Synthesis of 3,4-Dihydro-2H-1,3-thiazines from α-Enolic Dithioesters and 1,3,5-Triazinanes via a Formal (3 + 3) Annulation Reaction
Cheng, Bin; Li, Hui; Hou, Jieping; Zhang, Xinping; He, Yixuan; Sun, Haiyan; Xu, Wei; Wang, Taimin; Zhai, Hongbin; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.0c01984

data_4038847
_publ_section_title
;
 Synthesis of 3,4-Dihydro-2H-1,3-thiazines from \a-Enolic Dithioesters and
 1,3,5-Triazinanes via a Formal (3 + 3) Annulation Reaction
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01984
_journal_year                    2020
_chemical_formula_moiety         'C19 H19 N O S2'
_chemical_formula_sum            'C19 H19 N O S2'
_chemical_formula_weight         341.47
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-12-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4553(3)
_cell_length_b                   7.4507(3)
_cell_length_c                   24.9074(8)
_cell_measurement_reflns_used    1689
_cell_measurement_temperature    293.77(10)
_cell_measurement_theta_max      69.5750
_cell_measurement_theta_min      8.4940
_cell_volume                     1754.69(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.77(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.973
_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    -14.00  23.00   1.00    1.00    --    0.00 -38.00  90.00   37
  2  \w      5.00  94.00   1.00    1.00    --   54.00 -99.00 -30.00   89
  3  \w     51.00 113.00   1.00    1.00    --  108.00-111.00 -30.00   62
  4  \w     46.00 111.00   1.00    1.00    --  108.00 -25.00  30.00   65
  5  \w     53.00 124.00   1.00    1.00    --   54.00  77.00 -30.00   71
  6  \w    103.00 146.00   1.00    1.00    --  108.00 111.00 -60.00   43
  7  \w    145.00 175.00   1.00    1.00    --  108.00  50.00-150.00   30
  8  \w    108.00 162.00   1.00    1.00    --  108.00  61.00-176.00   54
  9  \w    103.00 145.00   1.00    1.00    --  108.00 111.00  90.00   42
 10  \w     -1.00  24.00   1.00    1.00    --    0.00  86.00  53.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0472383000
_diffrn_orient_matrix_UB_12      -0.0748581000
_diffrn_orient_matrix_UB_13      0.0548033000
_diffrn_orient_matrix_UB_21      -0.1062456000
_diffrn_orient_matrix_UB_22      -0.1554669000
_diffrn_orient_matrix_UB_23      -0.0058643000
_diffrn_orient_matrix_UB_31      0.1141503000
_diffrn_orient_matrix_UB_32      -0.1139333000
_diffrn_orient_matrix_UB_33      -0.0280592000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0224
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            3472
_diffrn_reflns_point_group_measured_fraction_full 0.715
_diffrn_reflns_point_group_measured_fraction_max 0.715
_diffrn_reflns_theta_full        66.578
_diffrn_reflns_theta_max         66.578
_diffrn_reflns_theta_min         5.939
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.767
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39885
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.159
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 585 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.001(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2211
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0350
_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^)+(0.0492P)^2^+0.0206P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0873
_refine_ls_wR_factor_ref         0.0899
_reflns_Friedel_coverage         0.433
_reflns_Friedel_fraction_full    0.444
_reflns_Friedel_fraction_max     0.444
_reflns_number_gt                2116
_reflns_number_total             2211
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01984_si_002.cif
_cod_data_source_block           lih_1227
_cod_original_cell_volume        1754.69(10)
_cod_database_code               4038847
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.698
_shelx_estimated_absorpt_t_min   0.594
_reflns_odcompleteness_completeness 96.76
_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 C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C21(H21A,H21B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C8(H8), C11(H11), C13(H13), C15(H15), C16(H16), C17(H17),
 C18(H18)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              17489
_shelx_hkl_checksum              15092
_olex2_date_sample_data_collection 2019-12-27
_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 2.138
_oxdiff_exptl_absorpt_empirical_full_min 0.653