Iron-catalyzed regioselective reductive cyclotrimerization of alkynyl bromides to 1,2,4-substituted arenes and D<sub>3</sub>-arenes.
Zhang, Xin; Luo, Yuhang; Zhao, Xinjie; Xiao, Tiebo; Jiang, Yubo; Qin, Guiping; Wei, Yubo; Organic & biomolecular chemistry 23 (2025) 6551–6556; doi:10.1039/d5ob00674k

data_7160592
_publ_section_title
;
 Iron-catalyzed regioselective reductive cyclotrimerization of alkynyl
 bromides to 1,2,4-substituted arenes and D<sub>3</sub>-arenes.
;
_journal_issue                   27
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6551
_journal_page_last               6556
_journal_paper_doi               10.1039/d5ob00674k
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C24 H18'
_chemical_formula_sum            'C24 H18'
_chemical_formula_weight         306.38
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-06-06
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-06-07 deposited with the CCDC.	2025-06-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.3109(6)
_cell_length_b                   17.7703(11)
_cell_length_c                   18.3580(9)
_cell_measurement_reflns_used    5581
_cell_measurement_temperature    142(50)
_cell_measurement_theta_max      73.1590
_cell_measurement_theta_min      4.8220
_cell_volume                     3363.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      142(50)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.942
_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     79.00 170.00   0.50    0.50    --   99.00 126.00  93.00  182
  2  \w    130.00 168.00   0.50    0.50    --   99.00 111.00  11.00   76
  3  \w     27.00  52.00   0.50    0.50    --   99.00 -45.00  90.00   50
  4  \w    -28.00  21.00   0.50    0.30    --   46.12 -15.00  77.00   98
  5  \w     27.00  52.00   0.50    0.50    --   99.00 -45.00   0.00   50
  6  \w     28.00  53.00   0.50    0.50    --   99.00 -45.00-120.00   50
  7  \w     43.00  78.00   0.50    0.30    --   46.12-125.00 -60.00   70
  8  \w     39.00 102.00   0.50    0.50    --   99.00-125.00  30.00  126
  9  \w    -18.00  27.00   0.50    0.30    --  -46.12  19.00 -60.00   90
 10  \w     -7.00  30.00   0.50    0.30    --  -46.12  15.00-112.00   74
 11  \w   -109.00 -34.00   0.50    0.50    --  -99.00 125.00-120.00  150
 12  \w   -172.00 -89.00   0.50    0.50    --  -99.00 -15.00  77.00  166
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1197196000
_diffrn_orient_matrix_UB_12      0.0484691000
_diffrn_orient_matrix_UB_13      0.0178745000
_diffrn_orient_matrix_UB_21      -0.0842922000
_diffrn_orient_matrix_UB_22      0.0714096000
_diffrn_orient_matrix_UB_23      -0.0041963000
_diffrn_orient_matrix_UB_31      -0.0302489000
_diffrn_orient_matrix_UB_32      -0.0069731000
_diffrn_orient_matrix_UB_33      0.0819332000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0518
_diffrn_reflns_av_unetI/netI     0.0535
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            10988
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.344
_diffrn_reflns_theta_min         4.818
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.516
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21673
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.210
_exptl_crystal_description       block
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.372
_refine_diff_density_rms         0.056
_refine_ls_extinction_coef       0.0015(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.127
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3185
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0562
_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^)+(0.0851P)^2^+1.3343P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1621
_refine_ls_wR_factor_ref         0.1777
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2560
_reflns_number_total             3185
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00674k2.cif
_cod_data_source_block           363-3
_cod_depositor_comments          'Adding full bibliography for 7160592.cif.'
_cod_database_code               7160592
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N S'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12),
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22),
  C23(H23), C24(H24)
;
_shelx_res_checksum              75435
_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 3.702
_oxdiff_exptl_absorpt_empirical_full_min 0.428