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_1575427
_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
'3(F6 Sb), F3.283 Sb0.412, 5(C22 H12 S2), 2(C6 H5 Cl), F2.717 Sb0.588'
_chemical_formula_sum            'C122 H70 Cl2 F24 S10 Sb4'
_chemical_formula_weight         2870.28
_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             2025-02-17
_audit_creation_method
;
Olex2 1.5-ac7-012
(compiled 2024.11.06 svn.r97f918c9 for Rigaku Oxford Diffraction, GUI svn.r7082)
;
_audit_update_record
;
2025-07-06 deposited with the CCDC.	2025-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                88.9760(10)
_cell_angle_beta                 72.8890(10)
_cell_angle_gamma                84.4640(10)
_cell_formula_units_Z            2
_cell_length_a                   14.8806(2)
_cell_length_b                   17.37740(10)
_cell_length_c                   21.5631(2)
_cell_measurement_reflns_used    56737
_cell_measurement_temperature    200
_cell_measurement_theta_max      77.3840
_cell_measurement_theta_min      3.0870
_cell_volume                     5303.93(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac7-012 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-012 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      200
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.968
_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   -120.00 -36.00   0.50    1.00    --  -47.91 -53.00-133.00  168
  2  \w    -59.00  24.00   0.50    1.00    --  -47.91  53.00  11.00  166
  3  \w    -23.00  59.00   0.50    1.00    --   47.91 -53.00-133.00  164
  4  \w     37.00 120.00   0.50    1.00    --   47.91  53.00  11.00  166
  5  \w   -169.00 -85.00   0.50    3.00    --  -97.00 -53.00-133.00  168
  6  \w    -62.00 -25.00   0.50    3.00    --  -97.00  53.00  11.00   74
  7  \w     93.00 175.00   0.50    3.00    --  104.77  53.00  11.00  164
  8  \w   -119.00 -40.00   0.50    1.00    --  -47.91 -39.00 -89.01  158
  9  \w    -91.00 -23.00   0.50    1.00    --  -47.91 125.00   0.00  136
 10  \w    -24.00  27.00   0.50    1.00    --   47.91 -19.00   0.00  102
 11  \w    -24.00  27.00   0.50    1.00    --   47.91 -19.00 120.00  102
 12  \w   -166.00 -82.00   0.50    3.00    --  -97.00-125.00-150.00  168
 13  \w   -111.00 -28.00   0.50    3.00    --  -97.00 125.00 120.00  166
 14  \w   -167.00 -91.00   0.50    3.00    --  -97.00 -99.00 -30.00  152
 15  \w    -68.00 -25.00   0.50    3.00    --  -97.00  57.00-150.00   86
 16  \w   -104.00 -25.00   0.50    3.00    --  -97.00  77.00 -90.00  158
 17  \w   -167.00 -91.00   0.50    3.00    --  -97.00 -99.00 -30.00  152
 18  \w   -167.00 -91.00   0.50    3.00    --  -97.00 -99.00 -90.00  152
 19  \w   -167.00 -91.00   0.50    3.00    --  -97.00 -99.00   0.00  152
 20  \w     97.00 175.00   0.50    3.00    --  104.77  19.00  90.00  156
 21  \w     35.00 106.00   0.50    3.00    --  104.77 -99.00 -30.00  142
 22  \w     35.00 106.00   0.50    3.00    --  104.77 -99.00-150.00  142
 23  \w     35.00 106.00   0.50    3.00    --  104.77 -99.00-180.00  142
 24  \w     97.00 175.00   0.50    3.00    --  104.77  37.00 -60.00  156
 25  \w     33.00  63.00   0.50    3.00    --  104.77 -57.00 -30.00   60
