Rethinking aromaticity of reduced thienoquinoids: insights from an S-Pechmann dye dianion
Shiokawa, Takumi; Fukazawa, Aiko; Chemical Communications 61 (2025) 10095–10098; doi:10.1039/D5CC02327K

data_7134618
_publ_section_title
;
 Rethinking aromaticity of reduced thienoquinoids: insights from an
 S-Pechmann dye dianion
;
_journal_issue                   55
_journal_name_full               'Chemical Communications'
_journal_page_first              10095
_journal_page_last               10098
_journal_paper_doi               10.1039/D5CC02327K
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C28 H28 O2 S2'
_chemical_formula_sum            'C28 H28 O2 S2'
_chemical_formula_weight         460.62
_chemical_melting_point          316.6(5)
_chemical_name_common            1a
_chemical_name_systematic
5,5'-Bis(4-tert-butylphenyl)-3,3'-bi[thiophen-3(2H)-ylidene]-2,2'-dione
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-25
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7221)
;
_audit_update_record
;
2025-04-25 deposited with the CCDC.	2025-05-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   7.83060(10)
_cell_length_b                   30.1726(3)
_cell_length_c                   30.2525(3)
_cell_measurement_reflns_used    70698
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.4570
_cell_measurement_theta_min      1.6080
_cell_volume                     7147.74(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w      0.00 180.00   1.00    1.00    --    0.00  45.00   0.00  180
  2  \w      0.00 180.00   1.00    1.00    --    0.00  45.00 -90.00  180
  3  \w      0.00 180.00   1.00    1.00    --    0.00  45.00-180.00  180
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'esperanto-CrysAlisPro-abstract goniometer imported esperanto images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0169356000
_diffrn_orient_matrix_UB_12      -0.0130014000
_diffrn_orient_matrix_UB_13      0.0000740000
_diffrn_orient_matrix_UB_21      -0.0007074000
_diffrn_orient_matrix_UB_22      0.0001622000
_diffrn_orient_matrix_UB_23      0.0136875000
_diffrn_orient_matrix_UB_31      -0.0500707000
_diffrn_orient_matrix_UB_32      0.0043801000
_diffrn_orient_matrix_UB_33      -0.0002219000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.414
_diffrn_reflns_av_R_equivalents  0.0672
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            148754
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        14.383
_diffrn_reflns_theta_max         15.595
_diffrn_reflns_theta_min         1.568
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    0.068
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33178
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_description       needle
_exptl_crystal_F_000             2928
_exptl_crystal_preparation
'slow diffusion of hexane into a solution of 1a'
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.228
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     504
_refine_ls_number_reflns         8198
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0366
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0585P)^2^+1.4393P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1024
_refine_ls_wR_factor_ref         0.1062
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7262
_reflns_number_total             8198
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02327k2.cif
_cod_data_source_block           1a
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '316.2-317.1' was changed
to '316.6(5)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7134618--7134620.cif.
;
_cod_original_cell_volume        7147.75(14)
_cod_database_code               7134618
_shelx_shelxl_version_number     2019/3
_cell_oxdiff_angle_alpha         90.0405(9)
_cell_oxdiff_angle_beta          89.9900(9)
_cell_oxdiff_angle_gamma         90.0241(8)
_cell_oxdiff_length_a            7.83143(8)
_cell_oxdiff_length_b            30.1748(3)
_cell_oxdiff_length_c            30.2470(3)
_cell_oxdiff_measurement_reflns_used 69058
_cell_oxdiff_volume              7147.72(13)
_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
 C39-C40 \\sim C39-C40A
 with sigma of 0.02
 C39-C41 \\sim C39-C41A
 with sigma of 0.02
 C39-C42 \\sim C39-C42A
 with sigma of 0.02
 C11-C13 \\sim C11-C13A
 with sigma of 0.02
 C11-C12 \\sim C11-C12A
 with sigma of 0.02
 C11-C14 \\sim C11-C14A
 with sigma of 0.02
3. Others
 Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C40A)=Sof(H40D)=Sof(H40E)=
 Sof(H40F)=Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=1-FVAR(1)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=FVAR(1)
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(2)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(2)
4.a Aromatic/amide H refined with riding coordinates:
 C31(H31), C17(H17), C3(H3), C21(H21), C23(H23), C35(H35), C6(H6), C7(H7),
 C34(H34), C20(H20), C37(H37), C8(H8), C9(H9), C22(H22), C36(H36)
4.b Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C13(H13A,H13B,H13C), C12(H12A,H12B,
 H12C), C26(H26A,H26B,H26C), C14(H14A,H14B,H14C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C41A(H41D,H41E,H41F), C40A(H40D,H40E,H40F),
 C42A(H42D,H42E,H42F), C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F), C12A(H12D,
 H12E,H12F)
;
_shelx_res_checksum              47832
_shelx_hkl_checksum              29513
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.666
_oxdiff_exptl_absorpt_empirical_full_min 0.390