Switchable C2/C3 positional selectivity of thioisatins in a three-component domino reaction: combined computational and experimental studies
Liu, Baolin; Deng, Qingsong; Zhang, Lei; Meng, Xiangtai; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01764D

data_7158971
_publ_section_title
;
 Switchable C2/C3 positional selectivity of thioisatins in a
 three-component domino reaction: combined computational and experimental
 studies
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01764D
_journal_year                    2022
_chemical_formula_moiety         'C29 H26 N2 S, C H2 Cl2, C H Cl2'
_chemical_formula_sum            'C31 H29 Cl4 N2 S'
_chemical_formula_weight         603.42
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-09-06 deposited with the CCDC.	2022-11-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.1760(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.57330(10)
_cell_length_b                   25.8833(3)
_cell_length_c                   11.55000(10)
_cell_measurement_reflns_used    18974
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.0580
_cell_measurement_theta_min      1.7370
_cell_volume                     3100.97(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.89a (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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      8.00  69.00   0.50    1.00    --   42.30 -82.00  90.00  122
  2  \w    -46.00  13.00   0.50    1.00    --   42.30 -82.00 -60.00  118
  3  \w     72.00  98.00   0.50    1.00    --   42.30  82.00-180.00   52
  4  \w     38.00  70.00   0.50    1.00    --   42.30 -82.00 -30.00   64
  5  \w    -46.00  24.00   0.50    1.00    --   42.30 -82.00  60.00  140
  6  \w     74.00 128.00   0.50    1.00    --   42.30  54.00 -60.00  108
  7  \w     18.00  54.00   0.50    1.00    --   42.30  43.00  30.00   72
  8  \w    -46.00 -20.00   0.50    1.00    --   42.30 -43.00  90.00   52
  9  \w     28.00  70.00   0.50    1.00    --   42.30 -82.00 -90.00   84
 10  \w    -46.00  10.00   0.50    1.00    --   42.30 -54.00-150.00  112
 11  \w    -39.00 -14.00   0.50    1.00    --   42.30 -82.00 150.00   50
 12  \w     36.00  66.00   0.50    1.00    --   42.30 -82.00  60.00   60
 13  \w    -47.00   2.00   0.50    1.00    --   42.30 -54.00   0.00   98
 14  \w     12.00  69.00   0.50    1.00    --   42.30 -54.00   0.00  114
 15  \w    -18.00  65.00   0.50    1.00    --   42.30 -82.00-111.33  166
 16  \w     85.00 131.00   0.50    1.00    --   42.30  43.00  30.00   92
 17  \w     35.00  69.00   0.50    1.00    --   42.30 -82.00 150.00   68
 18  \w     32.00  61.00   0.50    1.00    --   42.30 -43.00  90.00   58
 19  \w    -10.00  21.00   0.50    1.00    --   42.30 -82.00 150.00   62
 20  \w     21.00  71.00   0.50    1.00    --   42.30  82.00-180.00  100
 21  \w     -7.00  20.00   0.50    1.00    --   42.30 -82.00 -90.00   54
 22  \w     47.00  72.00   0.50    1.00    --   42.30 -54.00-150.00   50
 23  \w    -20.00   5.00   0.50    1.00    --   42.30 -82.00  90.00   50
 24  \w     44.00  69.00   0.50    1.00    --   42.30 -82.00 -60.00   50
 25  \w      4.00 121.00   0.50    3.00    --   93.70 -82.00 120.00  234
 26  \w     13.00 121.00   0.50    3.00    --   93.70 -59.00 -30.00  216
 27  \w     35.00  80.00   0.50    3.00    --   93.70 -82.00 -60.00   90
 28  \w     87.00 113.00   0.50    3.00    --   93.70 -82.00 150.00   52
 29  \w     15.00 108.00   0.50    3.00    --   93.70 -82.00 -30.00  186
 30  \w     50.00  92.00   0.50    3.00    --   93.70 -82.00-180.00   84
 31  \w     99.00 175.00   0.50    3.00    --   93.70  68.00 -90.00  152
 32  \w      9.00 106.00   0.50    3.00    --   93.70 -82.00-120.00  194
 33  \w     41.00  85.00   0.50    3.00    --   93.70 -82.00  60.00   88
 34  \w      4.00  95.00   0.50    3.00    --   93.70 -82.00-157.95  182
 35  \w     26.00  52.00   0.50    3.00    --   93.70 -82.00  30.00   52
 36  \w     55.00  99.00   0.50    3.00    --   93.70 -82.00 -90.00   88
 37  \w     66.00 124.00   0.50    3.00    --   93.70 -42.00-180.00  116
 38  \w     53.00  92.00   0.50    3.00    --   93.70 -82.00  90.00   78
 39  \w     83.00 122.00   0.50    3.00    --   93.70 -50.00  60.00   78
 40  \w     26.00  53.00   0.50    3.00    --   93.70 -50.00  60.00   54
