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_1575425
_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
'0.98(C22 H12 S2), 0.8(F6 P), 0.4(C6 H4 Cl2), 0.02(C22 H10 S2)'
_chemical_formula_sum            'C24.4 H13.56 Cl0.8 F4.8 P0.8 S2'
_chemical_formula_weight         515.17
_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
_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                71.180(2)
_cell_angle_beta                 86.156(2)
_cell_angle_gamma                79.453(2)
_cell_formula_units_Z            5
_cell_length_a                   13.7529(3)
_cell_length_b                   14.0651(3)
_cell_length_c                   14.7342(3)
_cell_measurement_reflns_used    15351
_cell_measurement_temperature    300
_cell_measurement_theta_max      74.8840
_cell_measurement_theta_min      3.2720
_cell_volume                     2652.07(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.128a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.128a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      300.00
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.972
_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    -95.00 -26.00   0.50    0.70    --  -48.16 130.00  33.00  138
  2  \w   -101.00 -30.00   0.50    0.70    --  -48.16 139.00-152.00  142
  3  \w   -119.00 -73.00   0.50    0.70    --  -48.16-139.00 146.00   92
  4  \w     20.00  95.00   0.50    0.70    --   48.16-130.00 -39.00  150
  5  \w     67.00 119.00   0.50    0.70    --   48.16 139.00-152.00  104
  6  \w     25.00 102.00   0.50    0.70    --   48.16-139.00 146.00  154
  7  \w   -115.00 -27.00   0.50    2.50    --  -97.00 130.00  33.00  176
  8  \w   -169.00 -73.00   0.50    2.50    --  -97.00-139.00 146.00  192
  9  \w   -167.00 -79.00   0.50    2.50    --  -97.00-130.00 -39.00  176
 10  \w   -121.00 -30.00   0.50    2.50    --  -97.00 139.00-152.00  182
 11  \w     73.00 175.00   0.50    2.50    --  106.00 130.00  33.00  204
 12  \w     34.00 122.00   0.50    2.50    --  106.00-139.00 146.00  176
 13  \w     36.00 115.00   0.50    2.50    --  106.00-130.00 -39.00  158
 14  \w     67.00 174.00   0.50    2.50    --  106.00 139.00-152.00  214
 15  \w     41.00 120.00   0.50    0.70    --   48.16  37.00 120.00  158
 16  \w     28.00 119.00   0.50    0.70    --   48.16  77.00   0.00  182
 17  \w     41.00 120.00   0.50    0.70    --   48.16  37.00 120.00  158
 18  \w    -24.00  24.00   0.50    0.70    --   48.16 -19.00  30.00   96
 19  \w    -24.00  24.00   0.50    0.70    --   48.16 -19.00 120.00   96
 20  \w    -24.00  24.00   0.50    0.70    --   48.16 -19.00-120.00   96
 21  \w   -169.00 -83.00   0.50    2.50    --  -97.00 -61.00  90.00  172
 22  \w   -169.00 -83.00   0.50    2.50    --  -97.00 -61.00  90.00  172
 23  \w    -53.00 -25.00   0.50    2.50    --  -97.00  45.00  60.00   56
 24  \w    -53.00 -25.00   0.50    2.50    --  -97.00  45.00-120.00   56
 25  \w    -53.00 -25.00   0.50    2.50    --  -97.00  45.00   0.00   56
 26  \w   -169.00 -89.00   0.50    2.50    --  -97.00 -15.00-180.00  160
 27  \w    -53.00 -25.00   0.50    2.50    --  -97.00  45.00  30.00   56
 28  \w     34.00  69.00   0.50    2.50    --  106.00 -61.00-150.00   70
 29  \w     98.00 175.00   0.50    2.50    --  106.00  15.00-150.00  154
 30  \w     98.00 175.00   0.50    2.50    --  106.00  15.00 150.00  154
 31  \w     98.00 175.00   0.50    2.50    --  106.00  15.00 150.00  154
 32  \w     37.00 112.00   0.50    2.50    --  106.00-125.00  90.00  150
 33  \w     97.00 175.00   0.50    2.50    --  106.00  45.00  30.00  156
 34  \w     97.00 175.00   0.50    2.50    --  106.00  45.00 -60.00  156
 35  \w     37.00 112.00   0.50    2.50    --  106.00-125.00-180.00  150
