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_1575858
_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         '2(C H Cl3), C38 H24 O2 S3'
_chemical_formula_sum            'C40 H26 Cl6 O2 S3'
_chemical_formula_weight         847.49
_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             2024-01-22
_audit_creation_method
;FinalCif V131 by Daniel Kratzert, Freiburg 2024, 
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                 103.597(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.8640(18)
_cell_length_b                   21.852(2)
_cell_length_c                   24.844(3)
_cell_measurement_reflns_used    9188
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      27.930
_cell_measurement_theta_min      2.189
_cell_volume                     7315.7(15)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection
'Bruker BIS 8.5.1.2 Release/2023-09-07 and APEX5 2023.9-2'
_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 0.999
_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  0.0706
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            366677
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.300
_diffrn_reflns_theta_min         1.864
_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    0.679
_exptl_absorpt_correction_T_max  0.9949
_exptl_absorpt_correction_T_min  0.8528
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1543 before and 0.0508 after correction.
The Ratio of minimum to maximum transmission is 0.8572.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.539
_exptl_crystal_description       needle
_exptl_crystal_F_000             3456
_exptl_crystal_size_max          0.509
_exptl_crystal_size_mid          0.047
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.884
_refine_diff_density_min         -0.568
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1060
_refine_ls_number_reflns         18179
_refine_ls_number_restraints     136
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0438
_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^)+(0.0383P)^2^+9.8087P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0973
_refine_ls_wR_factor_ref         0.1063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14389
_reflns_number_total             18179
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06132f2.cif
_cod_data_source_block           mo_2205_cg_0m
_cod_depositor_comments
'Adding full bibliography for 1575851--1575858.cif.'
_cod_original_cell_volume        7315.8(16)
_cod_database_code               1575858
_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
 Cl4A-C2A \\sim Cl4B-C2B
 with sigma of 0.02
 Cl1A-C1A \\sim Cl1B-C1B
 with sigma of 0.02
 Cl5A-C2A \\sim Cl5B-C2B
 with sigma of 0.02
 Cl2A-C1A \\sim Cl2B-C1B
 with sigma of 0.02
 Cl6A-C2A \\sim Cl6B-C2B
 with sigma of 0.02
 Cl3A-C1A \\sim Cl3B-C1B
 with sigma of 0.02
 Cl4A-Cl5A \\sim Cl4B-Cl5B
 with sigma of 0.04
 C1A-H1A \\sim C1B-H1A
 with sigma of 0.02
 Cl1A-Cl2A \\sim Cl1B-Cl2B
 with sigma of 0.04
 Cl4A-Cl6A \\sim Cl4B-Cl6B
 with sigma of 0.04
 Cl5A-Cl6A \\sim Cl5B-Cl6B
 with sigma of 0.04
 Cl1A-Cl3A \\sim Cl1B-Cl3B
 with sigma of 0.04
 Cl1A-H1A \\sim Cl1B-H1A
 with sigma of 0.04
 Cl2A-Cl3A \\sim Cl2B-Cl3B
 with sigma of 0.04
 Cl2A-H1A \\sim Cl2B-H1A
 with sigma of 0.04
 Cl10-C4A \\sim Cl-C4B
 with sigma of 0.02
 Cl3A-H1A \\sim Cl3B-H1A
 with sigma of 0.04
 Cl11-C4A \\sim Cl2-C4B
 with sigma of 0.02
 Cl12-C4A \\sim Cl1-C4B
 with sigma of 0.02
 Cl10-Cl11 \\sim Cl-Cl2
 with sigma of 0.04
 Cl3B-C1B \\sim Cl3C-C1C
 with sigma of 0.02
 Cl1B-C1B \\sim Cl1C-C1C
 with sigma of 0.02
 Cl10-Cl12 \\sim Cl-Cl1
 with sigma of 0.04
 Cl11-Cl12 \\sim Cl2-Cl1
 with sigma of 0.04
 Cl2B-C1B \\sim Cl2C-C1C
 with sigma of 0.02
 C1B-H1B \\sim C1C-H1B
 with sigma of 0.02
 Cl3B-Cl1B \\sim Cl3C-Cl1C
 with sigma of 0.04
 Cl3B-Cl2B \\sim Cl3C-Cl2C
 with sigma of 0.04
 Cl3B-H1B \\sim Cl3C-H1B
 with sigma of 0.04
 Cl1B-Cl2B \\sim Cl1C-Cl2C
 with sigma of 0.04
 Cl1B-H1B \\sim Cl1C-H1B
 with sigma of 0.04
 Cl2B-H1B \\sim Cl2C-H1B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C2A) = Uanis(C2B)
Uanis(C1A) = Uanis(C1B)
4. Rigid body (RIGU) restrains
 Cl4A, C2A, Cl6A, Cl5A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl4B, C2B, Cl6B, Cl5B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl2A, Cl1A, C1A, Cl3A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl3B, C1B, Cl1B, Cl2B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl12, C4A, Cl11, Cl10
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl1, C4B, Cl2, Cl
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl1C, C1C, Cl2C, Cl3C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 1*[Sof(Cl1A)+Sof(Cl2A)+Sof(Cl3A)+Sof(C1A)+Sof(H1A)]+1*[Sof(Cl3B)+Sof(Cl1B)+
 Sof(Cl2B)+Sof(C1B)+Sof(H1B)]+1*[Sof(Cl2C)+Sof(C1C)+Sof(H1C)+Sof(Cl1C)+
 Sof(Cl3C)]=1 with esd of 0.00001
 Sof(Cl4B)=Sof(C2B)=Sof(H2B)=Sof(Cl6B)=Sof(Cl5B)=1-FVAR(1)
 Sof(Cl4A)=Sof(Cl5A)=Sof(Cl6A)=Sof(C2A)=Sof(H2A)=FVAR(1)
 Sof(Cl)=Sof(C4B)=Sof(H4B)=Sof(Cl1)=Sof(Cl2)=1-FVAR(2)
 Sof(Cl10)=Sof(Cl11)=Sof(Cl12)=Sof(C4A)=Sof(H4A)=FVAR(2)
 Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=Sof(C1A)=Sof(H1A)=FVAR(3)
 Sof(Cl3B)=Sof(Cl1B)=Sof(Cl2B)=Sof(C1B)=Sof(H1B)=FVAR(4)
 Sof(Cl2C)=Sof(C1C)=Sof(H1C)=Sof(Cl1C)=Sof(Cl3C)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C1A(H1A), C2A(H2A), C3A(H3A), C4A(H4A), C2B(H2B), C4B(H4B), C1B(H1B), C1C(H1C)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15),
 C16(H16), C24(H24), C25(H25), C27(H27), C28(H28), C29(H29), C31(H31), C32(H32),
  C33(H33), C34(H34), C3'(H3'), C6'(H6'), C7'(H7'), C9'(H9'), C10'(H10'),
 C13'(H13'), C14'(H14'), C15'(H15'), C16'(H16'), C24'(H24'), C25'(H25'),
 C27'(H27'), C28'(H28'), C29'(H29'), C31'(H31'), C32'(H32'), C33'(H33'),
 C34'(H34')
6.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C37'(H37D,H37E,H37F), C38'(H38D,
 H38E,H38F)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.724
_shelx_estimated_absorpt_t_max   0.980
_diffrn_measurement_ambient_temperature_device_make 'Oxford Cryostream 800'
_shelx_res_checksum              89552