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_1575031
_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         'C18 H13 F3 N2 O2 Se'
_chemical_formula_sum            'C18 H13 F3 N2 O2 Se'
_chemical_formula_weight         425.26
_chemical_name_systematic
;
(R,Z)-N-(4-oxo-3-phenyl-6-(trifluoromethyl)-1,3-selenazinan-2-ylidene)benzamide
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_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                 91.4505(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.51115(5)
_cell_length_b                   16.17558(9)
_cell_length_c                   10.71507(5)
_cell_measurement_reflns_used    43241
_cell_measurement_temperature    100
_cell_measurement_theta_max      74.9910
_cell_measurement_theta_min      4.6210
_cell_volume                     1647.968(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.94a (release 21-06-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.109a (Rigaku OD, 2024)'
_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      100
_diffrn_detector                 'hybrid photon counting detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Dectris PILATUS P200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -89.00  89.00   0.50    0.50    --    0.00  25.00 -35.00  356
  2  \w    -89.00  89.00   0.50    0.50    --    0.00  25.00 -35.00  356
  3  \w    -84.00  94.00   0.50    0.50    --    5.00  55.00 -43.94  356
  4  \w    -84.00  94.00   0.50    0.50    --    5.00  25.00 -35.00  356
  5  \w   -129.00  49.00   0.50    0.50    --  -40.00  55.00-179.28  356
  6  \w   -133.00  45.00   0.50    0.50    --  -44.00  55.00 -46.51  356
  7  \w   -133.00  45.00   0.50    0.50    --  -44.00  55.00  76.52  356
  8  \w   -137.00  41.00   0.50    0.50    --  -48.00  54.00  19.81  356
  9  \w   -145.00  33.00   0.50    0.50    --  -56.00  55.00-109.87  356
 10  \w   -145.00  33.00   0.50    0.50    --  -56.00  55.00 -70.27  356
 11  \w   -149.00  29.00   0.50    0.50    --  -60.00  55.00  75.62  356
 12  \w   -149.00  29.00   0.50    0.50    --  -60.00  54.00 160.15  356
 13  \w   -149.00  29.00   0.50    0.50    --  -60.00  55.00  32.92  356
 14  \w     -1.00  25.00   0.50    0.50    --  -64.00  55.00 136.39   52
 15  \w     -4.00  25.00   0.50    0.50    --  -64.00  55.00   3.11   58
 16  \w     -8.00  18.00   0.50    0.50    --  -68.00  55.00 -40.17   52
 17  \w    -11.00  20.00   0.50    0.50    --  -68.00  55.00-141.33   62
 18  \w     -9.00  19.00   0.50    0.50    --  -68.00  54.00 129.77   56
 19  \w    -18.00  17.00   0.50    0.50    --  -72.00  55.00 113.88   70
 20  \w    -11.00  15.00   0.50    0.50    --  -72.00  55.00 -55.89   52
 21  \w    -10.00  17.00   0.50    0.50    --  -72.00  55.00-115.04   54
 22  \w   -118.00 -52.00   0.50    0.50    --  -76.00  55.00-148.90  132
 23  \w    -14.00  12.00   0.50    0.50    --  -76.00  55.00-163.05   52
 24  \w    -24.00  12.00   0.50    0.50    --  -76.00  55.00  87.17   72
 25  \w    -16.00  12.00   0.50    0.50    --  -76.00  55.00   8.47   56
 26  \w    -74.00 -48.00   0.50    0.50    --  -76.00  55.00  87.17   52
 27  \w    -19.00  13.00   0.50    0.50    --  -76.00  55.00  41.74   64
 28  \w    -48.00  13.00   0.50    0.50    --  -76.00  55.00-148.90  122
 29  \w    -17.00  13.00   0.50    0.50    --  -76.00  55.00 -73.60   60
 30  \w   -118.00 -39.00   0.50    0.50    --  -76.00  55.00  41.74  158
 31  \w    -14.00  12.00   0.50    0.50    --  -76.00  52.00 -19.26   52
 32  \w   -143.00   8.00   0.50    0.50    --  -80.00  55.00  77.55  302
 33  \w    -23.00   5.00   0.50    0.50    --  -84.00  54.00 132.88   56
 34  \w   -133.00 -29.00   0.50    0.50    --  -84.00  54.00 132.88  208
 35  \w    -43.00  -3.00   0.50    0.50    --  -84.00  51.00 -80.26   80
 36  \w   -110.00 -84.00   0.50    0.50    --  -84.00  51.00 -80.26   52
 37  \w   -131.00  -3.00   0.50    0.50    --  -92.00  53.00 -22.53  256