 41  \w     10.00  47.00   0.50    3.00    --   93.70 -42.00-180.00   74
 42  \w    141.00 181.00   0.50    3.00    --   93.70  50.00  30.00   80
 43  \w     59.00 127.00   0.50    3.00    --   93.70  33.00  90.00  136
 44  \w     77.00 103.00   0.50    3.00    --   93.70  50.00  30.00   52
 45  \w    149.00 183.00   0.50    3.00    --   93.70   8.00  60.00   68
 46  \w     75.00 101.00   0.50    3.00    --   93.70 -82.00  30.00   52
 47  \w     69.00 101.00   0.50    3.00    --   93.70 -82.00   0.00   64
 48  \w     25.00  51.00   0.50    3.00    --   93.70 -82.00   0.00   52
 49  \w    109.00 173.00   0.50    3.00    --   93.70  59.00 -60.00  128
 50  \w     67.00  93.00   0.50    3.00    --   93.70 -82.00-150.00   52
 51  \w     38.00 142.00   0.50    3.00    --   93.70   8.00  60.00  208
 52  \w     64.00  91.00   0.50    3.00    --   93.70 -82.00 145.52   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1338537000
_diffrn_orient_matrix_UB_12      0.0120511000
_diffrn_orient_matrix_UB_13      0.0272309000
_diffrn_orient_matrix_UB_21      -0.0455694000
_diffrn_orient_matrix_UB_22      -0.0549069000
_diffrn_orient_matrix_UB_23      -0.0392666000
_diffrn_orient_matrix_UB_31      0.0453372000
_diffrn_orient_matrix_UB_32      -0.0195370000
_diffrn_orient_matrix_UB_33      0.1273398000
_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  0.0395
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            29665
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        65.079
_diffrn_reflns_theta_max         65.079
_diffrn_reflns_theta_min         3.415
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.267
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48333
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             1252
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.808
_refine_diff_density_min         -0.753
_refine_diff_density_rms         0.078
_refine_ls_extinction_coef       0.0036(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     425
_refine_ls_number_reflns         5233
_refine_ls_number_restraints     216
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0743
_refine_ls_R_factor_gt           0.0720
_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^)+(0.1455P)^2^+1.8051P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2094
_refine_ls_wR_factor_ref         0.2124
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4851
_reflns_number_total             5233
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01764d2.cif
_cod_data_source_block           mxtlbl2022060901_auto
_cod_database_code               7158971
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.361
_shelx_estimated_absorpt_t_min   0.280
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C20 \\sim C12 \\sim C32 \\sim C19 \\sim C21 \\sim C6: within 3.8A with sigma of
0.01 and sigma for terminal atoms of 0.03 within 3.8A
C6 \\sim C35 \\sim C21 \\sim C19 \\sim C32 \\sim C37 \\sim C12 \\sim C20 \\sim
C34: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.03 within
3.8A
3. Others
 Fixed Sof: C6(0.33333) H6A(0.33333) H6B(0.33333) H6C(0.33333) C12(0.33333)
 H12A(0.33333) H12B(0.33333) H12C(0.33333) C19(0.33333) H19A(0.33333)
 H19B(0.33333) H19C(0.33333) C32(0.33333) H32A(0.33333) H32B(0.33333)
 H32C(0.33333) C21(0.33333) H21A(0.33333) H21B(0.33333) H21C(0.33333)
 C20(0.33333) H20A(0.33333) H20B(0.33333) H20C(0.33333) C37(0.33333)
 H37A(0.33333) H37B(0.33333) H37C(0.33333) C35(0.33333) H35A(0.33333)
 H35B(0.33333) H35C(0.33333) C34(0.33333) H34A(0.33333) H34B(0.33333)
 H34C(0.33333) Cl3(0.5) Cl4(0.5) Cl5(0.5) H33A(0.5) H33B(0.5) Cl6(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C36(H36A,H36B), C33(H33A,H33B)
4.b Aromatic/amide H refined with riding coordinates:
 N12(H12), C18(H18), C31(H31), C25(H25), C22(H22), C27(H27), C16(H16),
 C15(H15), C23(H23), C24(H24), C30(H30), C28(H28), C29(H29)
4.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C12(H12A,H12B,H12C), C19(H19A,H19B,H19C), C32(H32A,H32B,
 H32C), C21(H21A,H21B,H21C), C20(H20A,H20B,H20C), C37(H37A,H37B,H37C), C35(H35A,
 H35B,H35C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              61565
_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 1.699
_oxdiff_exptl_absorpt_empirical_full_min 0.646