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_1575416
_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         '0.8(As F6), C22 H12 S2, 0.4(C6 H5 Cl)'
_chemical_formula_sum            'C24.4 H14 As0.8 Cl0.4 F4.8 S2'
_chemical_formula_weight         536.59
_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                70.477(3)
_cell_angle_beta                 85.804(2)
_cell_angle_gamma                78.781(2)
_cell_formula_units_Z            5
_cell_length_a                   13.6644(3)
_cell_length_b                   13.9317(4)
_cell_length_c                   14.6414(5)
_cell_measurement_reflns_used    20885
_cell_measurement_temperature    100
_cell_measurement_theta_max      74.3850
_cell_measurement_theta_min      3.2360
_cell_volume                     2576.71(14)
_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      100
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.961
_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    -94.00 -23.00   0.50    0.50    --  -40.41 125.00-129.00  142
  2  \w   -107.00 -33.00   0.50    0.50    --  -40.41 145.00  37.00  148
  3  \w     27.00 108.00   0.50    0.50    --   40.41-145.00 -15.00  162
  4  \w     17.00  94.00   0.50    0.50    --   40.41-125.00 152.00  154
  5  \w     62.00 114.00   0.50    0.50    --   40.41 145.00  37.00  104
  6  \w   -126.00 -33.00   0.50    1.70    --  -97.00 145.00  37.00  186
  7  \w   -170.00 -82.00   0.50    1.70    --  -97.00-125.00 152.00  176
  8  \w   -169.00 -68.00   0.50    1.70    --  -97.00-145.00 -15.00  202
  9  \w   -112.00 -24.00   0.50    1.70    --  -97.00 125.00-129.00  176
 10  \w     62.00 170.00   0.50    1.70    --  106.28 145.00  37.00  216
 11  \w     76.00 175.00   0.50    1.70    --  106.28 125.00-129.00  198
 12  \w     33.00 111.00   0.50    1.70    --  106.28-125.00 152.00  156
 13  \w     32.00 126.00   0.50    1.70    --  106.28-145.00 -15.00  188
 14  \w    -31.00  41.00   0.50    0.50    --  -40.41  19.00  30.00  144
 15  \w   -114.00 -16.00   0.50    0.50    --  -40.41 -57.00 150.00  196
 16  \w   -114.00 -16.00   0.50    0.50    --  -40.41 -57.00 150.00  196
 17  \w    -41.00  27.00   0.50    0.50    --   40.41 -19.00 150.00  136
 18  \w    -41.00  27.00   0.50    0.50    --   40.41 -19.00-150.00  136
 19  \w    -41.00  27.00   0.50    0.50    --   40.41 -19.00-180.00  136
 20  \w    -41.00  27.00   0.50    0.50    --   40.41 -19.00  60.00  136
 21  \w    -73.00 -22.00   0.50    1.70    --  -97.00  61.00-180.00  102
 22  \w    -53.00 -20.00   0.50    1.70    --  -97.00  45.00-150.00   66
 23  \w    -53.00 -20.00   0.50    1.70    --  -97.00  45.00  90.00   66
 24  \w   -112.00 -24.00   0.50    1.70    --  -97.00 125.00-150.00  176
 25  \w   -170.00 -82.00   0.50    1.70    --  -97.00-125.00 120.00  176
 26  \w    -53.00 -20.00   0.50    1.70    --  -97.00  45.00-180.00   66
 27  \w    -53.00 -20.00   0.50    1.70    --  -97.00  45.00  60.00   66
 28  \w    -53.00 -20.00   0.50    1.70    --  -97.00  45.00 150.00   66
 29  \w    -73.00 -22.00   0.50    1.70    --  -97.00  61.00  90.00  102
 30  \w   -173.00 -72.00   0.50    1.70    --  -97.00 -49.00-149.84  202
 31  \w    -73.00 -22.00   0.50    1.70    --  -97.00  61.00-150.00  102
 32  \w    -53.00 -20.00   0.50    1.70    --  -97.00  45.00   0.00   66
 33  \w     81.00 175.00   0.50    1.70    --  106.28  45.00 -90.00  188
 34  \w     32.00 100.00   0.50    1.70    --  106.28 -77.00   0.00  136
 35  \w     32.00 100.00   0.50    1.70    --  106.28 -77.00   0.00  136
 36  \w     30.00 105.00   0.50    1.70    --  106.28 -94.00   0.00  150
