02G), C02H(H02H), C02J(H02J),
 C02Q(H02Q), C02X(H02X)
5.d Idealised Me refined as rotating group:
 C022(H02P,H02R,H02S), C02F(H02A,H02B,H02C), C02K(H02D,H02E,H02F), C02L(H02U,
 H02V,H02W), C02U(H02Y,H,HA), C02W(H02I,H02K,H02L), C02Z(H02M,H02N,H02O),
 C032(H1,HB,HC), C034(H03A,H03B,H03C), C035(H2,HD,HE), C036(H03D,H03E,H03F),
 C037(H3,HF,HG), C038(H4,HH,HI), C039(H03G,H03H,H03I), C03A(H03J,H03K,H03L),
 C03B(H03M,H03N,H03O), C03C(H5,HJ,HK), C03D(H6,HL,HM), C03F(H7,HN,HO), C03G(H8,
 HP,HQ), C03J(H03P,H03Q,H03R), C03K(H03S,H03T,H03U), C03L(H9,HR,HS), C03M(H03V,
 H03W,H03X), C03O(H10,HT,HU), C03P(H11,HV,HW), C03Q(H03Y,HX,HY), C03T(H12,HZ,
 H16), C03U(H13,H17,H18), C03W(H03Z,H19,H20), C03X(H14,H21,H22), C03Y(H15,H23,
 H24), C03Z(H03,H25,H26), C040(H04I,H04J,H04K), C041(H04A,H04B,H04C), C042(H04L,
 H04M,H04N), C044(H04O,H04P,H04Q), C048(H04F,H04G,H04H), C049(H04U,H04V,H04W),
 C04A(H04X,H04Y,H27), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C0AA(H0AA,H0AB,H0AC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              5929
_shelx_fab_checksum              25206
_olex2_submission_special_instructions 'No special instructions were received'