Transition metal-free vs. metal-catalyzed cyclotrimerization of didehydro[8]annulenes (COTynes): a complex pathway to non-planar PAHs – Dewar benzenes vs. benzotri[8]annulenes
Bello-García, Jesús; Varela, Jesús A.; Saá, Carlos; Chemical Science 16 (2025) 10874–10880; doi:10.1039/D5SC03035H

data_1574592
_publ_section_title
;
 Transition metal-free vs. metal-catalyzed cyclotrimerization of
 didehydro[8]annulenes (COTynes): a complex pathway to non-planar PAHs --
 Dewar benzenes vs. benzotri[8]annulenes
;
_journal_issue                   24
_journal_name_full               'Chemical Science'
_journal_page_first              10874
_journal_page_last               10880
_journal_paper_doi               10.1039/D5SC03035H
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C16  H12'
_chemical_formula_sum            'C16 H12'
_chemical_formula_weight         204.26
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      19
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   dual
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4.5
_audit_creation_date             2022-11-28T08:58:45-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_update_record
;
2025-01-20 deposited with the CCDC.	2025-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4618(2)
_cell_length_b                   7.8144(2)
_cell_length_c                   22.3901(6)
_cell_measurement_reflns_used    7525
_cell_measurement_temperature    299(2)
_cell_measurement_theta_max      74.55
_cell_measurement_theta_min      6.00
_cell_measurement_wavelength     1.54178
_cell_volume                     1130.59(5)
_computing_cell_refinement       'SAINT V8.40B (Bruker AXS LLC, 2019)'
_computing_data_collection       'APPEX3v2022.1-1 (BRUKER AXS, 2021)'
_computing_data_reduction        'SAINT V8.40B (Bruker AXS LLC, 2019)'
_computing_molecular_graphics    'Ortep for Windows (Farrugia, 2012)'
_computing_publication_material  'WinGX publication routines (Farrugia, 2012)'
_computing_structure_refinement  'SHELXL-2019/1 (Sheldrick, 2019)'
_computing_structure_solution    'SHELXT-2018/2 (Sheldrick, 2015)'
_diffrn_ambient_temperature      299(2)
_diffrn_detector_area_resol_mean 7.3910
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON III-14'
_diffrn_measurement_method       'omega and phi'
_diffrn_radiation_monochromator  'Incoatec multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            13018
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.974
_diffrn_reflns_theta_min         5.998
_diffrn_source                   'INCOATEC microfocus sealed tube'
_diffrn_source_type              'Incoatec I\mS 3.0'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.512
_exptl_absorpt_correction_T_max  0.9582
_exptl_absorpt_correction_T_min  0.8677
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'BRUKER SADABS-2016/2'
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.2
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.077
_refine_diff_density_min         -0.089
_refine_diff_density_rms         0.024
_refine_ls_abs_structure_details
;
 Flack x determined using 776 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.4(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     145
_refine_ls_number_reflns         2140
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.035
_refine_ls_R_factor_gt           0.031
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0351P)^2^+0.0954P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0762
_refine_ls_wR_factor_ref         0.0802
_reflns_Friedel_coverage         0.678
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                1976
_reflns_number_total             2140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03035h10.cif
_cod_data_source_block           CS1JBG1250
_cod_depositor_comments
'Adding full bibliography for 1574592--1574593.cif.'
_cod_database_code               1574592
_shelx_estimated_absorpt_t_min   0.905
_shelx_estimated_absorpt_t_max   0.975
_shelx_shelxl_version_number     2019/1
_shelx_res_checksum              99345