 37  \w     81.00 175.00   0.50    1.70    --  106.28  45.00 -30.00  188
 38  \w     47.00 175.00   0.50    1.70    --  106.28  15.00  30.00  256
 39  \w     81.00 175.00   0.50    1.70    --  106.28  45.00 -30.00  188
 40  \w     30.00 105.00   0.50    1.70    --  106.28 -94.00 150.00  150
 41  \w     32.00  69.00   0.50    1.70    --  106.28 -61.00  60.00   74
 42  \w     47.00 175.00   0.50    1.70    --  106.28  15.00  30.00  256
 43  \w     32.00 100.00   0.50    1.70    --  106.28 -77.00 -60.00  136
 44  \w     32.00 100.00   0.50    1.70    --  106.28 -77.00-180.00  136
 45  \w     33.00 111.00   0.50    1.70    --  106.28-125.00-180.00  156
 46  \w     30.00 105.00   0.50    1.70    --  106.28 -94.00 -60.00  150
 47  \w     32.00  69.00   0.50    1.70    --  106.28 -61.00  30.00   74
 48  \w     32.00 100.00   0.50    1.70    --  106.28 -77.00 150.00  136
 49  \w     32.00  69.00   0.50    1.70    --  106.28 -61.00   0.00   74
 50  \w     10.00 114.00   0.50    0.50    --   40.41  77.00  60.00  208
 51  \w     10.00 114.00   0.50    0.50    --   40.41  77.00 -90.00  208
;
_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      0.0182030000
_diffrn_orient_matrix_UB_12      -0.0279373000
_diffrn_orient_matrix_UB_13      0.1091786000
_diffrn_orient_matrix_UB_21      -0.1082393000
_diffrn_orient_matrix_UB_22      -0.0179064000
_diffrn_orient_matrix_UB_23      0.0219195000
_diffrn_orient_matrix_UB_31      0.0341325000
_diffrn_orient_matrix_UB_32      -0.1145863000
_diffrn_orient_matrix_UB_33      0.0079699000
_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  0.0724
_diffrn_reflns_av_unetI/netI     0.0436
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            56391
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.606
_diffrn_reflns_theta_min         3.203
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.747
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54741
_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    1.729
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_refine_diff_density_max         1.500
_refine_diff_density_min         -1.095
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     851
_refine_ls_number_reflns         10146
_refine_ls_number_restraints     294
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0804
_refine_ls_R_factor_gt           0.0720
_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^)+(0.0831P)^2^+18.3153P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2013
_refine_ls_wR_factor_ref         0.2062
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8653
_reflns_number_total             10146
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt_asf6_100k
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_original_formula_sum        'C24.40 H14 As0.80 Cl0.40 F4.80 S2'
_cod_database_code               1575416
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C244  H140  Cl4  F48  S20  As8  '
_diffrn_oxdiff_digest_hkl
;
43b12110938b81fb239109c83966a78fb4a03f
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 As8-F16 \\sim As8-F16A
 with sigma of 0.02
 As8-F14 \\sim As8-F14A
 with sigma of 0.02
 S66-C77 \\sim S66A-C77A
 with sigma of 0.02
 C76-C77 \\sim C76A-C77A
 with sigma of 0.02
 C76-C75 \\sim C76A-C75A
 with sigma of 0.02
 C76-C67 \\sim C76A-C67A
 with sigma of 0.02
 C73-H73 \\sim C73A-H73A
 with sigma of 0.02
 C73-C74 \\sim C73A-C74A
 with sigma of 0.02
 C73-C72 \\sim C73A-C72A
 with sigma of 0.02
 C69-C68 \\sim C69A-C68A
 with sigma of 0.02
 C69-C74 \\sim C69A-C74A
 with sigma of 0.02
 C69-C70 \\sim C69A-C70A
 with sigma of 0.02
 C75-H75 \\sim C75A-H75A
 with sigma of 0.02
 C75-C74 \\sim C75A-C74A