 36  \w     97.00 175.00   0.50    2.50    --  106.00  45.00  30.00  156
 37  \w     97.00 175.00   0.50    2.50    --  106.00  45.00   0.00  156
 38  \w     98.00 175.00   0.50    2.50    --  106.00  30.00  90.00  154
 39  \w     34.00 106.00   0.50    2.50    --  106.00 -94.00-150.00  144
 40  \w     34.00  69.00   0.50    2.50    --  106.00 -61.00  90.00   70
 41  \w     34.00 106.00   0.50    2.50    --  106.00 -94.00 -60.00  144
 42  \w     98.00 175.00   0.50    2.50    --  106.00  15.00-150.00  154
 43  \w     37.00 112.00   0.50    2.50    --  106.00-125.00  60.00  150
 44  \w     34.00 104.00   0.50    2.50    --  106.00 -77.00-120.00  140
 45  \w     34.00 106.00   0.50    2.50    --  106.00 -94.00 -30.00  144
 46  \w     34.00 104.00   0.50    2.50    --  106.00 -77.00 -30.00  140
 47  \w     34.00 106.00   0.50    2.50    --  106.00 -94.00 -60.00  144
 48  \w     34.00  69.00   0.50    2.50    --  106.00 -61.00 -60.00   70
 49  \w     34.00 104.00   0.50    2.50    --  106.00 -77.00-180.00  140
 50  \w     76.00 137.00   0.50    2.50    --  106.00 125.00 -90.00  122
 51  \w     76.00 137.00   0.50    2.50    --  106.00 125.00 -90.00  122
 52  \w     73.00 106.00   0.50    2.50    --  106.00 -94.00-180.00   66
 53  \w     42.00 112.00   0.50    2.50    --  106.00-125.00-150.00  140
 54  \w     38.00 112.00   0.50    2.50    --  106.00-125.00 -60.00  148
 55  \w     76.00 112.00   0.50    2.50    --  106.00-125.00 -30.00   72
 56  \w     44.00  69.00   0.50    2.50    --  106.00 -61.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1131
_diffrn_reflns_av_unetI/netI     0.0584
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            76169
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.236
_diffrn_reflns_theta_min         3.269
_exptl_absorpt_coefficient_mu    4.266
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88914
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.128a (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    1.613
_exptl_crystal_description       plate
_exptl_crystal_F_000             1304
_refine_diff_density_max         0.680
_refine_diff_density_min         -0.456
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     907
_refine_ls_number_reflns         11084
_refine_ls_number_restraints     1123
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.1161
_refine_ls_R_factor_gt           0.0888
_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^)+(0.1829P)^2^+0.7369P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2599
_refine_ls_wR_factor_ref         0.2843
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7465
_reflns_number_total             11084
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9482\% 
around [0.66 -0.71 -0.24] (reciprocal) or [0.70 -0.71 -0.00] (direct)
;
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt-pf6-odcb-bb-300k
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_original_formula_sum        'C24.40 H13.56 Cl0.80 F4.80 P0.80 S2'
_cod_database_code               1575425
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H S P F Cl'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 S005-C01C \\sim S0-C1
 with sigma of 0.02
 C012-C01F \\sim C0-C4
 with sigma of 0.02
 C012-C01G \\sim C0-C5
 with sigma of 0.02
 C012-C01I \\sim C0-C6
 with sigma of 0.02
 C01A-C01B \\sim C3-C2
 with sigma of 0.02
 C01A-C01U \\sim C3-C01V
 with sigma of 0.02
 C01B-C01C \\sim C2-C1
 with sigma of 0.02
 C01B-C01F \\sim C2-C4
 with sigma of 0.02
 C01F-H01F \\sim C4-H4
 with sigma of 0.02
 C01G-C01T \\sim C5-C7
 with sigma of 0.02
 C01G-C01U \\sim C5-C01V
 with sigma of 0.02
 C01I-H01I \\sim C6-H6
 with sigma of 0.02
 C01I-C01N \\sim C6-C8
 with sigma of 0.02
 C01N-H01N \\sim C8-H8
 with sigma of 0.02
