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_1569294
_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
'6(F6 Sb), 2(C7 H8 O), 5(C3 H6 O), 2(C63 H70 N7)'
_chemical_formula_sum            'C155 H186 F36 N14 O7 Sb6'
_chemical_formula_weight         3771.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-12-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-12-23 deposited with the CCDC.	2023-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.397(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   55.5390(14)
_cell_length_b                   8.6589(3)
_cell_length_c                   32.5046(8)
_cell_measurement_reflns_used    17623
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.93
_cell_measurement_theta_min      2.20
_cell_volume                     15631.3(8)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.892
_diffrn_measurement_device_type  'Rigaku Saturn724'
_diffrn_measurement_method       \w
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1198
_diffrn_reflns_av_unetI/netI     0.1463
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.892
_diffrn_reflns_limit_h_max       76
_diffrn_reflns_limit_h_min       -60
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            72644
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.188
_diffrn_reflns_theta_min         1.447
_diffrn_source                   'Rotating anode'
_exptl_absorpt_coefficient_mu    1.125
_exptl_absorpt_correction_T_max  0.989
_exptl_absorpt_correction_T_min  0.202
_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            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.603
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             7600
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.272
_refine_diff_density_min         -1.741
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1266
_refine_ls_number_reflns         22603
_refine_ls_number_restraints     1421
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.1845
_refine_ls_R_factor_gt           0.0896
_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^)+(0.0954P)^2^+56.5398P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1950
_refine_ls_wR_factor_ref         0.2449
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11030
_reflns_number_total             22603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc07037e2.cif
_cod_data_source_block           xcalibur
_cod_database_code               1569294
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.832
_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
 C64-C65 = C65-C66 = C66-C67 = C67-C68 = C68-C69 = C69-C64 = C64A-C65A = C65A-
 C66A = C66A-C67A = C67A-C68A = C68A-C69A = C69A-C64A
 1.39 with sigma of 0.02
 C64-O1 = C64A-O1A
 1.4 with sigma of 0.02
 O1-C70 = O1-C70A
 1.43 with sigma of 0.02
 O4-C78
 1.23 with sigma of 0.02
 C77-C78 = C78-C79
 1.5 with sigma of 0.02
 C64-C66 = C65-C67 = C66-C68 = C67-C69 = C68-C64 = C69-C65 = C64A-C66A = C65A-
 C67A = C66A-C68A = C67A-C69A = C68A-C64A = C69A-C65A
 2.41 with sigma of 0.04
 C65-O1 = C69-O1 = C65A-O1A = C69A-O1A
 2.45 with sigma of 0.04
 C64-C70 = C64A-C70A
 2.3 with sigma of 0.04
 C77-C79
 2.53 with sigma of 0.04
 Sb3-F13 \\sim Sb3-F14 \\sim Sb3-F15 \\sim Sb3-F16 \\sim Sb3-F17 \\sim Sb3-F18
\\sim Sb3A-F13A \\sim Sb3A-
 F14A \\sim Sb3A-F15A \\sim Sb3A-F16A
 with sigma of 0.02
3. Restrained planarity
 O1, C64, C65, C66, C67, C68, C69
 with sigma of 0.1
 O1A, C64A, C65A, C66A, C67A, C68A, C69A
 with sigma of 0.1
4. Rigid bond restraints
 Sb1, F1, F2, F3, F4, F5, F6, F1A, F2A, F3A, F4A, F5A, F6A, Sb2, F7, F8, F9,
 F10, F11, F12, Sb2A, F7A, F8A, F9A, F10A, F11A, F12A, Sb3, F13, F14, F15, F16,
 F17, F18, Sb3A, F13A, F14A, F15A, F16A, F17A, F18A, O1, C64, C65, C66, C67,
 C68, C69, C70, O1A, C64A, C65A, C66A, C67A, C68A, C69A, C70A, O4, C77, C78, C79
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Sb1 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F1A \\sim F2A
\\sim F3A \\sim F4A \\sim F5A \\sim F6A \\sim Sb2 \\sim F7 \\sim F8 \\sim F9
