Isothiourea catalysed enantioselective generation of point and axially chiral iminothia- and iminoselenazinanones
Nimmo, Alastair J.; Goodfellow, Alister S.; Guntley, Jacob T.; McKay, Aidan P.; Cordes, David B.; Bühl, Michael; Smith, Andrew D.; Chemical Science 16 (2025) 10494–10502; doi:10.1039/D5SC02435H

data_1575029
_publ_section_title
;
 Isothiourea catalysed enantioselective generation of point and axially
 chiral iminothia- and iminoselenazinanones
;
_journal_issue                   23
_journal_name_full               'Chemical Science'
_journal_page_first              10494
_journal_page_last               10502
_journal_paper_doi               10.1039/D5SC02435H
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H11 F3 N4 O S, 0.333(C H Cl3)'
_chemical_formula_sum            'C19.33 H11.33 Cl F3 N4 O S'
_chemical_formula_weight         440.17
_chemical_name_systematic
'(R,Z)-4-((3-(4-cyanophenyl)-4-oxo-6-(trifluoromethyl)-1,3-thiazinan-2-ylidene)amino)benzonitrile chloroform solvate'
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-17 deposited with the CCDC.	2025-04-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   21.67271(16)
_cell_length_b                   21.67271(16)
_cell_length_c                   10.76754(10)
_cell_measurement_reflns_used    36400
_cell_measurement_temperature    173
_cell_measurement_theta_max      66.0750
_cell_measurement_theta_min      4.0730
_cell_volume                     4379.99(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.82a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.82a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.82a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      173
_diffrn_detector                 'hybrid photon counting detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Dectris PILATUS P100K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -83.00   4.00   1.00    1.00    --    0.00 -37.00 -30.00   87
  2  \w    -83.00 -12.00   1.00    1.00    --    0.00 -19.00  30.00   71
  3  \w    -23.00  47.00   1.00    1.00    --    0.00 -82.00-150.00   70
  4  \w    -20.00  35.00   1.00    1.00    --    0.00  77.00-150.00   55
  5  \w     12.00  89.00   1.00    1.00    --    0.00  19.00  90.00   77
  6  \w    -33.00  48.00   1.00    1.00    --    5.00 -77.00  60.00   81
  7  \w    -15.00  35.00   1.00    1.00    --    5.00  77.00  30.00   50
  8  \w    -78.00  -7.00   1.00    1.00    --    5.00 -19.00 150.00   71
  9  \w    -15.00  35.00   1.00    1.00    --    5.00  77.00 -30.00   50
 10  \w    -15.00  35.00   1.00    1.00    --    5.00  77.00 150.00   50
 11  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00  60.00  116
 12  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00 -60.00  116
 13  \w    -60.00  32.00   1.00    1.00    --  -57.40  37.00  60.00   92
 14  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00 150.00  116
 15  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00-120.00  116
 16  \w    -78.00  32.00   1.00    1.00    --  -57.40  77.00 -60.00  110
 17  \w    -70.00  32.00   1.00    1.00    --  -57.40  57.00 -90.00  102
 18  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00 120.00  116
 19  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00   0.00  116
 20  \w   -141.00 -25.00   1.00    1.00    --  -57.40 -57.00-150.00  116
 21  \w    -78.00  32.00   1.00    1.00    --  -57.40  77.00  90.00  110
 22  \w   -167.00 -47.00   1.00    1.00    --  -83.30 -67.00 -52.00  120
 23  \w   -167.00 -45.00   1.00    1.00    --  -83.30 -70.00 -80.55  122
 24  \w   -167.00 -51.00   1.00    1.00    --  -83.30 -57.00 -30.00  116
 25  \w   -167.00 -51.00   1.00    1.00    --  -83.30 -57.00  90.00  116
 26  \w   -167.00 -45.00   1.00    1.00    --  -83.30 -71.00-166.62  122
 27  \w   -167.00 -51.00   1.00    1.00    --  -83.30 -57.00-120.00  116
 28  \w   -167.00 -51.00   1.00    1.00    --  -83.30 -57.00-150.00  116
 29  \w   -167.00 -47.00   1.00    1.00    --  -83.30 -67.00-164.64  120
 30  \w   -167.00 -46.00   1.00    1.00    --  -83.30 -69.00 142.99  121
 31  \w    -84.00 -51.00   1.00    1.00    --  -83.30 -57.00  30.00   33
 32  \w    -72.00 -45.00   1.00    1.00    --  -83.30 -71.00 156.08   27
 33  \w    -73.00 -48.00   1.00    1.00    --  -83.30 -66.00 -29.70   25
