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_1575853
_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_absolute_configuration ad
_chemical_formula_moiety         'C H2 Cl2, 2(C38 H18 F6 S3)'
_chemical_formula_sum            'C77 H38 Cl2 F12 S6'
_chemical_formula_weight         1454.33
_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             2023-11-22
_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                90
_cell_angle_beta                 97.027(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.6491(5)
_cell_length_b                   7.9062(2)
_cell_length_c                   24.9766(8)
_cell_measurement_reflns_used    5749
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      78.678
_cell_measurement_theta_min      3.027
_cell_volume                     3263.00(17)
_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 0.998
_diffrn_measured_fraction_theta_max 0.980
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0637
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            13383
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         78.779
_diffrn_reflns_theta_min         2.674
_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    3.385
_exptl_absorpt_correction_T_max  0.754205
_exptl_absorpt_correction_T_min  0.603796
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0870 before and 0.0577 after correction.
 
For component 2:
 wR2(int) was 0.0953 before and 0.0619 after correction.
 The Ratio of minimum to maximum transmission is 0.56.

Final HKLF 4 output contains 98840 reflections, Rint = 0.0637
 (67179 with I > 3sig(I), Rint = 0.0578)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.480
_exptl_crystal_description       plate
_exptl_crystal_F_000             1476
_exptl_crystal_recrystallization_method
'from a mixture of dichloromethane and hexane.'
_exptl_crystal_size_max          0.189
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.033
_refine_diff_density_max         0.212
_refine_diff_density_min         -0.205
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 5365 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1119
_refine_ls_number_reflns         13383
_refine_ls_number_restraints     357
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0410
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0640P)^2^+0.6205P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.803
_reflns_Friedel_fraction_full    0.977
_reflns_Friedel_fraction_max     0.913
_reflns_number_gt                12799
_reflns_number_total             13383
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
'The data was integrated as a 2-component twin.'
_twin_individual_id              2
_twin_individual_twin_matrix_11  0.00038
_twin_individual_twin_matrix_12  -0.00021
_twin_individual_twin_matrix_13  -1.00004
_twin_individual_twin_matrix_21  -1.0
_twin_individual_twin_matrix_22  0.0001
_twin_individual_twin_matrix_23  -7e-05
_twin_individual_twin_matrix_31  0.00091
_twin_individual_twin_matrix_32  1.00004
_twin_individual_twin_matrix_33  0.36703
_cod_data_source_file            d5sc06132f2.cif
_cod_data_source_block           cu_2158_cg_0m_4
_cod_depositor_comments
'Adding full bibliography for 1575851--1575858.cif.'
_cod_database_code               1575853
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6349(13)
 0.3651(13)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 Cl2F-C1SF = Cl1F-C1SF
 1.771 with sigma of 0.01
 Cl1D-C1SD = Cl2D-C1SD
 1.771 with sigma of 0.01
 Cl1D-Cl2D
 2.916 with sigma of 0.03
 Cl2B-C1SB = Cl1B-C1SB
 1.771 with sigma of 0.01
 Cl2B-Cl1B
 2.916 with sigma of 0.03
 Cl2F-Cl1F
 2.916 with sigma of 0.03
 Cl2E-C1SE = Cl1E-C1SE
 1.771 with sigma of 0.01
 Cl2E-Cl1E
 2.916 with sigma of 0.03
 Cl1S-C1SA = Cl2S-C1SA
 1.771 with sigma of 0.01
 Cl1S-Cl2S
 2.916 with sigma of 0.03
 Cl2C-C1SC = Cl1C-C1SC
 1.771 with sigma of 0.01
 Cl2C-Cl1C
 2.916 with sigma of 0.03
 F4A-C30 \\sim F4B-C30
 with sigma of 0.02
 F6A-C30 \\sim F6B-C30
 with sigma of 0.02
 F5A-C30 \\sim F5B-C30
 with sigma of 0.02
 F5B-F4B \\sim F4B-F6B \\sim F6B-F5B
 with sigma of 0.02
 F5A-F6A \\sim F6A-F4A \\sim F4A-F5A
 with sigma of 0.02
 F10A-C67A \\sim F10B-C67B
 with sigma of 0.02
 C64-C67A \\sim C64-C67B
 with sigma of 0.02
 F11A-C67A \\sim F11B-C67B
 with sigma of 0.02
 F12A-C67A \\sim F12B-C67B
 with sigma of 0.02
 F10A-C64 \\sim F10B-C64
 with sigma of 0.04
 F10A-F11A \\sim F10B-F11B
 with sigma of 0.04
 F10A-F12A \\sim F10B-F12B
 with sigma of 0.04
 C64-F11A \\sim C64-F11B
 with sigma of 0.04
 C64-F12A \\sim C64-F12B
 with sigma of 0.04