 26  \w     33.00  63.00   0.50    3.00    --  104.77 -57.00-150.00   60
 27  \w     97.00 175.00   0.50    3.00    --  104.77  37.00  60.00  156
 28  \w     35.00 106.00   0.50    3.00    --  104.77 -99.00 120.00  142
 29  \w     35.00 106.00   0.50    3.00    --  104.77 -99.00 150.00  142
 30  \w     36.00 111.00   0.50    3.00    --  104.77-125.00 120.00  150
 31  \w     36.00 111.00   0.50    3.00    --  104.77-125.00 -60.00  150
 32  \w     35.00 106.00   0.50    3.00    --  104.77 -99.00 120.00  142
 33  \w     36.00 111.00   0.50    3.00    --  104.77-125.00  60.00  150
 34  \w     33.00 100.00   0.50    3.00    --  104.77 -77.00 -30.00  134
 35  \w     35.00 107.00   0.50    3.00    --  104.77-102.00  67.95  144
 36  \w     36.00 111.00   0.50    3.00    --  104.77-125.00 -30.00  150
 37  \w     33.00  63.00   0.50    3.00    --  104.77 -57.00  30.00   60
 38  \w   -120.00 -27.00   0.50    1.00    --  -47.91 -77.00  30.00  186
 39  \w   -120.00 -35.00   0.50    1.00    --  -47.91 -57.00  60.00  170
 40  \w   -120.00 -35.00   0.50    1.00    --  -47.91 -57.00-180.00  170
 41  \w   -120.00 -27.00   0.50    1.00    --  -47.91 -77.00 150.00  186
 42  \w     27.00 120.00   0.50    1.00    --   47.91  77.00 150.00  186
 43  \w     27.00 120.00   0.50    1.00    --   47.91  77.00 -60.00  186
 44  \w     27.00 120.00   0.50    1.00    --   47.91  77.00-120.00  186
 45  \w   -169.00-127.00   0.50    3.00    --  -97.00 -77.00  90.00   84
 46  \w   -169.00 -76.00   0.50    3.00    --  -97.00 -77.00 150.00  186
 47  \w   -169.00 -76.00   0.50    3.00    --  -97.00 -77.00  60.00  186
 48  \w   -169.00 -76.00   0.50    3.00    --  -97.00 -77.00-150.00  186
 49  \w   -169.00 -76.00   0.50    3.00    --  -97.00 -77.00 120.00  186
 50  \w   -169.00 -80.00   0.50    3.00    --  -97.00 -67.00   5.64  178
 51  \w   -169.00 -81.00   0.50    3.00    --  -97.00 -65.00 -27.41  176
 52  \w   -169.00 -82.00   0.50    3.00    --  -97.00 -62.00 -88.55  174
 53  \w   -169.00 -81.00   0.50    3.00    --  -97.00 -65.00 -56.93  176
 54  \w   -169.00 -82.00   0.50    3.00    --  -97.00 -63.00 167.60  174
;
_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      -0.0766898000
_diffrn_orient_matrix_UB_12      0.0471662000
_diffrn_orient_matrix_UB_13      -0.0234293000
_diffrn_orient_matrix_UB_21      -0.0750267000
_diffrn_orient_matrix_UB_22      -0.0496927000
_diffrn_orient_matrix_UB_23      0.0419149000
_diffrn_orient_matrix_UB_31      -0.0182061000
_diffrn_orient_matrix_UB_32      0.0569223000
_diffrn_orient_matrix_UB_33      0.0572970000
_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  0.0683
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            160329
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.588
_diffrn_reflns_theta_min         2.144
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.129
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.19937
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
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    1.797
_exptl_crystal_description       block
_exptl_crystal_F_000             2832
_refine_diff_density_max         3.261
_refine_diff_density_min         -1.270
