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_1575851
_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         'C36 H18 F2 S3'
_chemical_formula_sum            'C36 H18 F2 S3'
_chemical_formula_weight         584.68
_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_Hall           'F 2 -2d'
_space_group_name_H-M_alt        'F d d 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-08-08 deposited with the CCDC.	2025-09-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   32.560(5)
_cell_length_b                   6.5554(6)
_cell_length_c                   25.584(5)
_cell_measurement_reflns_used    9986
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      30.474
_cell_measurement_theta_min      2.503
_cell_volume                     5460.7(14)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_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_temperature      100.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0301
_diffrn_reflns_av_unetI/netI     0.0119
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            60382
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.479
_diffrn_reflns_theta_min         2.025
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.311
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8665
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1464 before and 0.0395 after correction.
The Ratio of minimum to maximum transmission is 0.8665.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_description       plate
_exptl_crystal_F_000             2400
_exptl_crystal_recrystallization_method
'from a mixture of ethyl acetate and hexane.'
_exptl_crystal_size_max          0.629
_exptl_crystal_size_mid          0.302
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.254
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1954 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.031(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         4165
_refine_ls_number_restraints     105
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0220
_refine_ls_R_factor_gt           0.0214
_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^)+(0.0333P)^2^+2.2379P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0561
_refine_ls_wR_factor_ref         0.0567
_reflns_Friedel_coverage         0.960
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4082
_reflns_number_total             4165
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06132f2.cif
_cod_data_source_block           2124_fdd2
_cod_depositor_comments
'Adding full bibliography for 1575851--1575858.cif.'
_cod_database_code               1575851
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F1A-C16A \\sim F1B-C16B
 with sigma of 0.02
 C13-C14A \\sim C13-C14B
 with sigma of 0.02
 C13-C18A \\sim C13-C18B
 with sigma of 0.02
 C14A-C15A \\sim C14B-C15B
 with sigma of 0.02
 C15A-C16A \\sim C15B-C16B
 with sigma of 0.02
 C16A-C17A \\sim C16B-C17B
 with sigma of 0.02
 C17A-C18A \\sim C17B-C18B
 with sigma of 0.02
 F1A-C15A \\sim F1B-C15B
 with sigma of 0.04
 F1A-C17A \\sim F1B-C17B
 with sigma of 0.04
 C13-C15A \\sim C13-C15B
 with sigma of 0.04
 C13-C17A \\sim C13-C17B
 with sigma of 0.04
 C14A-C16A \\sim C14B-C16B
 with sigma of 0.04
 C15A-C17A \\sim C15B-C17B
 with sigma of 0.04
 C16A-C18A \\sim C16B-C18B
 with sigma of 0.04
 C14B-C13 \\sim C14A-C13
 with sigma of 0.02
 C18B-C13 \\sim C18A-C13
 with sigma of 0.02
 C18B-C17B \\sim C18A-C17A
 with sigma of 0.02
 C17B-C16B \\sim C17A-C16A
 with sigma of 0.02
 C16A-C15A \\sim C16B-C15B
 with sigma of 0.02
 F1B-C16B \\sim F1A-C16A
 with sigma of 0.02
 C15A-C14A \\sim C15B-C14B
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F1A, C13, C14A, C15A, C16A, C17A, C18A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F1B, C13, C14B, C15B, C16B, C17B, C18B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Others
 Sof(F1B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(C17B)=
 Sof(H17B)=Sof(C18B)=Sof(H18B)=1-FVAR(1)
 Sof(F1A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(C17A)=
 Sof(H17A)=Sof(C18A)=Sof(H18A)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C9(H9), C10(H10), C14A(H14A), C14B(H14B), C15A(H15A),
 C15B(H15B), C17A(H17A), C17B(H17B), C18A(H18A), C18B(H18B)
;
_shelx_res_checksum              11540
_olex2_submission_special_instructions 'No special instructions were received'