N-doped nonalternant aromatic belt via a six-fold annulative double N-arylation
Sato, Hiroki; Suizu, Rie; Kato, Tomoki; Yagi, Akiko; Segawa, Yasutomo; Awaga, Kunio; Itami, Kenichiro; Chemical Science  (2022) –; doi:10.1039/D2SC02647C

data_1567467
_publ_section_title
;
 N-doped nonalternant aromatic belt via a six-fold annulative double
 N-arylation
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC02647C
_journal_year                    2022
_chemical_formula_moiety
'B C24 F20, C45 H32.5 N3 O3, 2(C0.5 H Cl), 1.5(C6 H14)'
_chemical_formula_sum            'C79 H55.5 B Cl2 F20 N3 O3'
_chemical_formula_weight         1556.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc29lntd
_audit_creation_date             2021-09-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6403)
;
_audit_update_record
;
2022-01-07 deposited with the CCDC.	2022-07-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.618(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   32.5289(11)
_cell_length_b                   13.8777(4)
_cell_length_c                   32.5269(15)
_cell_measurement_reflns_used    13731
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      30.4500
_cell_measurement_theta_min      2.5960
_cell_volume                     14585.7(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.921
_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   -110.00  70.00   0.30   48.00    --  -20.00  45.00   0.00  600
  2  \w   -110.00  70.00   0.30   48.00    --  -20.00  45.00  90.00  600
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0006505000
_diffrn_orient_matrix_UB_12      -0.0470099000
_diffrn_orient_matrix_UB_13      0.0084445000
_diffrn_orient_matrix_UB_21      0.0218678000
_diffrn_orient_matrix_UB_22      -0.0029850000
_diffrn_orient_matrix_UB_23      0.0011870000
_diffrn_orient_matrix_UB_31      0.0017569000
_diffrn_orient_matrix_UB_32      0.0198053000
_diffrn_orient_matrix_UB_33      0.0202419000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0908
_diffrn_reflns_av_unetI/netI     0.1586
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.921
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            68811
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         31.260
_diffrn_reflns_theta_min         2.394
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.192
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77327
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.418
_exptl_crystal_description       needle
_exptl_crystal_F_000             6348
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.961
_refine_diff_density_min         -1.030
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1017
_refine_ls_number_reflns         21919
_refine_ls_number_restraints     152
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.2728
_refine_ls_R_factor_gt           0.1162
_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^)+(0.1966P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3059
_refine_ls_wR_factor_ref         0.3935
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7841
_reflns_number_total             21919
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02647c2.cif
_cod_data_source_block           2dication
_cod_original_formula_sum        'C79 H55.50 B Cl2 F20 N3 O3'
_cod_database_code               1567467
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C163 H124 B2 Cl2 F40 N6 O6'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C83-C82 = C82-C81 = C81-C80 = C79-C80 = C79-C78
 1.56 with sigma of 0.01
 Cl3-C71 = Cl2-C71
 1.76 with sigma of 0.01
 C80-C78
 2.56 with sigma of 0.03
 Cl3-Cl2
 2.87 with sigma of 0.02
 C81-C79
 2.56 with sigma of 0.03
 C83-C81
 2.56 with sigma of 0.03
 C82-C80
 2.56 with sigma of 0.03
 C75-C76 = C75-C74 = C72-C73
 1.56 with sigma of 0.01
 C74-C72
 2.56 with sigma of 0.02
 C76-C77
 1.56 with sigma of 0.01
 C77-C75
 2.56 with sigma of 0.02
 C76-C74
 2.56 with sigma of 0.02
 C75-C73
 2.56 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C71) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(C78) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C81)
\\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C76) \\sim Ueq,
Uanis(C75) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C72)
\\sim Ueq, Uanis(C77) \\sim Ueq: with sigma of 0.02 and sigma for terminal
atoms of 0.02
4. Rigid body (RIGU) restrains
 C78, C79, C80, C81, C82, C83, C76, C75, C74, C73, C72, C77
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H23(0.5) H70A(0.5) H70B(0.5) C78(0.5) H78A(0.5) H78B(0.5)
 H78C(0.5) C79(0.5) H79A(0.5) H79B(0.5) C80(0.5) H80A(0.5) H80B(0.5) C81(0.5)
 H81A(0.5) H81B(0.5) C82(0.5) H82A(0.5) H82B(0.5) C83(0.5) H83A(0.5) H83B(0.5)
 H83C(0.5) Cl2(0.5) Cl3(0.5) C71(0.5) H71A(0.5) H71B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C70(H70A,H70B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,
 H82B), C76(H76A,H76B), C75(H75A,H75B), C74(H74A,H74B), C73(H73A,H73B),
 C71(H71A,H71B)
6.b Me refined with riding coordinates:
 C78(H78A,H78B,H78C), C83(H83A,H83B,H83C), C72(H72A,H72B,H72C), C77(H77A,H77B,
 H77C)
6.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C12(H12), C4(H4), C7(H7), C8(H8), C23(H23), C20(H20), C9(H9),
 C16(H16), C17(H17), C37(H37), C33(H33), C34(H34), C29(H29), C30(H30), C36(H36),
  C26(H26), C27(H27), C40(H40), C1(H1), C24(H24), C44(H44), C43(H43), C41(H41)
6.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C38(H38A,H38B,H38C), C45(H45A,H45B,H45C)
;
_shelx_res_checksum              17395
_shelx_hkl_checksum              59330
_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 1.218
_oxdiff_exptl_absorpt_empirical_full_min 0.846