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_1575857
_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 H18 F6 S3'
_chemical_formula_sum            'C38 H18 F6 S3'
_chemical_formula_weight         684.70
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-16
_audit_creation_method
;FinalCif V130 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                67.511(2)
_cell_angle_beta                 73.705(2)
_cell_angle_gamma                86.208(3)
_cell_formula_units_Z            4
_cell_length_a                   13.2828(15)
_cell_length_b                   14.2038(9)
_cell_length_c                   18.067(2)
_cell_measurement_reflns_used    9325
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      32.537
_cell_measurement_theta_min      2.301
_cell_volume                     3019.6(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection
'Bruker BIS 8.5.0.27 Release/2023-03-20 and APEX4 2022.10-1'
_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 0.997
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE dual wavelength Mo/Ag'
_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  0.0366
_diffrn_reflns_av_unetI/netI     0.0178
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            231245
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.564
_diffrn_reflns_theta_min         2.047
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.312
_exptl_absorpt_correction_T_max  0.9943
_exptl_absorpt_correction_T_min  0.9122
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1309 before and 0.0390 after correction.
The Ratio of minimum to maximum transmission is 0.9174.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.506
_exptl_crystal_description       plank
_exptl_crystal_F_000             1392
_exptl_crystal_recrystallization_method
'from a mixture of dichloromethane and hexane.'
_exptl_crystal_size_max          0.596
_exptl_crystal_size_mid          0.117
_exptl_crystal_size_min          0.093
_refine_diff_density_max         0.511
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1016
_refine_ls_number_reflns         21939
_refine_ls_number_restraints     195
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0435
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0466P)^2^+1.2144P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0886
_refine_ls_wR_factor_ref         0.0953
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18748
_reflns_number_total             21939
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06132f2.cif
_cod_data_source_block           mo_2149_cg_0m
_cod_depositor_comments
'Adding full bibliography for 1575851--1575858.cif.'
_cod_original_cell_volume        3019.7(5)
_cod_database_code               1575857
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F7A-C71A \\sim F7B-C71B
 with sigma of 0.02
 F11A-C50A \\sim F11B-C50B
 with sigma of 0.02
 F12A-C50A \\sim F12B-C50B
 with sigma of 0.02
 F10A-F11A \\sim F10B-F11B
 with sigma of 0.04
 F10A-F12A \\sim F10B-F12B
 with sigma of 0.04
 F10A-C50A \\sim F10B-C50B
 with sigma of 0.02
 F11A-F12A \\sim F11B-F12B
 with sigma of 0.04
 F11A-C47 \\sim F11B-C47
 with sigma of 0.04
 F12A-C47 \\sim F12B-C47
 with sigma of 0.04
 F8A-C71A \\sim F8B-C71B
 with sigma of 0.02
 F11B-C50B \\sim F11C-C50C
 with sigma of 0.02
 F10B-F11B \\sim F10C-F11C
 with sigma of 0.04
 F11B-F12B \\sim F11C-F12C
 with sigma of 0.04
 F11B-C47 \\sim F11C-C47
 with sigma of 0.04
 F9A-C71A \\sim F9B-C71B
 with sigma of 0.02
 C47-C50A \\sim C47-C50B
 with sigma of 0.02
 C68-C71A \\sim C68-C71B
 with sigma of 0.02
 F7A-F8A \\sim F7B-F8B
 with sigma of 0.04
 F7A-F9A \\sim F7B-F9B
 with sigma of 0.04
 F7A-C68 \\sim F7B-C68
 with sigma of 0.04
 F10A-C47 \\sim F10B-C47
 with sigma of 0.04
 F8A-F9A \\sim F8B-F9B
 with sigma of 0.04
 F8A-C68 \\sim F8B-C68
 with sigma of 0.04
 F9A-C68 \\sim F9B-C68
 with sigma of 0.04
 F10B-C50B \\sim F10C-C50C
 with sigma of 0.02
 F12B-C50B \\sim F12C-C50C
 with sigma of 0.02
 C47-C50B \\sim C47-C50C
 with sigma of 0.02
 F10B-F12B \\sim F10C-F12C
 with sigma of 0.04
 F10B-C47 \\sim F10C-C47
 with sigma of 0.04
 F1A-C28 \\sim F1B-C28
 with sigma of 0.02
 F2A-C28 \\sim F2B-C28
 with sigma of 0.02
 F12B-C47 \\sim F12C-C47
 with sigma of 0.04
 F3A-C28 \\sim F3B-C28
 with sigma of 0.02
 F1A-C28 \\sim F2C-C28
 with sigma of 0.02
 F2A-C28 \\sim F3C-C28
 with sigma of 0.02
 F3A-C28 \\sim F1C-C28
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F11C) \\sim Ueq, Uanis(F11B) \\sim Ueq, Uanis(F12A) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 F10B, F11B, F12B, C47, C50B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F10A, F11A, F12A, C47, C50A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F10C, C50C, F11C, F12C, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F10B, F11B, F12B, C50B, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F1A, F2A, F3A, C28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F1C, F2C, F3C, C28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 1*[Sof(F1A)+Sof(F2A)+Sof(F3A)]+1*[Sof(F1B)+Sof(F2B)+Sof(F3B)]+1*[Sof(F1C)+
 Sof(F2C)+Sof(F3C)]=1 with esd of 0.0001
 1*[Sof(F10A)+Sof(F11A)+Sof(F12A)+Sof(C50A)]+1*[Sof(F10B)+Sof(F11B)+Sof(F12B)+
 Sof(C50B)]+1*[Sof(F10C)+Sof(C50C)+Sof(F11C)+Sof(F12C)]=1 with esd of 0.0001
 Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(C71B)=1-FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(C71A)=FVAR(1)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(C50A)=FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(3)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=FVAR(4)
 Sof(F1C)=Sof(F2C)=Sof(F3C)=FVAR(5)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=Sof(C50B)=FVAR(6)
 Sof(F10C)=Sof(C50C)=Sof(F11C)=Sof(F12C)=FVAR(7)
6.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C11(H11), C12(H12), C14(H14),
 C15(H15), C23(H23), C24(H24), C26(H26), C27(H27), C29(H29), C33(H33), C34(H34),
  C35(H35), C36(H36), C42(H42), C45(H45), C46(H46), C48(H48), C49(H49),
 C57(H57), C61(H61), C62(H62), C63(H63), C64(H64), C66(H66), C67(H67), C69(H69),
  C70(H70), C73(H73), C74(H74), C75(H75), C76(H76)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.836
_shelx_estimated_absorpt_t_max   0.972
_diffrn_measurement_ambient_temperature_device_make 'Oxford Cryostream 800'
_shelx_res_checksum              93533