 38  \w   -109.00 -83.00   0.50    0.50    --  -96.50  54.00-163.32   52
 39  \w   -183.00  -9.00   0.50    0.50    --  -96.50  55.00  33.10  348
 40  \w   -139.00  -8.00   0.50    0.50    --  -96.50  54.00 163.58  262
 41  \w   -163.00-136.00   0.50    0.50    --  -96.50  54.00-163.32   54
 42  \w   -147.00  -8.00   0.50    0.50    --  -96.50  53.00-119.00  278
 43  \w   -123.00  -8.00   0.50    0.50    --  -96.50  55.00 -47.33  230
 44  \w   -179.00-152.00   0.50    0.50    --  -96.50  55.00 -47.33   54
 45  \w   -120.00 -10.00   0.50    0.50    --  -96.50  54.00-170.94  220
 46  \w   -185.00-124.00   0.50    0.50    --  -96.50  54.00-170.94  122
 47  \w   -184.00 -11.00   0.50    0.50    --  -96.50  55.00  67.50  346
 48  \w    -39.00  -9.00   0.50    0.50    --  -96.50  55.00 120.66   60
 49  \w   -178.00 -45.00   0.50    0.50    --  -96.50  55.00 120.66  266
 50  \w   -185.00  -8.00   0.50    0.50    --  -96.50  55.00 -97.91  354
 51  \w    -42.00  -8.00   0.50    0.50    --  -96.50  55.00  -0.89   68
 52  \w   -114.00 -49.00   0.50    0.50    --  -96.50  55.00  -0.89  130
 53  \w    -49.00  -9.00   0.50    0.50    --  -96.50  54.00-163.32   80
 54  \w   -176.00-129.00   0.50    0.50    --  -96.50  55.00  -0.89   94
 55  \w    -82.00 -54.00   0.50    0.50    --  -96.50  54.00-163.32   56
 56  \w    -53.00 -27.00   0.50    0.50    --  -96.50  25.00 -35.00   52
 57  \w   -132.00-106.00   0.50    0.50    --  -96.50  25.00 -35.00   52
;
_diffrn_measurement_device       'AFC11: Quarter \c 4 circle'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200K'
_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      -0.0314904000
_diffrn_orient_matrix_UB_12      0.0236236000
_diffrn_orient_matrix_UB_13      0.1356913000
_diffrn_orient_matrix_UB_21      0.1508083000
_diffrn_orient_matrix_UB_22      0.0335069000
_diffrn_orient_matrix_UB_23      0.0175452000
_diffrn_orient_matrix_UB_31      -0.0501841000
_diffrn_orient_matrix_UB_32      0.0859846000
_diffrn_orient_matrix_UB_33      -0.0442292000
_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  0.0709
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            61612
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.618
_diffrn_reflns_theta_min         4.127
_diffrn_source                   'Rotating Anode'
_diffrn_source_type              'Rigaku MM-007HF'
_exptl_absorpt_coefficient_mu    3.538
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72712
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.109a (Rigaku Oxford Diffraction, 2024)
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    1.714
_exptl_crystal_description       plate
_exptl_crystal_F_000             848
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Hexane into ethyl acetate'
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.437
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 3000 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.046(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         6656
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0280
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0547P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0752
_refine_ls_wR_factor_ref         0.0755
_reflns_Friedel_coverage         0.899
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                6489
_reflns_number_total             6656
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02435h2.cif
_cod_data_source_block           53
_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_database_code               1575031
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.965
_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
2.a Ternary CH refined with riding coordinates:
 C6(H6), C26(H26)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C29(H29),
  C30(H30), C31(H31), C32(H32), C33(H33)
;
_shelx_res_checksum              40977