Metal-Free Dehydrogenative Double C-H Sulfuration To Access Thieno[2,3-<i>b</i>]indoles Using Elemental Sulfur.
Liu, Jianming; Zhang, Yanyan; Yue, Yuanyuan; Wang, Zhixian; Shao, Huibin; Zhuo, Kelei; Lv, Qingzhang; Zhang, Zhiguo; The Journal of organic chemistry 84 (2019) 12946–12959; doi:10.1021/acs.joc.9b01586

data_4034082
_publ_section_title
;
 Metal-Free Dehydrogenative Double C-H Sulfuration To Access
 Thieno[2,3-<i>b</i>]indoles Using Elemental Sulfur.
;
_journal_issue                   20
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12946
_journal_page_last               12959
_journal_paper_doi               10.1021/acs.joc.9b01586
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C27 H17 N O S'
_chemical_formula_sum            'C27 H17 N O S'
_chemical_formula_weight         403.48
_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
_audit_creation_date             2018-09-12
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.0110(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5839(2)
_cell_length_b                   15.2015(2)
_cell_length_c                   10.71110(10)
_cell_measurement_reflns_used    6931
_cell_measurement_temperature    296.06(10)
_cell_measurement_theta_max      71.2370
_cell_measurement_theta_min      4.5950
_cell_volume                     2017.77(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296.06(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_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   -103.00 -19.00   1.00    1.00    --  -35.37 -57.00 -60.00   84
  2  \w      1.00  74.00   1.00    1.00    --   35.37 -99.00 -90.00   73
  3  \w      1.00  74.00   1.00    1.00    --   35.37 -99.00 150.00   73
  4  \w     23.00  89.00   1.00    1.00    --   35.37-125.00   0.00   66
  5  \w     16.00 105.00   1.00    1.00    --   35.37  38.00-180.00   89
  6  \w     16.00 105.00   1.00    1.00    --   35.37  38.00  90.00   89
  7  \w     19.00 103.00   1.00    1.00    --   35.37  57.00  30.00   84
  8  \w     88.00 173.00   1.00    3.20    --  106.50  61.00-150.00   85
  9  \w     40.00 125.00   1.00    3.20    --  106.50 -61.00  60.00   85
 10  \w     88.00 173.00   1.00    3.20    --  106.50  61.00-180.00   85
 11  \w     37.00 109.00   1.00    3.20    --  106.50 -95.00   0.00   72
 12  \w     88.00 173.00   1.00    3.20    --  106.50  61.00 -90.00   85
 13  \w    100.00 176.00   1.00    3.20    --  106.50 111.00 150.00   76
 14  \w     37.00 112.00   1.00    3.20    --  106.50-111.00-120.00   75
 15  \w     37.00 109.00   1.00    3.20    --  106.50 -95.00 -90.00   72
 16  \w     37.00 109.00   1.00    3.20    --  106.50 -95.00  60.00   72
 17  \w   -103.00 -31.00   1.00    1.00    --  -35.37 -57.00-150.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0461084000
_diffrn_orient_matrix_UB_12      0.0032141000
_diffrn_orient_matrix_UB_13      0.1240992000
_diffrn_orient_matrix_UB_21      -0.0080835000
_diffrn_orient_matrix_UB_22      -0.1011933000
_diffrn_orient_matrix_UB_23      -0.0005246000
_diffrn_orient_matrix_UB_31      0.1150847000
_diffrn_orient_matrix_UB_32      -0.0058197000
_diffrn_orient_matrix_UB_33      0.0769412000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0176
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            11568
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.319
_diffrn_reflns_theta_min         4.604
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.563
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74445
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.328
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         3865
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0394
_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^)+(0.0393P)^2^+0.8099P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1036
_refine_ls_wR_factor_ref         0.1073
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3274
_reflns_number_total             3865
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01586_si_003.cif
_cod_data_source_block           zyy-20180912
_cod_database_code               4034082
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C1 H1 O1 N1'
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.669
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N9(H9), C22(H22), C18(H18), C4(H4), C14(H14), C30(H30), C29(H29), C24(H24),
 C5(H5), C7(H7), C17(H17), C6(H6), C27(H27), C25(H25), C26(H26), C16(H16),
 C15(H15)
;
_olex2_date_sample_data_collection 2018-09-12
_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 1.530
_oxdiff_exptl_absorpt_empirical_full_min 0.631