 with sigma of 0.02
 C68-H68 \\sim C68A-H68A
 with sigma of 0.02
 C68-C67 \\sim C68A-C67A
 with sigma of 0.02
 C70-H70 \\sim C70A-H70A
 with sigma of 0.02
 C70-C71 \\sim C70A-C71A
 with sigma of 0.02
 C72-H72 \\sim C72A-H72A
 with sigma of 0.02
 C72-C71 \\sim C72A-C71A
 with sigma of 0.02
 C71-H71 \\sim C71A-H71A
 with sigma of 0.02
 S66-C76 \\sim S66A-C76A
 with sigma of 0.04
 C76-H75 \\sim C76A-H75A
 with sigma of 0.04
 C76-C68 \\sim C76A-C68A
 with sigma of 0.04
 C76-C74 \\sim C76A-C74A
 with sigma of 0.04
 C73-C69 \\sim C73A-C69A
 with sigma of 0.04
 C73-C75 \\sim C73A-C75A
 with sigma of 0.04
 C73-H72 \\sim C73A-H72A
 with sigma of 0.04
 C73-C71 \\sim C73A-C71A
 with sigma of 0.04
 H73-C74 \\sim H73A-C74A
 with sigma of 0.04
 H73-C72 \\sim H73A-C72A
 with sigma of 0.04
 C69-C75 \\sim C69A-C75A
 with sigma of 0.04
 C69-H68 \\sim C69A-H68A
 with sigma of 0.04
 C69-C67 \\sim C69A-C67A
 with sigma of 0.04
 C69-H70 \\sim C69A-H70A
 with sigma of 0.04
 C69-C71 \\sim C69A-C71A
 with sigma of 0.04
 C77-C75 \\sim C77A-C75A
 with sigma of 0.04
 C77-C67 \\sim C77A-C67A
 with sigma of 0.04
 C75-C67 \\sim C75A-C67A
 with sigma of 0.04
 H75-C74 \\sim H75A-C74A
 with sigma of 0.04
 C68-C74 \\sim C68A-C74A
 with sigma of 0.04
 C68-C70 \\sim C68A-C70A
 with sigma of 0.04
 H68-C67 \\sim H68A-C67A
 with sigma of 0.04
 C74-C70 \\sim C74A-C70A
 with sigma of 0.04
 C74-C72 \\sim C74A-C72A
 with sigma of 0.04
 C70-C72 \\sim C70A-C72A
 with sigma of 0.04
 C70-H71 \\sim C70A-H71A
 with sigma of 0.04
 H70-C71 \\sim H70A-C71A
 with sigma of 0.04
 C72-H71 \\sim C72A-H71A
 with sigma of 0.04
 H72-C71 \\sim H72A-C71A
 with sigma of 0.04
3. Restrained planarity
 C67A, C76A, C68A, C75A, C77A, C69A, H68A, H75A, C74A, S66A, C70A, C73A, H70A,
 C71A, H73A, C72A, H71A, H72A
 with sigma of 0.1
 C77, S66, C76, C75, C67, H75, C74, C68, C69, C73, H68, C70, H73, C72, H70,
 C71, H72, H71
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C67A \\sim C75A \\sim H75A \\sim C76A \\sim C74A \\sim C77A \\sim C69A \\sim
C73A \\sim S66A \\sim C68A \\sim C70A \\sim H73A \\sim C72A \\sim H68A \\sim
H70A \\sim C71A \\sim H72A \\sim H71A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C77A) = Uanis(S66A)
Uanis(C76A) = Uanis(C68A) = Uanis(C69A) = Uanis(C70A) = Uanis(C71A) =
Uanis(C72A) = Uanis(C73A) = Uanis(C75A)
5. Rigid body (RIGU) restrains
 C77A, C75A, H75A, C76A, C74A, C67A, C69A, C73A, S66A, C68A, C70A, H73A, C72A,
 H68A, H70A, C71A, H72A, H71A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C75A)=Sof(H75A)=Sof(S66A)=Sof(C77A)=Sof(C76A)=Sof(C67A)=Sof(C74A)=
 Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(C73A)=Sof(H73A)=Sof(C70A)=Sof(H70A)=
 Sof(C72A)=Sof(H72A)=Sof(C71A)=Sof(H71A)=1-FVAR(1)
 Sof(S66)=Sof(C76)=Sof(C73)=Sof(H73)=Sof(C69)=Sof(C77)=Sof(C75)=Sof(H75)=
 Sof(C68)=Sof(H68)=Sof(C74)=Sof(C67)=Sof(C70)=Sof(H70)=Sof(C72)=Sof(H72)=
 Sof(C71)=Sof(H71)=FVAR(1)
 Fixed Sof: F16(0.6) F17(0.4) F14(0.6) F14A(0.4) F16A(0.4) F9(0.6) F8(0.4)
 F10(0.6) F1(0.4) F11(0.6) F13(0.4) F12(0.6)
7.a Aromatic/amide H refined with riding coordinates:
 C32(H32), C50(H50), C63(H63), C73(H73), C39(H39), C21(H21), C37(H37),
 C34(H34), C56(H56), C28(H28), C43(H43), C46(H46), C24(H24), C58(H58), C61(H61),
  C23(H23), C36(H36), C60(H60), C25(H25), C75(H75), C68(H68), C48(H48),
 C26(H26), C83(H83), C59(H59), C45(H45), C35(H35), C70(H70), C82(H82), C72(H72),
  C79(H79), C81(H81), C47(H47), C80(H80), C71(H71), C75A(H75A), C68A(H68A),
 C73A(H73A), C70A(H70A), C72A(H72A), C71A(H71A)
;
_shelx_res_checksum              5402
_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 1.713
_oxdiff_exptl_absorpt_empirical_full_min 0.588