Chemoselective Ullmann Reaction of α-Trisubstituted Thioamides: Synthesis of Novel 2-Iminobenzothiolanes.
Bhattacharya, Anwesha; Thirupathi, Annaram; Natarajan, Pradeep; Peruncheralathan, Saravanan; ACS omega 6 (2021) 21169–21180; doi:10.1021/acsomega.1c03410

data_4519003
_publ_section_title
;
 Chemoselective Ullmann Reaction of \a-Trisubstituted Thioamides:
 Synthesis of Novel 2-Iminobenzothiolanes.
;
_journal_issue                   32
_journal_name_full               'ACS omega'
_journal_page_first              21169
_journal_page_last               21180
_journal_paper_doi               10.1021/acsomega.1c03410
_journal_volume                  6
_journal_year                    2021
_chemical_formula_moiety         'C16 H14 N2 O S'
_chemical_formula_sum            'C16 H14 N2 O S'
_chemical_formula_weight         282.37
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     direct
_audit_creation_date             2021-02-17
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                96.180(2)
_cell_angle_beta                 92.803(2)
_cell_angle_gamma                108.433(3)
_cell_formula_units_Z            2
_cell_length_a                   6.4476(2)
_cell_length_b                   9.4727(3)
_cell_length_c                   12.1525(3)
_cell_measurement_reflns_used    9680
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      75.2110
_cell_measurement_theta_min      3.6850
_cell_volume                     697.34(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.9816
_diffrn_measured_fraction_theta_max 0.9809
_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    -86.00  -6.00   0.50    0.38    --  -38.50 125.00 139.00  160
  2  \w   -102.00 -16.00   0.50    0.38    --  -38.50 146.00 -54.00  172
  3  \w     38.00 114.00   0.50    0.38    --   49.56-146.00-105.00  152
  4  \w     97.00 168.00   0.50    1.48    --  102.63 125.00 139.00  142
  5  \w     86.00 166.00   0.50    1.48    --  102.63 146.00 -54.00  160
  6  \w     38.00 112.00   0.50    1.48    --  102.63-125.00  61.00  148
  7  \w    -50.00  24.00   0.50    0.38    --  -38.50  57.00 -30.00  148
  8  \w    -42.00  28.00   0.50    0.38    --  -38.50  38.00 -90.00  140
  9  \w    -44.00  31.00   0.50    0.38    --  -38.50  19.00-120.00  150
 10  \w   -101.00 -27.00   0.50    0.38    --  -38.50 -57.00-120.00  148
 11  \w     28.00 101.00   0.50    0.38    --   49.56-125.00  61.00  146
 12  \w     38.00 107.00   0.50    1.48    --  102.63 -45.00   0.00  138
 13  \w     40.00 116.00   0.50    1.48    --  102.63 -61.00-150.00  152
 14  \w     98.00 167.00   0.50    1.48    --  102.63  45.00  60.00  138
 15  \w     35.00 106.00   0.50    1.48    --  102.63 -30.00 -90.00  142
 16  \w     90.00 165.00   0.50    1.48    --  102.63  61.00 -30.00  150
 17  \w     38.00 126.00   0.50    1.48    --  102.63 -77.00  30.00  176
 18  \w     98.00 167.00   0.50    1.48    --  102.63  45.00 -60.00  138
 19  \w     40.00 116.00   0.50    1.48    --  102.63 -61.00 -90.00  152
 20  \w     35.00 106.00   0.50    1.48    --  102.63 -30.00  30.00  142
 21  \w     90.00 165.00   0.50    1.48    --  102.63  61.00  30.00  150
 22  \w     97.00 168.00   0.50    1.48    --  102.63 125.00 -90.00  142
 23  \w     38.00 112.00   0.50    1.48    --  102.63-125.00 -30.00  148
 24  \w     90.00 165.00   0.50    1.48    --  102.63  61.00 -90.00  150
 25  \w     34.00 107.00   0.50    1.48    --  102.63 -94.00-150.00  146
 26  \w     38.00 112.00   0.50    1.48    --  102.63-125.00 150.00  148
 27  \w     35.00 106.00   0.50    1.48    --  102.63 -30.00 120.00  142
 28  \w     97.00 168.00   0.50    1.48    --  102.63 125.00 150.00  142
 29  \w     38.00 107.00   0.50    1.48    --  102.63 -45.00-180.00  138
 30  \w     39.00 128.00   0.50    1.48    --  102.63-146.00-105.00  178
 31  \w     38.00 107.00   0.50    0.38    --   49.56  57.00 150.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0232630000
_diffrn_orient_matrix_UB_12      0.1677653000
_diffrn_orient_matrix_UB_13      0.0219745000
_diffrn_orient_matrix_UB_21      -0.0372642000
_diffrn_orient_matrix_UB_22      0.0033208000
_diffrn_orient_matrix_UB_23      -0.1257520000
_diffrn_orient_matrix_UB_31      -0.2489905000
_diffrn_orient_matrix_UB_32      -0.0416560000
_diffrn_orient_matrix_UB_33      0.0094432000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0461
_diffrn_reflns_av_unetI/netI     0.0422
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10340
_diffrn_reflns_theta_full        75.4136
_diffrn_reflns_theta_max         75.41
_diffrn_reflns_theta_min         3.67
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.027
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74888
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            clear
_exptl_crystal_colour_lustre     clear
_exptl_crystal_density_diffrn    1.3447
_exptl_crystal_description       needle
_exptl_crystal_F_000             297.4742
_exptl_crystal_preparation       'Slow diffusion method'
_exptl_crystal_recrystallization_method 'Sloww diffusion method'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.4761
_refine_diff_density_min         -0.5019
_refine_diff_density_rms         0.1819
_refine_ls_d_res_high            0.7966
_refine_ls_d_res_low             12.0351
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0423
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    25
_refine_ls_number_parameters     183
_refine_ls_number_reflns         2827
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0423
_refine_ls_R_factor_all          0.0421
_refine_ls_R_factor_gt           0.0385
_refine_ls_shift/su_max          0.0002
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0614P)^2^+0.3139P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1051
_refine_ls_wR_factor_ref         0.1054
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              8
_reflns_limit_h_min              -8
_reflns_limit_k_max              11
_reflns_limit_k_min              -11
_reflns_limit_l_max              15
_reflns_limit_l_min              0
_reflns_number_gt                2787
_reflns_number_total             2827
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            ao1c03410_si_003.cif
_cod_data_source_block           PERU-AW-126
_cod_database_code               4519003
_chemical_oxdiff_formula         'C34 H26 N2 O2 S2 '
_diffrn_oxdiff_digest_frames
;
01c173412983e03366fedadbc873a52d230461692dc
;
_diffrn_oxdiff_digest_hkl
;
0148c6cbc59c88ad36608c219bd28697d4380f
;
_reflns_odcompleteness_completeness 99.96
_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,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C7(H7), C16(H16), C14(H14), C4(H4), C6(H6), C15(H15), C5(H5),
 C13(H13)
2.b X=CH2 refined with riding coordinates:
 N18(H18a,H18b)
2.c Idealised Me refined as rotating group:
 C20(H20a,H20b,H20c)
;
_olex2_submission_original_sample_id Peru_AW_126
_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 1.725
_oxdiff_exptl_absorpt_empirical_full_min 0.610