Substituent effects on paratropicity and diatropicity in π-extended hexapyrrolohexaazacoronene
Takase, Masayoshi; Takata, Toranosuke; Oki, Kosuke; Mori, Shigeki; Uno, Hidemitsu; Chemical Science 14 (2023) 7036–7043; doi:10.1039/D2SC07037E

data_1569295
_publ_section_title
;
 Substituent effects on paratropicity and diatropicity in \p-extended
 hexapyrrolohexaazacoronene
;
_journal_issue                   25
_journal_name_full               'Chemical Science'
_journal_page_first              7036
_journal_page_last               7043
_journal_paper_doi               10.1039/D2SC07037E
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C61 H60 F5 N6, F6 Sb, 3(C7 H8 O)'
_chemical_formula_sum            'C82 H84 F11 N6 O3 Sb'
_chemical_formula_weight         1532.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-12-03
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-23 deposited with the CCDC.	2023-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.915(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.1475(5)
_cell_length_b                   13.0806(3)
_cell_length_c                   28.6942(7)
_cell_measurement_reflns_used    39566
_cell_measurement_temperature    100
_cell_measurement_theta_max      31.2840
_cell_measurement_theta_min      1.8820
_cell_volume                     7031.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.952
_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   0.50   32.00    --  -20.00  45.00   0.00  360
  2  \w   -110.00  70.00   0.50   32.00    --  -20.00  45.00  90.00  360
  3  \w   -110.00  70.00   0.50   32.00    --  -20.00  45.00 180.00  360
  4  \w   -110.00  70.00   0.50   32.00    --  -20.00  45.00 270.00  360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0752
_diffrn_reflns_av_unetI/netI     0.0687
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            132290
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.181
_diffrn_reflns_theta_min         1.717
_diffrn_source                   'Rigaku VariMax'
_exptl_absorpt_coefficient_mu    0.478
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78653
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (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    1.447
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3168
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.233
_refine_diff_density_min         -1.074
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1036
_refine_ls_number_reflns         21665
_refine_ls_number_restraints     948
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.1378
_refine_ls_R_factor_gt           0.0840
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0764P)^2^+24.2095P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1938
_refine_ls_wR_factor_ref         0.2173
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13922
_reflns_number_total             21665
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc07037e2.cif
_cod_data_source_block           homohphac_c6f5
_cod_database_code               1569295
_shelx_shelxl_version_number     2019/2
_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
 C38A-C39A = C38-C39
 1.54 with sigma of 0.02
 C13-C38A = C13-C38
 1.5 with sigma of 0.02
 O2-C69
 1.4 with sigma of 0.02
 O2-C75
 1.43 with sigma of 0.02
 C69-C74 = C74-C73 = C73-C72 = C72-C71 = C71-C70 = C70-C69
 1.39 with sigma of 0.02
 O3-C76 = O3A-C76A
 1.4 with sigma of 0.02
 O3-C82 = O3A-C82A
 1.43 with sigma of 0.02
 C76-C77 = C77-C78 = C78-C79 = C79-C80 = C80-C81 = C81-C76 = C76A-C77A = C77A-
 C78A = C78A-C79A = C79A-C80A = C80A-C81A = C81A-C76A
 1.39 with sigma of 0.02
 C69-C73 = C74-C72 = C73-C71 = C72-C70 = C71-C69 = C70-C74
 2.41 with sigma of 0.04