\\sim F10 \\sim F11 \\sim F12 \\sim Sb2A \\sim F7A \\sim F8A \\sim F9A \\sim
F10A \\sim F11A \\sim F12A \\sim Sb3 \\sim F13 \\sim F14 \\sim F15 \\sim F16
\\sim F17 \\sim F18 \\sim Sb3A \\sim F13A \\sim F14A \\sim F15A \\sim F16A
\\sim F17A \\sim F18A \\sim O1 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim
C68 \\sim C69 \\sim C70 \\sim O1A \\sim C64A \\sim C65A \\sim C66A \\sim C67A
\\sim C68A \\sim C69A \\sim C70A \\sim O4 \\sim C77 \\sim C78 \\sim C79: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
Uanis(Sb1) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F3) \\sim
Ueq, Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(F1A)
\\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F4A) \\sim Ueq,
Uanis(F5A) \\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(Sb2) \\sim Ueq, Uanis(F7)
\\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F10) \\sim Ueq,
Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(Sb2A) \\sim Ueq, Uanis(F7A)
\\sim Ueq, Uanis(F8A) \\sim Ueq, Uanis(F9A) \\sim Ueq, Uanis(F10A) \\sim Ueq,
Uanis(F11A) \\sim Ueq, Uanis(F12A) \\sim Ueq, Uanis(Sb3) \\sim Ueq, Uanis(F13)
\\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F16) \\sim Ueq,
Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(Sb3A) \\sim Ueq, Uanis(F13A)
\\sim Ueq, Uanis(F14A) \\sim Ueq, Uanis(F15A) \\sim Ueq, Uanis(F16A) \\sim Ueq,
Uanis(F17A) \\sim Ueq, Uanis(F18A) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C64)
\\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq,
Uanis(C68) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(O1A)
\\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C65A) \\sim Ueq, Uanis(C66A) \\sim Ueq,
Uanis(C67A) \\sim Ueq, Uanis(C68A) \\sim Ueq, Uanis(C69A) \\sim Ueq,
Uanis(C70A) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C78)
\\sim Ueq, Uanis(C79) \\sim Ueq: with sigma of 0.04 and sigma for terminal
atoms of 0.08
6. Same fragment restrains
{Sb1, F1A, F2A, F3A, F4A, F5A, F6A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Sb1, F1, F2, F3, F4, F5, F6}
{Sb2A, F7A, F8A, F9A, F10A, F11A, F12A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Sb2, F7, F8, F9, F10, F11, F12}
{Sb3A, F13A, F14A, F15A, F16A, F17A, F18A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{Sb3, F13, F14, F15, F16, F17, F18}
7. Others
 Sof(O1A)=Sof(C64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=Sof(H66A)=Sof(C67A)=
 Sof(H67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70D)=
 Sof(H70E)=Sof(H70F)=1-FVAR(1)
 Sof(O1)=Sof(C64)=Sof(C65)=Sof(H65)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67)=
 Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=
 FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(Sb2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=1-FVAR(3)
 Sof(Sb2A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(3)
 Sof(Sb3A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(4)
 Sof(Sb3)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=Sof(F18)=FVAR(4)
 Fixed Sof: O4(0.5) C77(0.5) H77A(0.5) H77B(0.5) H77C(0.5) C78(0.5) C79(0.5)
 H79A(0.5) H79B(0.5) H79C(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C40(H40A,H40B), C42(H42A,H42B), C44(H44A,H44B), C46(H46A,
 H46B), C48(H48A,H48B), C50(H50A,H50B), C52(H52A,H52B), C54(H54A,H54B),
 C56(H56A,H56B), C58(H58A,H58B), C60(H60A,H60B)
8.b Aromatic/amide H refined with riding coordinates:
 C65(H65), C66(H66), C67(H67), C68(H68), C69(H69), C65A(H65A), C66A(H66A),
 C67A(H67A), C68A(H68A), C69A(H69A), C33(H33), C34(H34), C36(H36), C37(H37)
8.c Idealised Me refined with riding coordinates:
 C39(H39A,H39B,H39C), 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), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C),
 C61(H61A,H61B,H61C)
8.d Idealised Me refined as rotating group:
 C70(H70A,H70B,H70C), C70A(H70D,H70E,H70F), C77(H77A,H77B,H77C), C79(H79A,H79B,
 H79C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C76(H76A,
 H76B,H76C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C)
;
_shelx_res_checksum              94112
_olex2_submission_special_instructions 'No special instructions were received'