Radical cation salts of dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene: characteristic crystal structures and properties
Dhara, Barun; Bulgarevich, Kirill; Takimiya, Kazuo; CrystEngComm 27 (2025) 6333–6340; doi:10.1039/D5CE00680E

data_1575413
_publ_section_title
;
 Radical cation salts of
 dinaphtho[2,3-b:2&#x2032;,3&#x2032;-f]thieno[3,2-b]thiophene:
 characteristic crystal structures and properties
;
_journal_issue                   38
_journal_name_full               CrystEngComm
_journal_page_first              6333
_journal_page_last               6340
_journal_paper_doi               10.1039/D5CE00680E
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C22 H12 S2, 0.667(Cl O4), 0.667(C6 H5 Cl)'
_chemical_formula_sum            'C26 H15.33 Cl1.33 O2.67 S2'
_chemical_formula_weight         481.77
_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             2024-09-26
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-07-06 deposited with the CCDC.	2025-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                101.434(4)
_cell_angle_beta                 108.011(4)
_cell_angle_gamma                101.058(4)
_cell_formula_units_Z            3
_cell_length_a                   10.3630(5)
_cell_length_b                   10.4488(5)
_cell_length_c                   15.7822(7)
_cell_measurement_reflns_used    14516
_cell_measurement_temperature    100
_cell_measurement_theta_max      76.5360
_cell_measurement_theta_min      3.0030
_cell_volume                     1533.07(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.946
_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    -81.00  -6.00   0.50    0.30    --  -47.79 105.00 -76.00  150
  2  \w      0.00  81.00   0.50    0.30    --   47.79-105.00-176.00  162
  3  \w   -106.00 -27.00   0.50    1.00    --  -97.00 105.00 -76.00  158
  4  \w   -167.00 -92.00   0.50    1.00    --  -97.00-105.00-176.00  150
  5  \w     35.00 107.00   0.50    1.00    --  104.77-105.00-176.00  144
  6  \w     86.00 175.00   0.50    1.00    --  104.77 105.00 -76.00  178
  7  \w   -120.00 -27.00   0.50    0.30    --  -47.79 -77.00 150.00  186
  8  \w    -91.00 -23.00   0.50    0.30    --  -47.79 125.00 -30.00  136
  9  \w    -25.00  24.00   0.50    0.30    --   47.79 -19.00 150.00   98
 10  \w    -25.00  24.00   0.50    0.30    --   47.79 -19.00 -90.00   98
 11  \w     40.00 120.00   0.50    0.30    --   47.79  37.00-180.00  160
 12  \w    -24.00  40.00   0.50    0.30    --   47.79 -37.00-180.00  128
 13  \w   -111.00 -28.00   0.50    1.00    --  -97.00 125.00 120.00  166
 14  \w   -169.00 -87.00   0.50    1.00    --  -97.00 -46.00-141.21  164
 15  \w   -169.00 -76.00   0.50    1.00    --  -97.00 -78.00 -57.82  186
 16  \w   -111.00 -28.00   0.50    1.00    --  -97.00 125.00-150.00  166
 17  \w   -169.00 -81.00   0.50    1.00    --  -97.00 -65.00 -90.03  176
 18  \w   -167.00 -91.00   0.50    1.00    --  -97.00 -99.00-150.00  152
 19  \w     92.00 175.00   0.50    1.00    --  104.77  57.00  30.00  166
 20  \w     33.00  64.00   0.50    1.00    --  104.77 -57.00  90.00   62
 21  \w     36.00 111.00   0.50    1.00    --  104.77-125.00 120.00  150
 22  \w     33.00  64.00   0.50    1.00    --  104.77 -57.00-180.00   62
 23  \w     33.00 105.00   0.50    1.00    --  104.77 -77.00  30.00  144
