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_4519004
_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 H12 N2 S'
_chemical_formula_sum            'C16 H12 N2 S'
_chemical_formula_weight         264.35
_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     dual
_audit_creation_date             2021-02-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                106.308(2)
_cell_angle_beta                 104.374(2)
_cell_angle_gamma                103.637(2)
_cell_formula_units_Z            2
_cell_length_a                   8.1526(2)
_cell_length_b                   9.0963(2)
_cell_length_c                   10.4069(2)
_cell_measurement_reflns_used    9073
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.9820
_cell_measurement_theta_min      4.7100
_cell_volume                     677.68(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      291(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9750
_diffrn_measured_fraction_theta_max 0.9750
_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   -105.00 -36.00   0.15    0.20    --  -38.50 -35.00 143.00  460
  2  \w    -42.00  27.90   0.15    0.20    --  -38.50  35.00 -59.00  466
  3  \w    -18.00  51.90   0.15    0.20    --   49.31 -35.00 143.00  466
  4  \w     46.00 115.00   0.15    0.20    --   49.31  35.00 -59.00  460
  5  \w    103.00 172.00   0.15    0.80    --  106.38  35.00 -59.00  460
  6  \w     40.00 109.00   0.15    0.80    --  106.38 -35.00 143.00  460
  7  \w    -42.00  27.00   0.15    0.20    --  -38.50  37.00-180.00  460
  8  \w   -108.00 -33.00   0.15    0.20    --  -38.50 -19.00   0.00  500
  9  \w     24.00  99.00   0.15    0.20    --   49.31-125.00   0.00  500
 10  \w     46.00 115.00   0.15    0.20    --   49.31  37.00-180.00  460
 11  \w      2.00  83.90   0.15    0.20    --   49.31 -99.00  60.00  546
 12  \w    102.00 171.00   0.15    0.80    --  106.38  45.00 -30.00  460
 13  \w     38.00 113.90   0.15    0.80    --  106.38 -15.00 -30.00  506
 14  \w     38.00 110.00   0.15    0.80    --  106.38 -30.00 -60.00  480
 15  \w     98.00 173.90   0.15    0.80    --  106.38  15.00 -90.00  506
 16  \w     44.00 119.00   0.15    0.80    --  106.38 -61.00  60.00  500
 17  \w    102.00 171.00   0.15    0.80    --  106.38  45.00 -90.00  460
 18  \w     42.00 117.00   0.15    0.80    --  106.38-125.00-120.00  500
 19  \w     42.00 117.00   0.15    0.80    --  106.38-125.00 120.00  500
 20  \w     44.00 119.00   0.15    0.80    --  106.38 -61.00-120.00  500
 21  \w     42.00 111.00   0.15    0.80    --  106.38 -45.00  60.00  460
 22  \w     44.00 119.00   0.15    0.80    --  106.38 -61.00 -90.00  500
 23  \w    103.00 175.00   0.15    0.80    --  106.38  30.00   0.00  480
 24  \w     44.00 119.00   0.15    0.80    --  106.38 -61.00-180.00  500
 25  \w     42.00 117.00   0.15    0.80    --  106.38-125.00 -60.00  500
 26  \w     42.00 117.00   0.15    0.80    --  106.38-125.00-180.00  500
 27  \w     38.00 110.00   0.15    0.80    --  106.38 -94.00   0.00  480
 28  \w     38.00 110.00   0.15    0.80    --  106.38 -94.00-180.00  480
 29  \w     26.00 113.00   0.15    0.20    --   49.31  77.00-150.00  580
 30  \w     26.00 113.00   0.15    0.20    --   49.31  77.00   0.00  580
 31  \w     26.00 113.00   0.15    0.20    --   49.31  77.00 -60.00  580
 32  \w     38.00 110.90   0.15    0.20    --   49.31  57.00  90.00  486
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0841162000
_diffrn_orient_matrix_UB_12      0.1859345000
_diffrn_orient_matrix_UB_13      0.0547707000
_diffrn_orient_matrix_UB_21      -0.1600161000
_diffrn_orient_matrix_UB_22      0.0183068000
_diffrn_orient_matrix_UB_23      0.0489204000
_diffrn_orient_matrix_UB_31      0.0998904000
_diffrn_orient_matrix_UB_32      -0.0003164000
_diffrn_orient_matrix_UB_33      0.1464473000
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            10388
_diffrn_reflns_theta_full        77.3902
_diffrn_reflns_theta_max         77.39
_diffrn_reflns_theta_min         4.70
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.996
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50304
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.2954
_exptl_crystal_description       needle
_exptl_crystal_F_000             277.3708
_exptl_crystal_preparation       'Slow diffusion'
_exptl_crystal_recrystallization_method 'Slow evapouration'
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.1951
_refine_diff_density_min         -0.2711
_refine_diff_density_rms         0.0445
_refine_ls_d_res_high            0.7900
_refine_ls_d_res_low             9.4034
_refine_ls_goodness_of_fit_ref   1.0462
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    22
_refine_ls_number_parameters     173
_refine_ls_number_reflns         2813
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0462
_refine_ls_R_factor_all          0.0424
_refine_ls_R_factor_gt           0.0408
_refine_ls_shift/su_max          0.0000
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0539P)^2^+0.2015P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1094
_refine_ls_wR_factor_ref         0.1105
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              9
_reflns_limit_h_min              -10
_reflns_limit_k_max              10
_reflns_limit_k_min              -11
_reflns_limit_l_max              13
_reflns_limit_l_min              0
_reflns_number_gt                2645
_reflns_number_total             2813
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            ao1c03410_si_002.cif
_cod_data_source_block           PERU_AW_73
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_ambient_temperature' value '291 (2)' was changed
to '291(2)' -- the value was reformatted.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               4519004
_chemical_oxdiff_formula         'C32 H24 N4 S2 '
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C24(H24), C5(H5), C12(H12), C6(H6), C14(H14), C7(H7), C13(H13), C16(H16),
 C15(H15)
2.b Idealised Me refined as rotating group:
 C19(H19a,H19b,H19c)
;
_olex2_submission_original_sample_id AW_74
_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 3.036
_oxdiff_exptl_absorpt_empirical_full_min 0.382