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_1575516
_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      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-19
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   39.5906(7)
_cell_length_b                   7.17130(10)
_cell_length_c                   7.64230(10)
_cell_measurement_reflns_used    26475
_cell_measurement_temperature    113
_cell_measurement_theta_max      29.3760
_cell_measurement_theta_min      2.8370
_cell_volume                     2169.77(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (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 1.000
_diffrn_measured_fraction_theta_max 0.956
_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    -87.00  75.00   0.25    5.00    --  -15.00  45.00 193.00  648
  2  \w    -78.00  75.00   0.25    5.00    --  -15.00  45.00 300.00  612
  3  \w    -78.00  75.00   0.25    5.00    --  -15.00  45.00 122.00  612
  4  \w      1.00  60.00   0.25    5.00    --  -15.00  45.00  51.00  236
  5  \w    -82.00  61.25   0.25    5.00    --  -15.00  45.00 228.00  573
  6  \w    -68.25  58.25   0.25    5.00    --  -15.00  45.00 157.00  506
  7  \w     28.00  73.00   0.25    5.00    --  -15.00  45.00  15.00  180
  8  \w     28.00  73.00   0.25    5.00    --  -15.00  45.00  86.00  180
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0094935000
_diffrn_orient_matrix_UB_12      -0.0279300000
_diffrn_orient_matrix_UB_13      -0.0742553000
_diffrn_orient_matrix_UB_21      -0.0151909000
_diffrn_orient_matrix_UB_22      -0.0165969000
_diffrn_orient_matrix_UB_23      -0.0466310000
_diffrn_orient_matrix_UB_31      0.0001296000
_diffrn_orient_matrix_UB_32      0.0934021000
_diffrn_orient_matrix_UB_33      -0.0304918000
_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  0.0405
_diffrn_reflns_av_unetI/netI     0.0296
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       52
_diffrn_reflns_limit_h_min       -53
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            40303
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.882
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.444
_diffrn_reflns_theta_min         2.058
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.265
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62510
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.379
_exptl_crystal_description       plate
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.648
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 1881 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     372
_refine_ls_number_reflns         5315
_refine_ls_number_restraints     747
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0423
_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^)+(0.0429P)^2^+1.1547P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0942
_refine_ls_wR_factor_ref         0.0962
_reflns_Friedel_coverage         0.725
_reflns_Friedel_fraction_full    0.943
_reflns_Friedel_fraction_max     0.798
_reflns_number_gt                4978
_reflns_number_total             5315
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02623g24.cif
_cod_data_source_block           FormII
_cod_depositor_comments
'Adding full bibliography for 1575516--1575517.cif.'
_cod_database_code               1575516
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.949
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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-C24 \\sim N2A-C24A
 with sigma of 0.02
 C19-C22 \\sim C19-C22A
 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
 C23-C28 \\sim C23A-C28A
 with sigma of 0.02
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 C27-C26 \\sim C27A-C26A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 S2-N2 \\sim S2A-N2A
 with sigma of 0.04
 S2-C19 \\sim S2A-C19
 with sigma of 0.04
 S2-C24 \\sim S2A-C24A
 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-C25 \\sim N2A-C25A
 with sigma of 0.04
 C22-C24 \\sim C22A-C24A
 with sigma of 0.04
 C22-C23 \\sim C22A-C23A
 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
 C23-C27 \\sim C23A-C27A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C27-C25 \\sim C27A-C25A
 with sigma of 0.04
 C28-C26 \\sim C28A-C26A
 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
C2 \\sim S1 \\sim C9 \\sim C11 \\sim C3 \\sim C10 \\sim C4 \\sim C12 \\sim N1
\\sim C8 \\sim C5 \\sim C7 \\sim C16 \\sim C1 \\sim C13 \\sim C6 \\sim C21
\\sim C17 \\sim C14 \\sim C20 \\sim C18 \\sim C15 \\sim C19 \\sim C22 \\sim
C22A \\sim S2 \\sim N2 \\sim S2A \\sim N2A \\sim C23 \\sim C24 \\sim C23A \\sim
C24A \\sim C25A \\sim C28 \\sim C25 \\sim C28A \\sim C26A \\sim C27 \\sim C26
\\sim C27A: 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 0.001 and sigma for 1-3 distances of 0.001
 C2, S1, C9, C11, C3, C10, C4, C12, N1, C8, C5, C7, C16, C1, C13, C6, C21, C17,
  C14, C20, C18, C15, C19, C22, C22A, S2, N2, S2A, N2A, C23, C24, C23A, C24A,
 C25A, C28, C25, C28A, C26A, C27, C26, C27A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C22A)=Sof(S2A)=Sof(N2A)=Sof(C24A)=Sof(C23A)=Sof(C28A)=Sof(H28A)=Sof(C27A)=
 Sof(H27A)=Sof(C26A)=Sof(H26A)=Sof(C25A)=Sof(H25A)=1-FVAR(1)
 Sof(S2)=Sof(N2)=Sof(C22)=Sof(C24)=Sof(C23)=Sof(C27)=Sof(H27)=Sof(C28)=
 Sof(H28)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B)
6.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C4(H4), C3(H3), C1(H1), C17(H17), C5(H5), C8(H8),
 C27(H27), C18(H18), C28(H28), C6(H6), C7(H7), C25(H25), C26(H26), C28A(H28A),
 C27A(H27A), C26A(H26A), C25A(H25A)
6.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              24699
_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 1.471
_oxdiff_exptl_absorpt_empirical_full_min 0.667