Heterogeneous visible-light promoted dehydrogenative [4 + 2] annulation of benzothioamides and alkynes under aerobic conditions
Guo, Yanmin; Chang, Rong; Fu, Zhen; Zhou, Cong-Ying; Guo, Zhen; Green Chemistry 25 (2023) 5206–5212; doi:10.1039/D3GC01329D

data_7246831
_publ_section_title
;
 Heterogeneous visible-light promoted dehydrogenative [4 + 2] annulation
 of benzothioamides and alkynes under aerobic conditions
;
_journal_issue                   13
_journal_name_full               'Green Chemistry'
_journal_page_first              5206
_journal_page_last               5212
_journal_paper_doi               10.1039/D3GC01329D
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety         'C22 H16 Br N S'
_chemical_formula_sum            'C22 H16 Br N S'
_chemical_formula_weight         406.33
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-09
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-11-29 deposited with the CCDC.	2023-05-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.70389(13)
_cell_length_b                   13.29859(7)
_cell_length_c                   5.82409(3)
_cell_measurement_reflns_used    16569
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      67.0040
_cell_measurement_theta_min      3.8460
_cell_volume                     1758.466(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_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     81.00 120.00   0.50    0.05    --   83.87 125.00   0.00   78
  2  \w     90.00 119.00   0.50    0.05    --   83.87 104.00 -26.00   58
  3  \w    128.00 154.00   0.50    0.05    --   83.87 104.00 -26.00   52
  4  \w     95.00 154.00   0.50    0.05    --   83.87  38.00 -90.00  118
  5  \w    -86.00 -50.00   0.50    0.05    --  -86.37  77.00-180.00   72
  6  \w    -40.00 -15.00   0.50    0.05    --  -86.37  77.00-180.00   50
  7  \w    -40.00 -14.00   0.50    0.05    --  -86.37  38.00 -60.00   52
  8  \w    -41.00 -16.00   0.50    0.05    --  -86.37  38.00-120.00   50
  9  \w    -41.00 -16.00   0.50    0.05    --  -86.37  38.00  30.00   50
 10  \w    -41.00 -16.00   0.50    0.05    --  -86.37  38.00  60.00   50
 11  \w    -55.00 -14.00   0.50    0.05    --  -86.37  57.00 120.00   82
 12  \w    -48.00 -18.00   0.50    0.05    --  -86.37  57.00  90.00   60
 13  \w    -39.00 -14.00   0.50    0.05    --  -86.37  38.00 -90.00   50
 14  \w    -13.00  35.00   0.50    0.05    --   -1.25  57.00   0.00   96
 15  \w      1.00  69.00   0.50    0.05    --   -1.25  38.00  90.00  136
 16  \w     32.00  69.00   0.50    0.05    --   -1.25  38.00 120.00   74
 17  \w     15.00 106.00   0.50    0.05    --   83.87 -77.00 -30.00  182
 18  \w     40.00  68.00   0.50    0.05    --   83.87 -57.00-120.00   56
 19  \w     36.00  62.00   0.50    0.05    --   83.87 -57.00 -90.00   52
 20  \w     14.00  45.00   0.50    0.05    --   83.87 -57.00 -30.00   62
 21  \w     13.00  39.00   0.50    0.05    --   83.87 -38.00 120.00   52
 22  \w     18.00  66.00   0.50    0.05    --   83.87 -99.00 150.00   96
 23  \w     60.00 106.00   0.50    0.05    --   83.87-125.00 -60.00   92
 24  \w     18.00 106.00   0.50    0.05    --   83.87-125.00-150.00  176
 25  \w     59.00  84.00   0.50    0.05    --   83.87-104.00-127.00   50
 26  \w     55.00 105.00   0.50    0.05    --   83.87 -99.00  60.00  100
 27  \w     12.00  51.00   0.50    0.05    --   83.87 -99.00  60.00   78
 28  \w   -144.00 -83.00   0.50    0.05    --  -86.37 -38.00 -60.00  122
 29  \w   -132.00 -87.00   0.50    0.05    --  -86.37-104.00-127.00   90
 30  \w    -18.00  11.00   0.50    0.05    --   -1.25 -99.00-180.00   58
 31  \w    -17.00  27.00   0.50    0.05    --   -1.25 -99.00 -30.00   88
 32  \w    -98.00 -66.00   0.50    0.05    --  -86.37 104.00 -26.00   64
 33  \w   -103.00 -15.00   0.50    0.05    --  -86.37 125.00-180.00  176
;
_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      -0.0139819000
_diffrn_orient_matrix_UB_12      -0.1014064000
_diffrn_orient_matrix_UB_13      -0.1156609000
_diffrn_orient_matrix_UB_21      0.0638438000
_diffrn_orient_matrix_UB_22      -0.0063062000
_diffrn_orient_matrix_UB_23      -0.0884592000
_diffrn_orient_matrix_UB_31      0.0182428000
_diffrn_orient_matrix_UB_32      -0.0556376000
_diffrn_orient_matrix_UB_33      0.2208418000
_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  0.0227
_diffrn_reflns_av_unetI/netI     0.0137
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -6
_diffrn_reflns_number            17577
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.075
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         3.852
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.306
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68922
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.535
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.291
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.131
_refine_diff_density_max         0.150
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1233 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.021(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         3067
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0168
_refine_ls_R_factor_gt           0.0167
_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^)+(0.0237P)^2^+0.5900P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0430
_refine_ls_wR_factor_ref         0.0430
_reflns_Friedel_coverage         0.690
_reflns_Friedel_fraction_full    0.970
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                3057
_reflns_number_total             3067
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc01329d2.cif
_cod_data_source_block           cr-jianxiu-g-xia-20221005
_cod_depositor_comments
'Adding full bibliography for 7246831--7246835.cif.'
_cod_original_cell_volume        1758.467(17)
_cod_database_code               7246831
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_olex2_refinement_description
;
1.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C16(H16),
 C17(H17), C18(H18), C19(H19), C20(H20)
1.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_shelx_res_checksum              98806
_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 1.650
_oxdiff_exptl_absorpt_empirical_full_min 0.793