Spontaneous chiral symmetry breaking in a single crystal.
Oketani, Ryusei; Okada, Musashi; Takaji, Kentaro; Shigemitsu, Hajime; Kida, Toshiyuki; Nakashima, Takuya; Hisaki, Ichiro; Chemical science 16 (2025) 17621–17629; doi:10.1039/d5sc02623g

data_1575517
_publ_section_title
;
 Spontaneous chiral symmetry breaking in a single crystal.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              17621
_journal_page_last               17629
_journal_paper_doi               10.1039/d5sc02623g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C28 H22 N2 S2'
_chemical_formula_sum            'C28 H22 N2 S2'
_chemical_formula_weight         450.59
_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             2024-11-12
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-11-12 deposited with the CCDC.	2025-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.991(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.5534(3)
_cell_length_b                   5.5300(2)
_cell_length_c                   22.8598(7)
_cell_measurement_reflns_used    8955
_cell_measurement_temperature    113
_cell_measurement_theta_max      29.7980
_cell_measurement_theta_min      2.5570
_cell_volume                     1077.18(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_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      113
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.931
_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   -102.00  78.00   0.25    5.00    --  -12.00  45.00 193.00  720
  2  \w    -85.25  62.00   0.25    5.00    --  -12.00  45.00  86.00  589
  3  \w     -8.00  72.00   0.25    5.00    --  -12.00  45.00 -20.00  320
  4  \w    -62.00  62.00   0.25    5.00    --  -12.00  45.00 122.00  496
  5  \w    -80.00  49.00   0.25    5.00    --  -12.00  45.00 264.00  516
  6  \w   -102.00 -27.00   0.25    5.00    --  -12.00  45.00 157.00  300
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0385500000
_diffrn_orient_matrix_UB_12      0.0116012000
_diffrn_orient_matrix_UB_13      0.0286203000
_diffrn_orient_matrix_UB_21      0.0721736000
_diffrn_orient_matrix_UB_22      0.0204765000
_diffrn_orient_matrix_UB_23      -0.0122994000
_diffrn_orient_matrix_UB_31      -0.0152296000
_diffrn_orient_matrix_UB_32      0.1260694000
_diffrn_orient_matrix_UB_33      -0.0006541000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0535
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            20477
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.873
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.818
_diffrn_reflns_theta_min         2.478
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.267
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60972
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.95a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       plate
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.319
_exptl_crystal_size_mid          0.297
_exptl_crystal_size_min          0.016
_refine_diff_density_max         1.028
_refine_diff_density_min         -0.594
_refine_diff_density_rms         0.147
_refine_ls_abs_structure_details
;
 Flack x determined using 1697 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     372
_refine_ls_number_reflns         5392
_refine_ls_number_restraints     735
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0798
_refine_ls_R_factor_gt           0.0688
_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^)+(0.1333P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1778
_refine_ls_wR_factor_ref         0.1881
_reflns_Friedel_coverage         0.710
_reflns_Friedel_fraction_full    0.949
_reflns_Friedel_fraction_max     0.801
_reflns_number_gt                4644
_reflns_number_total             5392
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02623g24.cif
_cod_data_source_block           FormI
_cod_depositor_comments
'Adding full bibliography for 1575516--1575517.cif.'
_cod_database_code               1575517
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.920
_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. Restrained distances
 S2-C22 \\sim S2A-C22A
 with sigma of 0.02
 S2-C23 \\sim S2A-C23A
 with sigma of 0.02
 N2-C22 \\sim N2A-C22A
 with sigma of 0.02
 N2-C28 \\sim N2A-C28A
 with sigma of 0.02
 C24-C23 \\sim C24A-C23A
 with sigma of 0.02
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C22-C19 \\sim C22A-C19
 with sigma of 0.02
 C28-C23 \\sim C28A-C23A
 with sigma of 0.02
 C28-C27 \\sim C28A-C27A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 S2-N2 \\sim S2A-N2A
 with sigma of 0.04
 S2-C24 \\sim S2A-C24A
 with sigma of 0.04
 S2-C19 \\sim S2A-C19
 with sigma of 0.04
 S2-C28 \\sim S2A-C28A
 with sigma of 0.04
 N2-C19 \\sim N2A-C19
 with sigma of 0.04
 N2-C23 \\sim N2A-C23A
 with sigma of 0.04
 N2-C27 \\sim N2A-C27A
 with sigma of 0.04
 C24-C28 \\sim C24A-C28A
 with sigma of 0.04
 C24-C26 \\sim C24A-C26A
 with sigma of 0.04
 C22-C28 \\sim C22A-C28A
 with sigma of 0.04
 C22-C23 \\sim C22A-C23A
 with sigma of 0.04
 C28-C26 \\sim C28A-C26A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C23-C27 \\sim C23A-C27A
 with sigma of 0.04
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C22 \\sim N2: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 1.7A
C19 \\sim S1 \\sim C9 \\sim C11 \\sim C8 \\sim C10 \\sim C1 \\sim C12 \\sim C7
\\sim N1 \\sim C5 \\sim C2 \\sim C4 \\sim C6 \\sim C13 \\sim C16 \\sim C3 \\sim
C14 \\sim C21 \\sim C17 \\sim C15 \\sim C20 \\sim C18 \\sim C22 \\sim C22A
\\sim S2 \\sim N2 \\sim N2A \\sim S2A \\sim C23 \\sim C28 \\sim C28A \\sim C23A
\\sim C24 \\sim C27 \\sim C27A \\sim C24A \\sim C25 \\sim C26 \\sim C26A \\sim
C25A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 1.7A
4. Rigid body (RIGU) restrains
 C22, N2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, C9, C11, C8, C10, C1, C12, C7, N1, C5, C2, C4, C6, C13, C16, C3, C14, C21,
  C17, C15, C20, C18, C19, C22, C22A, S2, N2, N2A, S2A, C23, C28, C28A, C23A,
 C24, C27, C27A, C24A, C25, C26, C26A, C25A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C22A)=Sof(N2A)=Sof(C28A)=Sof(C27A)=Sof(H27A)=Sof(C26A)=Sof(H26A)=
 Sof(C25A)=Sof(H25A)=Sof(C24A)=Sof(H24A)=Sof(C23A)=Sof(S2A)=1-FVAR(1)
 Sof(S2)=Sof(N2)=Sof(C24)=Sof(H24)=Sof(C22)=Sof(C28)=Sof(C23)=Sof(C25)=
 Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C13(H13A,H13B)
6.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C21(H21), C24(H24), C1(H1), C20(H20), C17(H17), C8(H8), C7(H7),
 C3(H3), C25(H25), C6(H6), C26(H26), C4(H4), C27(H27), C5(H5), C27A(H27A),
 C26A(H26A), C25A(H25A), C24A(H24A)
6.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              39056
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.409
_oxdiff_exptl_absorpt_empirical_full_min 0.699