 24  \w     36.00 111.00   0.50    1.00    --  104.77-125.00  30.00  150
 25  \w     33.00 120.00   0.50    1.00    --  104.77-136.00  32.82  174
 26  \w     33.00  64.00   0.50    1.00    --  104.77 -57.00  30.00   62
 27  \w     36.00 111.00   0.50    1.00    --  104.77-125.00-150.00  150
 28  \w     35.00 106.00   0.50    1.00    --  104.77 -99.00  30.00  142
 29  \w     76.00 174.00   0.50    1.00    --  104.77 125.00-120.00  196
 30  \w     33.00 105.00   0.50    1.00    --  104.77 -77.00-180.00  144
 31  \w     33.00  64.00   0.50    1.00    --  104.77 -57.00  60.00   62
 32  \w   -120.00 -27.00   0.50    0.30    --  -47.79 -77.00-150.00  186
 33  \w   -120.00 -27.00   0.50    0.30    --  -47.79 -77.00 -90.00  186
 34  \w   -120.00 -27.00   0.50    0.30    --  -47.79 -77.00 -30.00  186
 35  \w   -120.00 -27.00   0.50    0.30    --  -47.79 -77.00  60.00  186
 36  \w   -120.00 -35.00   0.50    0.30    --  -47.79 -57.00 -30.00  170
 37  \w     27.00 120.00   0.50    0.30    --   47.79  77.00  90.00  186
 38  \w     35.00 120.00   0.50    0.30    --   47.79  57.00  60.00  170
 39  \w   -169.00-134.00   0.50    1.00    --  -97.00 -56.00  75.32   70
 40  \w   -169.00 -78.00   0.50    1.00    --  -97.00 -72.00 160.48  182
 41  \w   -169.00 -89.00   0.50    1.00    --  -97.00 -37.00   0.00  160
 42  \w   -169.00 -87.00   0.50    1.00    --  -97.00 -46.00  99.86  164
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0893057000
_diffrn_orient_matrix_UB_12      -0.0189083000
_diffrn_orient_matrix_UB_13      -0.0611377000
_diffrn_orient_matrix_UB_21      -0.1341419000
_diffrn_orient_matrix_UB_22      -0.0837196000
_diffrn_orient_matrix_UB_23      -0.0832978000
_diffrn_orient_matrix_UB_31      -0.0202783000
_diffrn_orient_matrix_UB_32      0.1306216000
_diffrn_orient_matrix_UB_33      -0.0269786000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1088
_diffrn_reflns_av_unetI/netI     0.0597
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            32271
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.666
_diffrn_reflns_theta_min         3.063
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.191
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63882
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.565
_exptl_crystal_description       needle
_exptl_crystal_F_000             742
_refine_diff_density_max         1.289
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     521
_refine_ls_number_reflns         6178
_refine_ls_number_restraints     838
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0776
_refine_ls_R_factor_gt           0.0661
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1258P)^2^+0.6685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1854
_refine_ls_wR_factor_ref         0.1989
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5010
_reflns_number_total             6178
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt-clo4-100k
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_original_cell_volume        1533.07(13)
_cod_database_code               1575413
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O Cl S'
_chemical_oxdiff_usercomment     ' '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 S13-C1 \\sim S13A-C1A
 with sigma of 0.02
 S13-C12 \\sim S13A-C12A
 with sigma of 0.02
 S24-C2 \\sim S24A-C2A