 C01N-C020 \\sim C8-C9
 with sigma of 0.02
 C01T-H01T \\sim C7-H7
 with sigma of 0.02
 C01T-C020 \\sim C7-C9
 with sigma of 0.02
 C020-H020 \\sim C9-H9
 with sigma of 0.02
 S005-C01B \\sim S0-C2
 with sigma of 0.04
 C012-C01B \\sim C0-C2
 with sigma of 0.04
 C012-H01F \\sim C0-H4
 with sigma of 0.04
 C012-H01I \\sim C0-H6
 with sigma of 0.04
 C012-C01N \\sim C0-C8
 with sigma of 0.04
 C012-C01T \\sim C0-C7
 with sigma of 0.04
 C012-C01U \\sim C0-C01V
 with sigma of 0.04
 C01A-C01C \\sim C3-C1
 with sigma of 0.04
 C01A-C01F \\sim C3-C4
 with sigma of 0.04
 C01A-C01G \\sim C3-C5
 with sigma of 0.04
 C01B-H01F \\sim C2-H4
 with sigma of 0.04
 C01B-C01U \\sim C2-C01V
 with sigma of 0.04
 C01C-C01F \\sim C1-C4
 with sigma of 0.04
 C01F-C01G \\sim C4-C5
 with sigma of 0.04
 C01F-C01I \\sim C4-C6
 with sigma of 0.04
 C01G-C01I \\sim C5-C6
 with sigma of 0.04
 C01G-H01T \\sim C5-H7
 with sigma of 0.04
 C01G-C020 \\sim C5-C9
 with sigma of 0.04
 C01I-H01N \\sim C6-H8
 with sigma of 0.04
 C01I-C020 \\sim C6-C9
 with sigma of 0.04
 H01I-C01N \\sim H6-C8
 with sigma of 0.04
 C01N-C01T \\sim C8-C7
 with sigma of 0.04
 C01N-H020 \\sim C8-H9
 with sigma of 0.04
 H01N-C020 \\sim H8-C9
 with sigma of 0.04
 C01T-C01U \\sim C7-C01V
 with sigma of 0.04
 C01T-H020 \\sim C7-H9
 with sigma of 0.04
 H01T-C020 \\sim H7-C9
 with sigma of 0.04
 P2-F29 \\sim P2-F29A
 with sigma of 0.02
 P2-F31 \\sim P2-F31A
 with sigma of 0.02
 P2-F30 \\sim P2-F30A
 with sigma of 0.02
 P2-F32 \\sim P2-F32A
 with sigma of 0.02
 P2-F33 \\sim P2-F33A
 with sigma of 0.02
 P2-F28 \\sim P2-F28A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S005 \\sim C01C \\sim C01B \\sim C01A \\sim C01F \\sim C01U \\sim C012 \\sim
H01F \\sim H01U \\sim C01G \\sim C01I \\sim C01T \\sim H01I \\sim C01N \\sim
H01T \\sim C020 \\sim H01N \\sim H020 \\sim S0 \\sim C1 \\sim C2 \\sim C3 \\sim
C4 \\sim C01V \\sim H4 \\sim C0 \\sim C5 \\sim C6 \\sim C7 \\sim H6 \\sim C8
\\sim H7 \\sim C9 \\sim H8 \\sim H9: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
F29A \\sim P2 \\sim F29 \\sim F31 \\sim F30 \\sim F32 \\sim F33 \\sim F28 \\sim
F32A \\sim F31A \\sim F30A \\sim F33A \\sim F28A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 S005, C01C, C01B, C01A, C01F, C01U, C012, H01F, H01U, C01G, C01I, C01T, H01I,
 C01N, H01T, C020, H01N, H020, S0, C1, C2, C3, C4, C01V, H4, C0, C5, C6, C7, H6,
  C8, H7, C9, H8, H9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F29, P2, F31, F30, F32, F33, F28, F32A, F29A, F31A, F30A, F33A, F28A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F32A)=Sof(F29A)=Sof(F31A)=Sof(F30A)=Sof(F33A)=Sof(F28A)=1-FVAR(1)
 Sof(F29)=Sof(F31)=Sof(F30)=Sof(F32)=Sof(F33)=Sof(F28)=FVAR(1)
 Fixed Sof: S005(0.9) C012(0.9) C01A(0.9) C01B(0.9) C01C(0.9) C01F(0.9)
 H01F(0.9) C01G(0.9) C01I(0.9) H01I(0.9) C01N(0.9) H01N(0.9) C01T(0.9)
 H01T(0.9) C01U(0.9) H01U(0.9) C020(0.9) H020(0.9) C1(0.1) S0(0.1) C2(0.1)
 C3(0.1) C4(0.1) H4(0.1) C01V(0.1) C0(0.1) C5(0.1) C6(0.1) H6(0.1) C7(0.1)
 H7(0.1) C8(0.1) H8(0.1) C9(0.1) H9(0.1)
6.a Aromatic/amide H refined with riding coordinates:
 C00I(H00I), C00K(H00K), C00M(H00M), C00T(H00T), C00V(H00V), C00W(H00W),
 C00Z(H00Z), C010(H010), C014(H014), C016(H016), C018(H018), C019(H019),
 C01E(H01E), C01F(H01F), C01H(H01H), C01I(H01I), C01J(H01J), C01K(H01K),
 C01M(H01M), C01N(H01N), C01O(H01O), C01P(H01P), C01Q(H01Q), C01R(H01R),
 C01S(H01S), C01T(H01T), C01U(H01U), C01X(H01X), C01Y(H01Y), C01Z(H01Z),
 C020(H020), C021(H021), C024(H024), C028(H028), C4(H4), C6(H6), C7(H7), C8(H8),
  C9(H9)
;
_shelx_res_checksum              86231
_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 1.278
_oxdiff_exptl_absorpt_empirical_full_min 0.755
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2