 34  \w   -100.00 -36.00   1.00    1.00    --  -83.30  77.00-150.00   64
 35  \w    -79.00 -50.00   1.00    1.00    --  -83.30 -62.00   6.16   29
 36  \w    -84.00 -51.00   1.00    1.00    --  -83.30 -57.00  60.00   33
 37  \w   -133.00-106.00   1.00    1.00    -- -109.20 -73.00  35.03   27
 38  \w   -183.00-157.00   1.00    1.00    -- -109.20 -73.00  35.03   26
 39  \w   -192.00-128.00   1.00    1.00    -- -109.20 -64.00 -13.52   64
 40  \w   -131.00 -73.00   1.00    1.00    -- -109.20 -72.00 151.34   58
 41  \w    -98.00 -71.00   1.00    1.00    -- -109.20 -71.00 -58.83   27
 42  \w   -191.00-165.00   1.00    1.00    -- -109.20 -72.00 151.34   26
 43  \w    -97.00 -71.00   1.00    1.00    -- -109.20 -71.00 159.13   26
 44  \w   -165.00-139.00   1.00    1.00    -- -109.20 -37.00  90.00   26
 45  \w    -97.00 -21.00   1.00    1.00    -- -109.20  80.00-138.51   76
 46  \w   -145.00-112.00   1.00    1.00    -- -109.20 -37.00 -90.00   33
 47  \w    -99.00 -73.00   1.00    1.00    -- -109.20  77.00 -90.00   26
 48  \w   -191.00-130.00   1.00    1.00    -- -109.20 -71.00 -58.83   61
 49  \w    -90.00 -64.00   1.00    1.00    -- -109.20   3.00 168.55   26
 50  \w   -107.00 -79.00   1.00    1.00    -- -109.20 -56.00 177.08   28
 51  \w   -124.00 -77.00   1.00    1.00    -- -109.20 -58.00   0.59   47
 52  \w    -95.00 -50.00   1.00    1.00    -- -109.20  82.00-109.29   45
 53  \w    -46.00 -20.00   1.00    1.00    -- -109.20  82.00-109.29   26
 54  \w    -94.00 -69.00   1.00    1.00    -- -109.20 -73.00-129.37   25
 55  \w    -96.00 -63.00   1.00    1.00    -- -109.20  77.00 120.00   33
 56  \w   -187.00-162.00   1.00    1.00    -- -109.20 -71.00 159.13   25
 57  \w    -97.00 -42.00   1.00    1.00    -- -109.20  82.00 155.28   55
 58  \w   -160.00-124.00   1.00    1.00    -- -109.20 -16.00 -69.81   36
 59  \w   -138.00-112.00   1.00    1.00    -- -109.20 -73.00-129.37   26
 60  \w   -136.00 -77.00   1.00    1.00    -- -109.20 -59.00 114.13   59
 61  \w   -131.00 -82.00   1.00    1.00    -- -109.20 -59.00 -23.89   49
 62  \w    -98.00 -72.00   1.00    1.00    -- -109.20 -69.00-169.59   26
 63  \w    -94.00 -69.00   1.00    1.00    -- -109.20 -73.00-101.47   25
 64  \w   -147.00-121.00   1.00    1.00    -- -109.20 -72.00  41.47   26
 65  \w    -97.00 -22.00   1.00    1.00    -- -109.20  19.00  30.00   75
 66  \w   -154.00-128.00   1.00    1.00    -- -109.20 -69.00-169.59   26
 67  \w   -176.00-151.00   1.00    1.00    -- -109.20 -62.00 -79.18   25
 68  \w   -138.00 -76.00   1.00    1.00    -- -109.20 -61.00 -35.08   62
 69  \w   -188.00-162.00   1.00    1.00    -- -109.20 -69.00-169.59   26
 70  \w   -172.00-127.00   1.00    1.00    -- -109.20 -73.00-101.47   45
 71  \w   -100.00 -64.00   1.00    1.00    -- -109.20  77.00 -30.00   36
 72  \w   -107.00 -76.00   1.00    1.00    -- -109.20 -72.00-144.12   31
 73  \w    -97.00 -70.00   1.00    1.00    -- -109.20 -72.00  78.25   27
 74  \w   -169.00-119.00   1.00    1.00    -- -109.20 -72.00-144.12   50
 75  \w    -94.00 -69.00   1.00    1.00    -- -109.20  71.00   4.53   25
 76  \w   -111.00 -73.00   1.00    1.00    -- -109.20 -68.00 136.90   38
 77  \w   -188.00 -71.00   1.00    1.00    -- -109.20 -70.00  53.00  117
 78  \w    -98.00 -71.00   1.00    1.00    -- -109.20 -72.00 -37.87   27
 79  \w    -91.00 -66.00   1.00    1.00    -- -109.20  70.00 -21.74   25
 80  \w   -192.00-147.00   1.00    1.00    -- -109.20 -61.00 -35.08   45
 81  \w    -99.00 -73.00   1.00    1.00    -- -109.20 -68.00 177.50   26
 82  \w   -167.00 -79.00   1.00    1.00    -- -109.20 -60.00  84.84   88
 83  \w   -110.00 -69.00   1.00    1.00    -- -109.20 -73.00 112.62   41
 84  \w   -103.00 -77.00   1.00    1.00    -- -109.20 -62.00 -79.18   26
 85  \w    -95.00 -48.00   1.00    1.00    -- -109.20  80.00  -1.52   47
 86  \w   -118.00 -77.00   1.00    1.00    -- -109.20 -63.00 -93.49   41
 87  \w    -97.00 -55.00   1.00    1.00    -- -109.20  80.00  39.76   42
 88  \w    -97.00 -70.00   1.00    1.00    -- -109.20 -72.00  41.47   27
 89  \w   -165.00-115.00   1.00    1.00    -- -109.20 -73.00 112.62   50
 90  \w   -118.00 -71.00   1.00    1.00    -- -109.20 -73.00-118.89   47
 91  \w    -95.00 -69.00   1.00    1.00    -- -109.20 -73.00  92.03   26
