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_1567466
_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         'C90 H66 N6 O6, 1(C5 H12)'
_chemical_formula_sum            'C95 H78 N6 O6'
_chemical_formula_weight         1399.63
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc29lnsc
_audit_creation_date             2020-03-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-01-07 deposited with the CCDC.	2022-07-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   22.2142(14)
_cell_length_b                   22.2142(14)
_cell_length_c                   12.977(2)
_cell_measurement_reflns_used    1146
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      26.7320
_cell_measurement_theta_min      1.8510
_cell_volume                     5545.8(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_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    -13.00  93.00   0.50   30.00    --   13.83  51.00 118.00  212
  2  \w     39.00  90.00   0.50   30.00    --   13.83 179.00  60.00  102
  3  \w    -14.00  13.00   0.50   30.00    --  -13.44 -99.00   0.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0160960000
_diffrn_orient_matrix_UB_12      0.0325148000
_diffrn_orient_matrix_UB_13      0.0259599000
_diffrn_orient_matrix_UB_21      0.0164553000
_diffrn_orient_matrix_UB_22      0.0168694000
_diffrn_orient_matrix_UB_23      -0.0465261000
_diffrn_orient_matrix_UB_31      -0.0287752000
_diffrn_orient_matrix_UB_32      0.0042298000
_diffrn_orient_matrix_UB_33      -0.0122944000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0965
_diffrn_reflns_av_unetI/netI     0.1277
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            6084
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.992
_diffrn_reflns_theta_max         24.992
_diffrn_reflns_theta_min         1.833
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17257
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.39a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       block
_exptl_crystal_F_000             2214
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.639
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.988
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         2175
_refine_ls_number_restraints     58
_refine_ls_restrained_S_all      0.979
_refine_ls_R_factor_all          0.1804
_refine_ls_R_factor_gt           0.0815
_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^)+(0.1229P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1882
_refine_ls_wR_factor_ref         0.2443
_reflns_Friedel_coverage         0.000
_reflns_number_gt                981
_reflns_number_total             2175
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02647c2.cif
_cod_data_source_block           2
_cod_original_cell_volume        5545.8(12)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1567466
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C90 O6 N6 H66'
_chemical_oxdiff_usercomment     20190408_segawa_red
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.999
_diffrn_oxdiff_digest_frames
;
0155a7a6fabe68e3e68c7c22d7e59127fc003687e3e
;
_diffrn_oxdiff_digest_hkl
;
01509a61b05309931a7bf7e786ce2bc8d0c813
;
_reflns_odcompleteness_completeness 99.84
_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
 C19-C17
 2.54 with sigma of 0.02
 C17-C16 = C18-C17 = C19-C18 = C20-C19
 1.54 with sigma of 0.01
 C20-C18
 2.54 with sigma of 0.02
 C18-C16
 2.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of 0.03 and sigma for terminal
atoms of 0.03
4. Rigid body (RIGU) restrains
 C16, C17, C18, C19, C20
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Others
 Fixed Sof: C16(0.16667) H16A(0.16667) H16B(0.16667) H16C(0.16667)
 C17(0.16667) H17A(0.16667) H17B(0.16667) C18(0.16667) H18A(0.16667)
 H18B(0.16667) C19(0.16667) H19A(0.16667) H19B(0.16667) C20(0.16667)
 H20A(0.16667) H20B(0.16667) H20C(0.16667)
6.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B)
6.b Me refined with riding coordinates:
 C16(H16A,H16B,H16C), C20(H20A,H20B,H20C)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C7(H7), C10(H10), C11(H11), C13(H13), C14(H14)
6.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              15366
_shelx_hkl_checksum              15635
_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 4.191
_oxdiff_exptl_absorpt_empirical_full_min 0.375