 C75-C74 = C75-C70
 2.4 with sigma of 0.04
 C76-C78 = C77-C79 = C78-C80 = C79-C81 = C80-C76 = C81-C77 = C76A-C78A = C77A-
 C79A = C78A-C80A = C79A-C81A = C80A-C76A = C81A-C77A
 2.41 with sigma of 0.04
 O3-C77 = O3-C81 = O3A-C77A = O3A-C81A
 2.4 with sigma of 0.04
 C82-C76 = C82A-C76A
 2.42 with sigma of 0.04
 Sb1-F11 \\sim Sb1-F7 \\sim Sb1-F7 \\sim Sb1-F6 \\sim Sb1-F6 \\sim Sb1-F10
\\sim Sb1-F10 \\sim Sb1-F8 ~
 Sb1-F8 \\sim Sb1-F9 \\sim Sb1-F9 \\sim Sb1-F11
 with sigma of 0.02
3. Restrained planarity
 O2, C69, C70, C71, C72, C73, C74
 with sigma of 0.1
 O3, C76, C77, C78, C79, C80, C81
 with sigma of 0.1
 O3A, C76A, C77A, C78A, C79A, C80A, C81A
 with sigma of 0.1
4. Rigid bond restraints
 C13, C38, C39, C38A, C39A
 with sigma for 1-2 distances of 0.05 and sigma for 1-3 distances of 0.05
 O2, C69, C70, C71, C72, C73, C74, C75
 with sigma for 1-2 distances of 0.05 and sigma for 1-3 distances of 0.05
 O3, C76, C77, C78, C79, C80, C81, C82, O3A, C76A, C77A, C78A, C79A, C80A,
 C81A, C82A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Uiso/Uaniso restraints and constraints
C13 \\sim C38 \\sim C39 \\sim C38A \\sim C39A: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
O2 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O3 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim
O3A \\sim C76A \\sim C77A \\sim C78A \\sim C79A \\sim C80A \\sim C81A \\sim
C82A: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within
2A
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq,
Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq,
Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C38A) \\sim Ueq, Uanis(C39A) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(O2) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq,
Uanis(C75) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O3) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78)
\\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C81) \\sim Ueq,
Uanis(C82) \\sim Ueq, Uanis(O3A) \\sim Ueq, Uanis(C76A) \\sim Ueq, Uanis(C77A)
\\sim Ueq, Uanis(C78A) \\sim Ueq, Uanis(C79A) \\sim Ueq, Uanis(C80A) \\sim Ueq,
Uanis(C81A) \\sim Ueq, Uanis(C82A) \\sim Ueq: with sigma of 0.04 and sigma for
terminal atoms of 0.08
6. Others
 Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=1-FVAR(1)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(1)
 Sof(O3A)=Sof(C76A)=Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78A)=Sof(C79A)=
 Sof(H79A)=Sof(C80A)=Sof(H80A)=Sof(C81A)=Sof(H81A)=Sof(C82A)=Sof(H82D)=
 Sof(H82E)=Sof(H82F)=1-FVAR(2)
 Sof(O3)=Sof(C76)=Sof(C77)=Sof(H77)=Sof(C78)=Sof(H78)=Sof(C79)=Sof(H79)=
 Sof(C80)=Sof(H80)=Sof(C81)=Sof(H81)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=
 FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C34(H34A,H34B), C36(H36A,H36B), C40(H40A,H40B), C42(H42A,
 H42B), C44(H44A,H44B), C46(H46A,H46B), C48(H48A,H48B), C50(H50A,H50B),
 C52(H52A,H52B), C54(H54A,H54B), C38(H38A,H38B), C38A(H38C,H38D)
7.b Aromatic/amide H refined with riding coordinates:
 C63(H63), C64(H64), C65(H65), C66(H66), C67(H67), C70(H70), C71(H71),
 C72(H72), C73(H73), C74(H74), C77(H77), C78(H78), C79(H79), C80(H80), C81(H81),
  C77A(H77A), C78A(H78A), C79A(H79A), C80A(H80A), C81A(H81A)
7.c Idealised Me refined with riding coordinates:
 C75(H75A,H75B,H75C)
7.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C41(H41A,H41B,
 H41C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C49(H49A,
 H49B,H49C), C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C55(H55A,H55B,H55C),
 C39(H39A,H39B,H39C), C39A(H39D,H39E,H39F), C68(H68A,H68B,H68C), C82(H82A,H82B,
 H82C), C82A(H82D,H82E,H82F)
;
_shelx_res_checksum              30947
_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
;