 F11A-F12A \\sim F11B-F12B
 with sigma of 0.04
 F8A-C53 \\sim F8B-C53
 with sigma of 0.02
 F7A-C53 \\sim F7B-C53
 with sigma of 0.02
 F9A-C53 \\sim F9B-C53
 with sigma of 0.02
 F1A-C21 \\sim F3B-C21
 with sigma of 0.02
 F3A-C21 \\sim F2B-C21
 with sigma of 0.02
 F2A-C21 \\sim F1B-C21
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Cl1D \\sim Cl2D \\sim C1SD: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1B \\sim Cl2B \\sim C1SB: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1F \\sim Cl2F \\sim C1SF: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1E \\sim Cl2E \\sim C1SE: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1S \\sim Cl2S \\sim C1SA: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1C \\sim Cl2C \\sim C1SC: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C67A \\sim C67B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C1SD) \\sim Ueq: with sigma of 0.025 and sigma for terminal atoms of 0.03
Uanis(C1SB) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1SC) \\sim Ueq: with sigma of 0.015 and sigma for terminal atoms of 0.03
Uanis(C1SA) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 Cl1D, Cl2D, C1SD
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1B, Cl2B, C1SB
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl1B, Cl2B, C1SB, H1SA, H1SB
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F4A, F5A, F6A, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F4B, F5B, F6B, C30
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl1E, Cl2E, C1SE
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1S, Cl2S, C1SA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1C, Cl2C, C1SC
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1F, Cl2F, C1SF
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F10A, F11A, F12A, C64, C67A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 F10B, F11B, F12B, C64, C67B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 F7A, F8A, F9A, C53
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F7B, F8B, F9B, C53
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl1C, Cl2C, C1SC, H1SC, H1SD
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl1E, Cl2E, C1SE, H1SG, H1SH
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl1S, Cl2S, C1SA, H1SK, H1SL
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Cl1F, Cl2F, C1SF, H1SI, H1SJ
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F1A, F2A, F3A, C21
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F1B, F2B, F3B, C21
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 1*[Sof(Cl1S)+Sof(Cl2S)+Sof(C1SA)+Sof(H1SK)+Sof(H1SL)]+1*[Sof(Cl2B)+Sof(Cl1B)+
 Sof(C1SB)+Sof(H1SA)+Sof(H1SB)]+1*[Sof(Cl2C)+Sof(Cl1C)+Sof(C1SC)+Sof(H1SC)+
 Sof(H1SD)]+1*[Sof(Cl1D)+Sof(Cl2D)+Sof(C1SD)+Sof(H1SE)+Sof(H1SF)]+1*[Sof(Cl2E)+
 Sof(Cl1E)+Sof(C1SE)+Sof(H1SG)+Sof(H1SH)]+1*[Sof(Cl2F)+Sof(Cl1F)+Sof(C1SF)+
 Sof(H1SI)+Sof(H1SJ)]=1 with esd of 0.0001
 Sof(Cl1S)=Sof(Cl2S)=Sof(C1SA)=Sof(H1SK)=Sof(H1SL)=FVAR(1)
 Sof(Cl2B)=Sof(Cl1B)=Sof(C1SB)=Sof(H1SA)=Sof(H1SB)=FVAR(2)
 Sof(Cl2C)=Sof(Cl1C)=Sof(C1SC)=Sof(H1SC)=Sof(H1SD)=FVAR(3)
 Sof(Cl1D)=Sof(Cl2D)=Sof(C1SD)=Sof(H1SE)=Sof(H1SF)=FVAR(4)
 Sof(Cl2E)=Sof(Cl1E)=Sof(C1SE)=Sof(H1SG)=Sof(H1SH)=FVAR(5)
 Sof(Cl2F)=Sof(Cl1F)=Sof(C1SF)=Sof(H1SI)=Sof(H1SJ)=FVAR(6)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=Sof(C67B)=1-FVAR(7)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(C67A)=FVAR(7)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(8)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(8)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(9)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=FVAR(9)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(10)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(10)
7.a Free rotating group:
 Cl2B(Cl1B,C1SB), Cl2C(Cl1C,C1SC), Cl1D(Cl2D,C1SD), Cl2E(Cl1E,C1SE), Cl2F(Cl1F,
 C1SF), Cl1S(Cl2S,C1SA)
7.b Secondary CH2 refined with riding coordinates:
 C1SB(H1SA,H1SB), C1SC(H1SC,H1SD), C1SD(H1SE,H1SF), C1SE(H1SG,H1SH), C1SF(H1SI,
 H1SJ), C1SA(H1SK,H1SL)
7.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C16(H16), C17(H17), C19(H19),
 C20(H20), C25(H25), C26(H26), C28(H28), C29(H29), C31(H31), C35(H35), C36(H36),
  C37(H37), C38(H38), C45(H45), C48(H48), C49(H49), C51(H51), C52(H52),
 C54(H54), C55(H55), C56(H56), C57(H57), C62(H62), C63(H63), C65(H65), C66(H66),
  C68(H68), C71(H71), C72(H72), C73(H73), C74(H74)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.567
_shelx_estimated_absorpt_t_max   0.896
_diffrn_measurement_ambient_temperature_device_make 'Oxford Cryostream 800'
_shelx_res_checksum              1405