 with sigma of 0.02
 S24-C23 \\sim S24A-C23A
 with sigma of 0.02
 C10-C5 \\sim C10A-C5A
 with sigma of 0.02
 C10-C11 \\sim C10A-C11A
 with sigma of 0.02
 C10-C9 \\sim C10A-C9A
 with sigma of 0.02
 C17-C16 \\sim C17A-C16A
 with sigma of 0.02
 C17-C18 \\sim C17A-C18A
 with sigma of 0.02
 C16-C15 \\sim C16A-C15A
 with sigma of 0.02
 C16-C21 \\sim C16A-C21A
 with sigma of 0.02
 C14-C15 \\sim C14A-C15A
 with sigma of 0.02
 C14-C1 \\sim C14A-C1A
 with sigma of 0.02
 C14-C23 \\sim C14A-C23A
 with sigma of 0.02
 C5-C4 \\sim C5A-C4A
 with sigma of 0.02
 C5-C6 \\sim C5A-C6A
 with sigma of 0.02
 C3-C4 \\sim C3A-C4A
 with sigma of 0.02
 C3-C2 \\sim C3A-C2A
 with sigma of 0.02
 C3-C12 \\sim C3A-C12A
 with sigma of 0.02
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 C9-C8 \\sim C9A-C8A
 with sigma of 0.02
 C21-C20 \\sim C21A-C20A
 with sigma of 0.02
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 C18-C19 \\sim C18A-C19A
 with sigma of 0.02
 C20-C19 \\sim C20A-C19A
 with sigma of 0.02
 C6-C7 \\sim C6A-C7A
 with sigma of 0.02
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 C7-C8 \\sim C7A-C8A
 with sigma of 0.02
 S13-C14 \\sim S13A-C14A
 with sigma of 0.04
 S13-C3 \\sim S13A-C3A
 with sigma of 0.04
 S13-C11 \\sim S13A-C11A
 with sigma of 0.04
 S13-C2 \\sim S13A-C2A
 with sigma of 0.04
 S24-C14 \\sim S24A-C14A
 with sigma of 0.04
 S24-C3 \\sim S24A-C3A
 with sigma of 0.04
 S24-C1 \\sim S24A-C1A
 with sigma of 0.04
 S24-C22 \\sim S24A-C22A
 with sigma of 0.04
 C10-C4 \\sim C10A-C4A
 with sigma of 0.04
 C10-C6 \\sim C10A-C6A
 with sigma of 0.04
 C10-C12 \\sim C10A-C12A
 with sigma of 0.04
 C10-C8 \\sim C10A-C8A
 with sigma of 0.04
 C17-C15 \\sim C17A-C15A
 with sigma of 0.04
 C17-C21 \\sim C17A-C21A
 with sigma of 0.04
 C17-C19 \\sim C17A-C19A
 with sigma of 0.04
 C16-C14 \\sim C16A-C14A
 with sigma of 0.04
 C16-C18 \\sim C16A-C18A
 with sigma of 0.04
 C16-C20 \\sim C16A-C20A
 with sigma of 0.04
 C16-C22 \\sim C16A-C22A
 with sigma of 0.04
 C14-C2 \\sim C14A-C2A
 with sigma of 0.04
 C14-C22 \\sim C14A-C22A
 with sigma of 0.04
 C5-C3 \\sim C5A-C3A
 with sigma of 0.04
 C5-C11 \\sim C5A-C11A
 with sigma of 0.04
 C5-C9 \\sim C5A-C9A
 with sigma of 0.04
 C5-C7 \\sim C5A-C7A
 with sigma of 0.04
 C3-C11 \\sim C3A-C11A
 with sigma of 0.04
 C3-C1 \\sim C3A-C1A
 with sigma of 0.04
 C11-C9 \\sim C11A-C9A
 with sigma of 0.04
 C15-C1 \\sim C15A-C1A
 with sigma of 0.04
 C15-C21 \\sim C15A-C21A
 with sigma of 0.04
 C15-C23 \\sim C15A-C23A
 with sigma of 0.04
 C1-C12 \\sim C1A-C12A
 with sigma of 0.04
 C1-C23 \\sim C1A-C23A
 with sigma of 0.04
 C9-C7 \\sim C9A-C7A
 with sigma of 0.04
 C4-C2 \\sim C4A-C2A
 with sigma of 0.04
 C4-C6 \\sim C4A-C6A
 with sigma of 0.04
 C4-C12 \\sim C4A-C12A
 with sigma of 0.04
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 C21-C19 \\sim C21A-C19A
 with sigma of 0.04
 C2-C12 \\sim C2A-C12A
 with sigma of 0.04
 C2-C23 \\sim C2A-C23A
 with sigma of 0.04
 C18-C20 \\sim C18A-C20A
 with sigma of 0.04
 C20-C22 \\sim C20A-C22A
 with sigma of 0.04
 C6-C8 \\sim C6A-C8A
 with sigma of 0.04
3. Restrained planarity
 S24, S13, C1, C12, C14, C2, C3, C11, C15, C23, C4, C10, C16, C22, C5, C9, C17,
  C21, C6, C8, C18, C20, C7, C19
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C20 \\sim S13 \\sim C1 \\sim C12 \\sim C14 \\sim C2 \\sim C3 \\sim C11 \\sim
