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_7246835
_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         'C26 H25 N S'
_chemical_formula_sum            'C26 H25 N S'
_chemical_formula_weight         383.53
_chemical_melting_point          128.8
_chemical_name_systematic
(Z)-5-(tert-butyl)-3-methyl-N,4-diphenyl-1H-isothiochromen-1-imine
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_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                74.050(2)
_cell_angle_beta                 80.114(2)
_cell_angle_gamma                67.955(2)
_cell_formula_units_Z            4
_cell_length_a                   11.3822(2)
_cell_length_b                   12.2394(3)
_cell_length_c                   16.8294(4)
_cell_measurement_reflns_used    15014
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      66.6870
_cell_measurement_theta_min      2.7250
_cell_volume                     2083.27(9)
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.966
_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    104.00 155.00   0.50    0.13    --   83.87  77.00 -30.00  102
  2  \w    122.00 156.00   0.50    0.13    --   83.87 125.00  30.00   68
  3  \w     80.00 105.00   0.50    0.13    --   83.87 125.00  30.00   50
  4  \w     66.00  93.00   0.50    0.13    --   83.87  77.00 -30.00   54
  5  \w    121.00 153.00   0.50    0.13    --   83.87 104.00-176.00   64
  6  \w    -41.00 -16.00   0.50    0.13    --  -86.37  38.00 150.00   50
  7  \w    -46.00 -14.00   0.50    0.13    --  -86.37  77.00 150.00   64
  8  \w    -97.00 -59.00   0.50    0.13    --  -86.37  77.00 150.00   76
  9  \w    -40.00 -15.00   0.50    0.13    --  -86.37  38.00 120.00   50
 10  \w    -77.00 -39.00   0.50    0.13    --  -86.37  77.00  60.00   76
 11  \w   -103.00 -77.00   0.50    0.13    --  -86.37  77.00   0.00   52
 12  \w    -46.00 -14.00   0.50    0.13    --  -86.37  77.00   0.00   64
 13  \w     26.00  64.00   0.50    0.05    --   -1.25  38.00 -30.00   76
 14  \w    -66.00 -15.00   0.50    0.13    --  -86.37 125.00  30.00  102
 15  \w   -105.00 -72.00   0.50    0.13    --  -86.37 125.00  30.00   66
 16  \w   -108.00 -14.00   0.50    0.13    --  -86.37 125.00-180.00  188
 17  \w    -96.00 -49.00   0.50    0.13    --  -86.37 104.00-176.00   94
 18  \w    -73.00   9.00   0.50    0.05    --   -1.25 -57.00  30.00  164
 19  \w    -16.00  16.00   0.50    0.05    --   -1.25 -99.00 -90.00   64
 20  \w    -16.00  31.00   0.50    0.05    --   -1.25 -99.00 -60.00   94
 21  \w    -18.00   7.00   0.50    0.05    --   -1.25 -99.00   0.00   50
 22  \w   -156.00 -67.00   0.50    0.13    --  -86.37 -77.00 -30.00  178
 23  \w   -129.00 -87.00   0.50    0.13    --  -86.37-104.00  82.00   84
 24  \w    -17.00  28.00   0.50    0.05    --   -1.25 -99.00 120.00   90
 25  \w     58.00 106.00   0.50    0.13    --   83.87-125.00  30.00   96
 26  \w     67.00 106.00   0.50    0.13    --   83.87-104.00  82.00   78
 27  \w     12.00  62.00   0.50    0.13    --   83.87 -57.00 150.00  100
 28  \w     20.00  58.00   0.50    0.13    --   83.87 -57.00 120.00   76
 29  \w     12.00  40.00   0.50    0.13    --   83.87 -57.00  90.00   56
 30  \w     12.00  44.00   0.50    0.13    --   83.87 -38.00   0.00   64
 31  \w     12.00  45.00   0.50    0.13    --   83.87 -38.00 -30.00   66
 32  \w     13.00  45.00   0.50    0.13    --   83.87 -38.00 -60.00   64
 33  \w     12.00  45.00   0.50    0.13    --   83.87 -38.00 -90.00   66
 34  \w     15.00  44.00   0.50    0.13    --   83.87 -38.00-120.00   58
 35  \w     14.00 105.00   0.50    0.13    --   83.87 -99.00 -90.00  182
;
_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      -0.0220364000
_diffrn_orient_matrix_UB_12      0.0777328000
_diffrn_orient_matrix_UB_13      0.0629341000
_diffrn_orient_matrix_UB_21      -0.0553624000
_diffrn_orient_matrix_UB_22      0.1156376000
_diffrn_orient_matrix_UB_23      -0.0671491000
_diffrn_orient_matrix_UB_31      -0.1337889000
_diffrn_orient_matrix_UB_32      -0.0077318000
_diffrn_orient_matrix_UB_33      0.0254610000
_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  0.0281
_diffrn_reflns_av_unetI/netI     0.0313
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            21719
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.070
_diffrn_reflns_theta_max         67.070
_diffrn_reflns_theta_min         2.739
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.439
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.785
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.223
_exptl_crystal_description       block
_exptl_crystal_F_000             816
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2 and n-hexane'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.189
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     507
_refine_ls_number_reflns         7193
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0704
_refine_ls_R_factor_gt           0.0658
_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^)+(0.1228P)^2^+1.3118P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1765
_refine_ls_wR_factor_ref         0.1816
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6395
_reflns_number_total             7193
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc01329d2.cif
_cod_data_source_block           cr-ea-hex_auto
_cod_depositor_comments
'Adding full bibliography for 7246831--7246835.cif.'
_cod_database_code               7246835
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.911
_shelx_estimated_absorpt_t_min   0.742
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(S1) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C7) = Uanis(S1)
3.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C15(H15), C16(H16), C20(H20),
 C21(H21), C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29), C30(H30),
  C31(H31), C35(H35), C41(H41), C42(H42), C46(H46), C47(H47), C48(H48),
 C49(H49), C50(H50)
3.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C26(H26A,H26B,
 H26C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C52(H52A,
 H52B,H52C)
;
_shelx_res_checksum              18173
_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 1.350
_oxdiff_exptl_absorpt_empirical_full_min 0.790