_refine_diff_density_rms         0.200
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1525
_refine_ls_number_reflns         21870
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0921
_refine_ls_R_factor_gt           0.0845
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1134P)^2^+30.2047P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2311
_refine_ls_wR_factor_ref         0.2369
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19147
_reflns_number_total             21870
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt_sbf6_200k
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_database_code               1575427
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C244  H140  Cl4  F48  S20  Sb8  '
_diffrn_oxdiff_ac3_digest_hkl    41639bdd7780ff70eb7f179f700bbc8370eb2e
_diffrn_oxdiff_digest_hkl
;
4384ec77af1ff722ec9f57a3e5301b6ec04cdb
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 Sb23-F24 \\sim Sb23-F24A
 with sigma of 0.02
 Sb23-F2 \\sim Sb23-F2A
 with sigma of 0.02
 Sb23-F16 \\sim Sb23-F16A
 with sigma of 0.02
 Sb23-F9 \\sim Sb23-F9A
 with sigma of 0.02
 Sb23-F18 \\sim Sb23-F18A
 with sigma of 0.02
 Sb23-F1 \\sim Sb23-F1A
 with sigma of 0.02
 Sb23-F16A \\sim Sb23-F18 \\sim Sb23-F18A \\sim Sb23-F24 \\sim Sb23-F9A \\sim
Sb23-F9 \\sim Sb23-F2 ~
 Sb23-F24A \\sim Sb23-F1 \\sim Sb23-F16 \\sim Sb23-F1A \\sim Sb23-F2A
 with sigma of 0.02
 Sb23-F24 \\sim Sb-F24
 with sigma of 0.02
 Sb23-F2 \\sim Sb-F2
 with sigma of 0.02
 Sb23-F16 \\sim Sb-F16
 with sigma of 0.02
 Sb23-F9 \\sim Sb-F9
 with sigma of 0.02
 Sb23-F18 \\sim Sb-F18
 with sigma of 0.02
 Sb23-F1 \\sim Sb-F1
 with sigma of 0.02
 Sb23-F24A \\sim Sb-F24A
 with sigma of 0.02
 Sb23-F2A \\sim Sb-F2A
 with sigma of 0.02
 Sb23-F9A \\sim Sb-F9A
 with sigma of 0.02
 Sb23-F16A \\sim Sb-F16A
 with sigma of 0.02
 Sb23-F18A \\sim Sb-F18A
 with sigma of 0.02
 Sb23-F1A \\sim Sb-F1A
 with sigma of 0.02
 Sb-F18A \\sim Sb-F1A \\sim Sb-F2A \\sim Sb-F16A \\sim Sb-F24A \\sim Sb-F9A
 with sigma of 0.02
3. Others
 Sof(F24A)=Sof(F2A)=Sof(F9A)=Sof(F16A)=1-FVAR(1)
 Sof(F24)=Sof(F2)=Sof(F16)=Sof(F9)=FVAR(1)
 Sof(F18A)=Sof(F1A)=1-FVAR(2)
 Sof(F18)=Sof(F1)=FVAR(2)
 Sof(Sb)=1-FVAR(3)
 Sof(Sb23)=FVAR(3)
4.a Aromatic/amide H refined with riding coordinates:
 C105(H105), C46(H46), C26(H26), C70(H70), C33(H33), C39(H39), C76(H76),
 C98(H98), C94(H94), C111(H111), C28(H28), C63(H63), C103(H103), C92(H92),
 C87(H87), C83(H83), C132(H132), C68(H68), C44(H44), C52(H52), C41(H41),
 C100(H100), C125(H125), C57(H57), C59(H59), C113(H113), C65(H65), C29(H29),
 C31(H31), C89(H89), C78(H78), C118(H118), C30(H30), C139(H139), C154(H154),
 C55(H55), C127(H127), C91(H91), C130(H130), C102(H102), C43(H43), C136(H136),
 C90(H90), C42(H42), C138(H138), C54(H54), C67(H67), C143(H143), C66(H66),
 C81(H81), C116(H116), C140(H140), C101(H101), C141(H141), C129(H129),
 C115(H115), C56(H56), C114(H114), C128(H128), C80(H80), C79(H79), C158(H158),
 C156(H156), C151(H151), C157(H157), C147(H147), C150(H150), C155(H155),
 C149(H149), C148(H148)
;
_shelx_res_checksum              35716
_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 3.176
_oxdiff_exptl_absorpt_empirical_full_min 0.553