C15 \\sim C23 \\sim S24 \\sim C4 \\sim C10 \\sim C16 \\sim C22 \\sim C5 \\sim
C9 \\sim C17 \\sim C21 \\sim C6 \\sim C8 \\sim C18 \\sim C7 \\sim C19: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
S13 \\sim C1 \\sim C12 \\sim C2 \\sim C14 \\sim C3 \\sim C11 \\sim S24 \\sim
C15 \\sim C23 \\sim C4 \\sim C10 \\sim C16 \\sim C22 \\sim C5 \\sim C9 \\sim
C17 \\sim C21 \\sim C6 \\sim C8 \\sim C18 \\sim C20 \\sim C7 \\sim C19: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C7A \\sim C23A \\sim C14A \\sim S24A \\sim C22A \\sim C1A \\sim C15A \\sim C2A
\\sim C21A \\sim S13A \\sim C16A \\sim C3A \\sim C20A \\sim C12A \\sim C17A
\\sim C4A \\sim C19A \\sim C11A \\sim C18A \\sim C5A \\sim C10A \\sim C6A \\sim
C9A \\sim C8A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
Uanis(O1) = Uanis(O4) = Uanis(O3)
Uanis(C1A) = Uanis(C23A) = Uanis(C14A) = Uanis(S24A) = Uanis(C22A) =
Uanis(C15A) = Uanis(C2A) = Uanis(C21A) = Uanis(S13A) = Uanis(C16A) = Uanis(C3A)
= Uanis(C20A) = Uanis(C12A) = Uanis(C17A) = Uanis(C4A) = Uanis(C19A) =
Uanis(C11A) = Uanis(C18A) = Uanis(C5A) = Uanis(C10A) = Uanis(C6A) = Uanis(C9A)
= Uanis(C7A) = Uanis(C8A)
Uanis(C10A) = Uanis(C23A) = Uanis(C14A) = Uanis(S24A) = Uanis(C22A) =
Uanis(C1A) = Uanis(C15A) = Uanis(C2A) = Uanis(C21A) = Uanis(S13A) = Uanis(C16A)
= Uanis(C3A) = Uanis(C20A) = Uanis(C12A) = Uanis(C17A) = Uanis(C4A) =
Uanis(C19A) = Uanis(C11A) = Uanis(C18A) = Uanis(C5A) = Uanis(C6A) = Uanis(C9A)
= Uanis(C7A) = Uanis(C8A) = Uanis(C6)
5. Rigid body (RIGU) restrains
 C3, S13, C1, C12, C14, C2, C11, C15, C23, S24, C4, C10, C16, C22, C5, C9, C17,
  C21, C6, C8, C18, C20, C7, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, S13, C1, C12, C2, C3, C11, S24, C15, C23, C4, C10, C16, C22, C5, C9, C17,
  C21, C6, C8, C18, C20, C7, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10A, C23A, C14A, S24A, C22A, C1A, C15A, C2A, C21A, S13A, C16A, C3A, C20A,
 C12A, C17A, C4A, C19A, C11A, C18A, C5A, C6A, C9A, C7A, C8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C23A)=Sof(S13A)=Sof(C1A)=Sof(C12A)=Sof(C14A)=Sof(C2A)=Sof(C3A)=Sof(C11A)=
 Sof(H11A)=Sof(C15A)=Sof(H15A)=Sof(S24A)=Sof(C4A)=Sof(H4A)=Sof(C10A)=Sof(C16A)=
 Sof(C22A)=Sof(H22A)=Sof(C5A)=Sof(C9A)=Sof(H9A)=Sof(C17A)=Sof(H17A)=Sof(C21A)=
 Sof(C6A)=Sof(H6A)=Sof(C8A)=Sof(H8A)=Sof(C18A)=Sof(H18A)=Sof(C20A)=Sof(H20A)=
 Sof(C7A)=Sof(H7A)=Sof(C19A)=Sof(H19A)=1-FVAR(1)
 Sof(S13)=Sof(S24)=Sof(C10)=Sof(C17)=Sof(H17)=Sof(C16)=Sof(C14)=Sof(C5)=
 Sof(C3)=Sof(C11)=Sof(H11)=Sof(C15)=Sof(H15)=Sof(C1)=Sof(C9)=Sof(H9)=Sof(C4)=
 Sof(H4)=Sof(C21)=Sof(C2)=Sof(C18)=Sof(H18)=Sof(C20)=Sof(H20)=Sof(C6)=Sof(H6)=
 Sof(C12)=Sof(C22)=Sof(H22)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C23)=Sof(C19)=
 Sof(H19)=FVAR(1)
 Fixed Sof: O27(0.85) O26(0.85) O29(0.85) O1(0.15) O4(0.15) O3(0.15)
7.a Aromatic/amide H refined with riding coordinates:
 C39(H39), C17(H17), C36(H36), C37(H37), C11(H11), C15(H15), C34(H34), C9(H9),
 C4(H4), C32(H32), C18(H18), C20(H20), C35(H35), C6(H6), C22(H22), C7(H7),
 C8(H8), C47(H47), C19(H19), C43(H43), C45(H45), C46(H46), C44(H44), C11A(H11A),
  C15A(H15A), C4A(H4A), C22A(H22A), C9A(H9A), C17A(H17A), C6A(H6A), C8A(H8A),
 C18A(H18A), C20A(H20A), C7A(H7A), C19A(H19A)
;
_shelx_res_checksum              7929
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.909
_oxdiff_exptl_absorpt_empirical_full_min 0.340