 92  \w   -158.00-132.00   1.00    1.00    -- -109.20 -73.00  92.03   26
 93  \w    -99.00 -73.00   1.00    1.00    -- -109.20 -67.00 -55.53   26
 94  \w   -187.00-162.00   1.00    1.00    -- -109.20 -13.00 152.10   25
 95  \w    -97.00 -71.00   1.00    1.00    -- -109.20 -73.00 -25.13   26
 96  \w    -95.00 -70.00   1.00    1.00    -- -109.20 -73.00  75.17   25
 97  \w   -103.00 -77.00   1.00    1.00    -- -109.20 -58.00 -89.33   26
 98  \w    -96.00 -70.00   1.00    1.00    -- -109.20  77.00  90.00   26
 99  \w    -97.00 -71.00   1.00    1.00    -- -109.20 -71.00 123.16   26
100  \w   -150.00-124.00   1.00    1.00    -- -109.20 -37.00  60.00   26
101  \w   -118.00 -73.00   1.00    1.00    -- -109.20 -67.00 158.00   45
102  \w   -172.00-146.00   1.00    1.00    -- -109.20 -58.00 -89.33   26
103  \w   -192.00 -92.00   1.00    1.00    -- -109.20 -48.00-124.93  100
104  \w    -96.00 -70.00   1.00    1.00    -- -109.20  57.00-120.00   26
105  \w   -184.00-117.00   1.00    1.00    -- -109.20 -64.00   8.00   67
106  \w   -119.00 -93.00   1.00    1.00    -- -109.20 -51.00-130.40   26
107  \w   -108.00 -72.00   1.00    1.00    -- -109.20 -71.00-155.43   36
108  \w   -106.00 -79.00   1.00    1.00    -- -109.20 -57.00 -16.88   27
109  \w    -99.00 -72.00   1.00    1.00    -- -109.20 -73.00  35.03   27
110  \w   -123.00 -80.00   1.00    1.00    -- -109.20 -61.00 164.65   43
111  \w   -101.00 -72.00   1.00    1.00    -- -109.20 -70.00 152.62   29
112  \w   -102.00 -75.00   1.00    1.00    -- -109.20 -64.00 -13.52   27
;
_diffrn_measurement_device       'AFC12: Kappa 4 circle'
_diffrn_measurement_device_type  'Rigaku XtaLAB P100K'
_diffrn_measurement_method       'shutterless scans'
_diffrn_measurement_specimen_support Loop
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0030348000
_diffrn_orient_matrix_UB_12      -0.0656417000
_diffrn_orient_matrix_UB_13      0.0465573000
_diffrn_orient_matrix_UB_21      -0.0597411000
_diffrn_orient_matrix_UB_22      -0.0475178000
_diffrn_orient_matrix_UB_23      -0.0913093000
_diffrn_orient_matrix_UB_31      0.0562193000
_diffrn_orient_matrix_UB_32      0.0129350000
_diffrn_orient_matrix_UB_33      -0.0998192000
_diffrn_radiation_monochromator  'Rigaku Osmic Confocal Optical System'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0239
_diffrn_reflns_av_unetI/netI     0.0090
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            41954
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.587
_diffrn_reflns_theta_max         66.587
_diffrn_reflns_theta_min         4.080
_diffrn_source                   'Rotating Anode'
_diffrn_source_type              'Rigaku MM-007HF'
_exptl_absorpt_coefficient_mu    3.174
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83024
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.82a (Rigaku Oxford Diffraction, 2023)
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    1.502
_exptl_crystal_description       prism
_exptl_crystal_F_000             2010
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Hexanes into chloroform'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.172
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1700 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         3444
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0216
_refine_ls_R_factor_gt           0.0215
_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^)+(0.0349P)^2^+2.5968P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0560
_refine_ls_wR_factor_ref         0.0560
_reflns_Friedel_coverage         0.994
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                3438
_reflns_number_total             3444
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02435h2.cif
_cod_data_source_block           35
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/current/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 
;
_cod_original_cell_volume        4379.99(8)
_cod_original_sg_symbol_H-M      'R 3'
_cod_database_code               1575029
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.599
_shelx_estimated_absorpt_t_min   0.449
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C30(H30)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12), C15(H15), C16(H16), C18(H18), C19(H19)
;
_shelx_res_checksum              3617