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_7134620
_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, 2(C18 H36 K N2 O6), C4 H8 O'
_chemical_formula_sum            'C68 H108 K2 N4 O15 S2'
_chemical_formula_weight         1363.90
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2025-04-25
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-04-25 deposited with the CCDC.	2025-05-28 downloaded from the CCDC.
;
_cell_angle_alpha                73.723(5)
_cell_angle_beta                 69.097(5)
_cell_angle_gamma                70.197(6)
_cell_formula_units_Z            1
_cell_length_a                   11.4080(6)
_cell_length_b                   12.0912(8)
_cell_length_c                   14.9019(8)
_cell_measurement_reflns_used    10798
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      20.9760
_cell_measurement_theta_min      1.7180
_cell_volume                     1776.7(2)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    5.00    --    0.00  45.00   0.00  180
  2  \w      0.00 180.00   1.00    5.00    --    0.00  45.00 -90.00  180
  3  \w      0.00 180.00   1.00    5.00    --    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      -0.0087220000
_diffrn_orient_matrix_UB_12      0.0237838000
_diffrn_orient_matrix_UB_13      -0.0242703000
_diffrn_orient_matrix_UB_21      -0.0373239000
_diffrn_orient_matrix_UB_22      0.0134158000
_diffrn_orient_matrix_UB_23      0.0170777000
_diffrn_orient_matrix_UB_31      0.0124540000
_diffrn_orient_matrix_UB_32      0.0249750000
_diffrn_orient_matrix_UB_33      0.0058127000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.414
_diffrn_reflns_av_R_equivalents  0.0724
_diffrn_reflns_av_unetI/netI     0.0584
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            33615
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        14.383
_diffrn_reflns_theta_max         14.996
_diffrn_reflns_theta_min         1.486
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    0.071
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45670
_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            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       needle
_exptl_crystal_F_000             734
_exptl_crystal_preparation
'slow diffusion of a hexane solution of [2.2.2]cryptand into a THF solution of 1a_dianion'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     436
_refine_ls_number_reflns         7255
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0318P)^2^+0.7293P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0961
_refine_ls_wR_factor_ref         0.1014
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5982
_reflns_number_total             7255
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02327k2.cif
_cod_data_source_block           1a_dianion
_cod_depositor_comments
'Adding full bibliography for 7134618--7134620.cif.'
_cod_database_code               7134620
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.999
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C40(0.5) H40A(0.5) H40B(0.5) C41(0.5) H41A(0.5) H41B(0.5) O8(0.5)
 C39(0.5) H39A(0.5) H39B(0.5) C42(0.5) H42A(0.5) H42B(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C26(H26A,H26B), C21(H21A,H21B), C31(H31A,H31B), C34(H34A,
 H34B), C32(H32A,H32B), C30(H30A,H30B), C29(H29A,H29B), C20(H20A,H20B),
 C19(H19A,H19B), C27(H27A,H27B), C35(H35A,H35B), C28(H28A,H28B), C37(H37A,H37B),
  C36(H36A,H36B), C18(H18A,H18B), C15(H15A,H15B), C38(H38A,H38B), C40(H40A,
 H40B), C41(H41A,H41B), C39(H39A,H39B), C42(H42A,H42B)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C6(H6), C7(H7)
3.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              86476
_shelx_hkl_checksum              78968
_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 3.435
_oxdiff_exptl_absorpt_empirical_full_min 0.541