Convergent synthesis of thiodiazole dioxides from simple ketones and amines through an unusual nitrogen-migration mechanism.
Punjajom, Kunlayanee; Sinclair, Paul P.; Saha, Ishika; Seierstad, Mark; Ameriks, Michael K.; García-Reynaga, Pablo; Lebold, Terry P.; Sarpong, Richmond; Chemical science 15 (2023) 328–335; doi:10.1039/d3sc04478e

data_1570375
_publ_section_title
;
 Convergent synthesis of thiodiazole dioxides from simple ketones and
 amines through an unusual nitrogen-migration mechanism.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              328
_journal_page_last               335
_journal_paper_doi               10.1039/d3sc04478e
_journal_volume                  15
_journal_year                    2023
_chemical_formula_moiety         'C12 H13 F N2 O2 S'
_chemical_formula_sum            'C12 H13 F N2 O2 S'
_chemical_formula_weight         268.30
_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             2022-09-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-07-24 deposited with the CCDC.	2023-11-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.575(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.5943(5)
_cell_length_b                   5.87350(10)
_cell_length_c                   9.8361(2)
_cell_measurement_reflns_used    6963
_cell_measurement_temperature    100
_cell_measurement_theta_max      78.1730
_cell_measurement_theta_min      6.2380
_cell_volume                     1226.36(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.67a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.67a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.67a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -45.00  27.00   0.50    1.00    --  -50.71  37.00 -49.00  144
  2  \w   -128.00 -39.00   0.50    1.00    --  -50.71 -37.00 154.00  178
  3  \w     39.00 128.00   0.50    1.00    --   50.71  37.00 -49.00  178
  4  \w    -27.00  39.00   0.50    1.00    --   50.71 -37.00 154.00  132
  5  \w   -178.00 -87.00   0.50    4.00    -- -100.00 -37.00 154.00  182
  6  \w     95.00 175.00   0.50    4.00    --  107.75  37.00 -49.00  160
  7  \w    -30.00  29.00   0.50    1.00    --  -50.71  19.00  90.00  118
  8  \w     76.00 124.00   0.50    1.00    --   50.71 125.00   0.00   96
  9  \w     81.00 124.00   0.50    1.00    --   50.71  77.00-120.00   86
 10  \w    -28.00  24.00   0.50    1.00    --   50.71 -19.00   0.00  104
 11  \w     81.00 124.00   0.50    1.00    --   50.71  77.00  90.00   86
 12  \w   -108.00 -26.00   0.50    4.00    -- -100.00  77.00 -60.00  164
 13  \w    -54.00 -24.00   0.50    4.00    -- -100.00  45.00-120.00   60
 14  \w    -74.00 -29.00   0.50    4.00    -- -100.00  61.00  60.00   90
 15  \w     36.00  68.00   0.50    4.00    --  107.75 -61.00-150.00   64
 16  \w     34.00 102.00   0.50    4.00    --  107.75 -77.00-180.00  136
 17  \w     36.00  68.00   0.50    4.00    --  107.75 -61.00 150.00   64
 18  \w     83.00 175.00   0.50    4.00    --  107.75 111.00  60.00  184
 19  \w     34.00 102.00   0.50    4.00    --  107.75 -77.00 150.00  136
 20  \w     35.00 109.00   0.50    4.00    --  107.75-111.00  60.00  148
 21  \w     36.00  68.00   0.50    4.00    --  107.75 -61.00-120.00   64
 22  \w     34.00 102.00   0.50    4.00    --  107.75 -77.00  90.00  136
 23  \w     94.00 175.00   0.50    4.00    --  107.75  30.00 -90.00  162
 24  \w     94.00 175.00   0.50    4.00    --  107.75  45.00 -30.00  162
 25  \w     34.00 102.00   0.50    4.00    --  107.75 -77.00 -30.00  136
 26  \w     34.00  83.00   0.50    4.00    --  107.75 -77.00  60.00   98
 27  \w     31.00  83.00   0.50    4.00    --  107.75 -94.00 -30.00  104
 28  \w     36.00  68.00   0.50    4.00    --  107.75 -61.00-180.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0695960000
_diffrn_orient_matrix_UB_12      0.0734293000
_diffrn_orient_matrix_UB_13      0.0337798000
_diffrn_orient_matrix_UB_21      -0.0053407000
_diffrn_orient_matrix_UB_22      0.0977273000
_diffrn_orient_matrix_UB_23      -0.1470517000
_diffrn_orient_matrix_UB_31      -0.0197808000
_diffrn_orient_matrix_UB_32      0.2322021000
_diffrn_orient_matrix_UB_33      0.0511577000
_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  0.0571
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            13506
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.464
_diffrn_reflns_theta_min         4.165
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.449
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85127
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.67a (Rigaku Oxford Diffraction, 2022)
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    1.453
_exptl_crystal_description       plate
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.280
_refine_diff_density_min         -0.440
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     164
_refine_ls_number_reflns         2513
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0614P)^2^+0.4970P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1050
_refine_ls_wR_factor_ref         0.1089
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2198
_reflns_number_total             2513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04478e2.cif
_cod_data_source_block           KPunjajom01_Sarpong
_cod_depositor_comments          'Adding full bibliography for 1570375.cif.'
_cod_database_code               1570375
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C F O S N H'
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.741
_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:
 C4(H4A,H4B), C5(H5A,H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12)
2.c X=CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C)
;
_shelx_res_checksum              88379
_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 3.000
_oxdiff_exptl_absorpt_empirical_full_min 0.559