Size-dependent properties and unusual reactivity of novel nonplanar heterocycloarenes
Zhu, Jiangyu; Li, Wenhao; Zhang, Ning; An, Dongyue; Zhao, Yan; Lu, Xuefeng; Liu, Yunqi; Chemical Science 13 (2022) 11174–11182; doi:10.1039/D2SC03167A

data_1567633
_publ_section_title
;
 Size-dependent properties and unusual reactivity of novel nonplanar
 heterocycloarenes
;
_journal_issue                   37
_journal_name_full               'Chemical Science'
_journal_page_first              11174
_journal_page_last               11182
_journal_paper_doi               10.1039/D2SC03167A
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C94 H82 N2 O4 S2, 1[CH3CN]'
_chemical_formula_sum            'C96 H85 N3 O4 S2'
_chemical_formula_weight         1408.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-14
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-08-15 deposited with the CCDC.	2022-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.813(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.891(5)
_cell_length_b                   8.271(3)
_cell_length_c                   44.433(12)
_cell_measurement_reflns_used    9966
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      57.88
_cell_measurement_theta_min      2.63
_cell_volume                     7486(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      173.0
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.966
_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  0.1091
_diffrn_reflns_av_unetI/netI     0.0791
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            74059
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        61.338
_diffrn_reflns_theta_max         61.338
_diffrn_reflns_theta_min         4.081
_diffrn_source_current           45.0
_diffrn_source_power             2.25
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.088
_exptl_absorpt_correction_T_max  0.7520
_exptl_absorpt_correction_T_min  0.5939
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1194 before and 0.0809 after correction.
The Ratio of minimum to maximum transmission is 0.7898.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_description       block
_exptl_crystal_F_000             2984
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.314
_refine_diff_density_min         -1.253
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.210
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     827
_refine_ls_number_reflns         11181
_refine_ls_number_restraints     71
_refine_ls_restrained_S_all      1.233
_refine_ls_R_factor_all          0.1718
_refine_ls_R_factor_gt           0.1193
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3121
_refine_ls_wR_factor_ref         0.3619
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6230
_reflns_number_total             11181
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03167a2.cif
_cod_data_source_block           PTZ1-0714
_cod_depositor_comments
'Adding full bibliography for 1567633--1567634.cif.'
_cod_original_cell_volume        7487(4)
_cod_database_code               1567633
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.899
_shelx_estimated_absorpt_t_min   0.854
_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
 C93-C94
 1.54 with sigma of 0.02
 C91-C86
 3 with sigma of 0.04
3. Rigid bond restraints
 O2, C91
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O3, C83
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C91, O2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O4, C87
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O1, C79
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O3, C46
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C45, O4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O2, C16
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 O1, C15
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C46, C45
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
Uanis(C91) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C92)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C93) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C83)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C91) = Uanis(C85) = Uanis(C86) = Uanis(C92)
Uanis(C93) = Uanis(C94) = Uanis(C84) = Uanis(C83)
Uanis(O3) = Uanis(C83) = Uanis(C84) = Uanis(C94) = Uanis(C93)
Uanis(O4) = Uanis(C87) = Uanis(C88) = Uanis(C89) = Uanis(C90)
Uanis(O2) = Uanis(C91) = Uanis(C85) = Uanis(C86) = Uanis(C92)
Uanis(O1) = Uanis(C79) = Uanis(C80) = Uanis(C81) = Uanis(C82)
5. Rigid body (RIGU) restrains
 O2, C91
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O4, C87
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, C79
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, C83
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed X: C83(0.32961) C91(1.13492)
 Fixed Y: C83(-0.196059) C91(0.120341)
 Fixed Z: C83(0.41978) C91(0.728121)
7.a Secondary CH2 refined with riding coordinates:
 C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C83(H83A,H83B), C84(H84A,
 H84B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B), C91(H91A,H91B),
 C94(H94A,H94B), C85(H85A,H85B), C86(H86A,H86B)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C6(H6), C8(H8), C11(H11), C14(H14), C19(H19), C22(H22),
 C24(H24), C23(H23), C27(H27), C30(H30), C33(H33), C36(H36), C37(H37), C38(H38),
  C41(H41), C44(H44), C49(H49), C52(H52), C53(H53), C54(H54), C57(H57),
 C60(H60), C63(H63), C65(H65), C72(H72), C74(H74)
7.c Idealised Me refined as rotating group:
 C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C76(H76A,H76B,
 H76C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C82(H82A,H82B,H82C), C90(H90A,
 H90B,H90C), C93(H93A,H93B,H93C), C92(H92A,H92B,H92C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 168 electrons were 
found in a volume of 940\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[CH3CN] per Asymmetric Unit 
which account for 88 electrons 
per unit cell.
;
_shelx_res_checksum              56774
_shelx_fab_checksum              65564
_olex2_submission_special_instructions 'No special instructions were received'