Harnessing Sulfur and Nitrogen in the Cobalt (III)-Catalyzed Unsymmetrical Double Annulation of Thioamides: Probing the Origin of Chemo- and Regioselectivity
Shankar, Majji; Saha, Arijit; Sau, Somratan; Ghosh, Arghadip; Gandon, Vincent; Sahoo, Akhila Kumar; Chemical Science  (2021) –; doi:10.1039/D1SC00765C

data_1561172
_publ_section_title
;
 Harnessing Sulfur and Nitrogen in the Cobalt (III)-Catalyzed
 Unsymmetrical Double Annulation of Thioamides: Probing the Origin of
 Chemo- and Regioselectivity
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC00765C
_journal_year                    2021
_chemical_formula_moiety         'C38 H25 N1.75 O2 S'
_chemical_formula_sum            'C38 H25 N1.75 O2 S'
_chemical_formula_weight         570.16
_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             2020-11-21
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2020-11-23 deposited with the CCDC.	2021-03-19 downloaded from the CCDC.
;
_cell_angle_alpha                103.8030(10)
_cell_angle_beta                 92.000(2)
_cell_angle_gamma                108.233(2)
_cell_formula_units_Z            2
_cell_length_a                   9.3410(2)
_cell_length_b                   11.8743(2)
_cell_length_c                   14.2000(2)
_cell_measurement_reflns_used    9621
_cell_measurement_temperature    306.42(11)
_cell_measurement_theta_max      25.7320
_cell_measurement_theta_min      2.0520
_cell_volume                     1442.47(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      306.42(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.954
_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    -32.00  12.00   0.50    4.53    --   16.22 -45.00 -30.00   88
  2  \w    -23.00  20.00   0.50    4.53    --  -14.97 -94.00 -60.00   86
  3  \w     21.00  48.00   0.50    4.53    --   16.22-142.00 -86.00   54
  4  \w     10.00  48.00   0.50    4.53    --   16.22 -94.00-120.00   76
  5  \w     21.00  63.00   0.50    4.53    --   16.22-125.00-150.00   84
  6  \w     -7.00  43.00   0.50    4.53    --   16.22 -61.00-120.00  100
  7  \w    -12.00  21.00   0.50    4.53    --  -14.97 -94.00-180.00   66
  8  \w    -37.00   0.00   0.50    4.53    --   16.22 -94.00-120.00   74
  9  \w    -36.00   1.00   0.50    4.53    --   16.22 -94.00 -90.00   74
 10  \w    -53.00 -25.00   0.50    4.53    --   16.22 -61.00-120.00   56
 11  \w    -88.00   7.00   0.50    4.53    --  -14.97 -30.00-120.00  190
 12  \w    -84.00  13.00   0.50    4.53    --  -14.97 -61.00   0.00  194
 13  \w    -33.00  -8.00   0.50    4.53    --  -14.97 -94.00  30.00   50
 14  \w    -18.00  20.00   0.50    4.53    --  -14.97 -94.00  60.00   76
 15  \w     45.00  70.00   0.50    4.53    --   16.22-128.00  84.00   50
 16  \w     16.00  54.00   0.50    4.53    --   16.22-125.00  30.00   76
 17  \w     37.00  95.00   0.50    4.53    --   16.22   0.00  60.00  116
 18  \w     34.00  59.00   0.50    4.53    --   16.22  45.00  60.00   50
 19  \w     48.00  85.00   0.50    4.53    --   16.22  61.00  60.00   74
 20  \w     -2.00  25.00   0.50    4.53    --   16.22   0.00  60.00   54
 21  \w    -56.00  18.00   0.50    4.53    --   16.22 -30.00 120.00  148
 22  \w    -63.00  10.00   0.50    4.53    --  -14.97 -45.00  90.00  146
 23  \w    -45.00 -14.00   0.50    4.53    --   16.22   0.00  60.00   62
 24  \w    -41.00 -10.00   0.50    4.53    --  -14.97 125.00  60.00   62
 25  \w    -74.00 -49.00   0.50    4.53    --  -14.97 142.00 -30.00   50
 26  \w    -38.00 -11.00   0.50    4.53    --  -14.97 125.00 -90.00   54
 27  \w    -66.00 -40.00   0.50    4.53    --  -14.97 128.00 159.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0731619000
_diffrn_orient_matrix_UB_12      0.0280255000
_diffrn_orient_matrix_UB_13      0.0269760000
_diffrn_orient_matrix_UB_21      0.0330908000
_diffrn_orient_matrix_UB_22      0.0011195000
_diffrn_orient_matrix_UB_23      -0.0441177000
_diffrn_orient_matrix_UB_31      -0.0059551000
_diffrn_orient_matrix_UB_32      0.0588405000
_diffrn_orient_matrix_UB_33      0.0030749000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0238
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            21430
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.996
_diffrn_reflns_theta_min         2.062
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.150
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83255
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_description       plate
_exptl_crystal_F_000             594
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.321
_refine_diff_density_min         -1.175
_refine_diff_density_rms         0.068
_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     389
_refine_ls_number_reflns         5991
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.1191
_refine_ls_R_factor_gt           0.0855
_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^)+(0.1824P)^2^+0.4061P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2790
_refine_ls_wR_factor_ref         0.3122
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3836
_reflns_number_total             5991
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00765c3.cif
_cod_data_source_block           aks71
_cod_database_code               1561172
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.952
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Others
 Fixed Sof: N2(0.75)
3.a Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C00L(H00L), C00M(H00M), C00N(H00N), C00O(H00O), C00P(H00P),
 C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U), C00V(H00V),
 C00X(H00X), C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011), C012(H012),
 C013(H013), C014(H014), C015(H015), C016(H016)
3.b Idealised Me refined as rotating group:
 C00W(H00A,H00B,H00C)
;
_shelx_res_checksum              38958
_shelx_hkl_checksum              43177
_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 1.324
_oxdiff_exptl_absorpt_empirical_full_min 0.764