Enantioselective synthesis and racemization dynamics of trithia[5]helicenes derived from the dithieno[2,3-<i>b</i>:3',2'-<i>d</i>]-thiophene unit.
Fu, Wei; Simon, Martin; Golz, Christopher; Alcarazo, Manuel; Chemical science 16 (2025) 19172–19177; doi:10.1039/d5sc06132f

data_1575855
_publ_section_title
;
 Enantioselective synthesis and racemization dynamics of
 trithia[5]helicenes derived from the
 dithieno[2,3-<i>b</i>:3',2'-<i>d</i>]-thiophene unit.
;
_journal_issue                   41
_journal_name_full               'Chemical science'
_journal_page_first              19172
_journal_page_last               19177
_journal_paper_doi               10.1039/d5sc06132f
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C38 H22.53 Br2.039 O2 S3'
_chemical_formula_sum            'C38 H22 Br2 O2 S3'
_chemical_formula_weight         766.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-20
_audit_creation_method
;FinalCif V131 by Daniel Kratzert, Freiburg 2023, 
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2025-08-08 deposited with the CCDC.	2025-09-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.9780(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9156(4)
_cell_length_b                   25.9710(14)
_cell_length_c                   13.2783(7)
_cell_measurement_reflns_used    9767
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      32.567
_cell_measurement_theta_min      2.213
_cell_volume                     3018.3(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection
'Bruker BIS V6.2.15/2021-03-16 and APEX4 2022.1-1'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE dual wavelength Mo/Cu'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            105396
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.626
_diffrn_reflns_theta_min         2.214
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.930
_exptl_absorpt_correction_T_max  0.8647
_exptl_absorpt_correction_T_min  0.5429
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1117 before and 0.0522 after correction.
The Ratio of minimum to maximum transmission is 0.6278.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.687
_exptl_crystal_description       block
_exptl_crystal_F_000             1536
_exptl_crystal_recrystallization_method
'from a mixture of ethyl acetate and hexane.'
_exptl_crystal_size_max          0.301
_exptl_crystal_size_mid          0.194
_exptl_crystal_size_min          0.165
_refine_diff_density_max         1.403
_refine_diff_density_min         -0.787
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     443
_refine_ls_number_reflns         10903
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0365P)^2^+2.4342P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0735
_refine_ls_wR_factor_ref         0.0762
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9690
_reflns_number_total             10903
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06132f2.cif
_cod_data_source_block           mo_2191_cg_0m
_cod_depositor_comments
'Adding full bibliography for 1575851--1575858.cif.'
_cod_database_code               1575855
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1A-C34 \\sim O1B-C34
 with sigma of 0.02
 O1A-C37A \\sim O1B-C37B
 with sigma of 0.02
 C37A-H37A \\sim C37B-H37A
 with sigma of 0.02
 C37A-H37B \\sim C37B-H37B
 with sigma of 0.02
 C37A-H37C \\sim C37B-H37C
 with sigma of 0.02
 O1A-H37A \\sim O1B-H37A
 with sigma of 0.04
 O1A-H37B \\sim O1B-H37B
 with sigma of 0.04
 O1A-H37C \\sim O1B-H37C
 with sigma of 0.04
 C34-C37A \\sim C34-C37B
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 C34, O1B, C37B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C34, O1A, C37A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Others
 Sof(C37B)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(O1B)=1-FVAR(1)
 Sof(O1A)=Sof(C37A)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C17(H17), C18(H18), C20(H20),
 C21(H21), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C35(H35),
  C36(H36)
5.b Idealised Me refined as rotating group:
 C37A(H37A,H37B,H37C), C38(H38A,H38B,H38C), C37B(H37D,H37E,H37F)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.472
_shelx_estimated_absorpt_t_max   0.643
_diffrn_measurement_ambient_temperature_device_make 'Oxford Cryostream 800'
_shelx_res_checksum              73590