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_1575418
_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         '0.4(C6 H5 Br), C22 H12 S2, 0.8(F6 P)'
_chemical_formula_sum            'C24.4 H14 Br0.4 F4.8 P0.8 S2'
_chemical_formula_weight         519.22
_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                70.766(2)
_cell_angle_beta                 85.7420(10)
_cell_angle_gamma                79.0270(10)
_cell_formula_units_Z            5
_cell_length_a                   13.5317(2)
_cell_length_b                   13.9267(2)
_cell_length_c                   14.6385(3)
_cell_measurement_reflns_used    24289
_cell_measurement_temperature    100
_cell_measurement_theta_max      77.5200
_cell_measurement_theta_min      3.8460
_cell_volume                     2556.85(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.136a 64-bit (release 23-08-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (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      100.00
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.981
_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    -24.00  27.00   0.50    0.10    --   47.91 -19.00 150.00  102
  2  \w    -24.00  27.00   0.50    0.10    --   47.91 -19.00   0.00  102
  3  \w    -24.00  27.00   0.50    0.10    --   47.91 -19.00-120.00  102
  4  \w    -24.00  27.00   0.50    0.10    --   47.91 -19.00-180.00  102
  5  \w     61.00 104.00   0.50    0.40    --  106.00 -94.00 -60.00   86
  6  \w     36.00 121.00   0.50    0.10    --   47.91-167.00 -27.00  170
  7  \w     37.00 112.00   0.50    0.40    --  106.00-125.00  90.00  150
  8  \w     37.00 112.00   0.50    0.40    --  106.00-125.00  60.00  150
  9  \w     36.00 140.00   0.50    0.40    --  106.00-167.00 -27.00  208
 10  \w     37.00 112.00   0.50    0.40    --  106.00-125.00-150.00  150
 11  \w     37.00 112.00   0.50    0.40    --  106.00-125.00-150.00  150
 12  \w     37.00 112.00   0.50    0.40    --  106.00-125.00-120.00  150
 13  \w     43.00 112.00   0.50    0.40    --  106.00-125.00 -90.00  138
 14  \w     43.00 112.00   0.50    0.40    --  106.00-125.00 -90.00  138
 15  \w     37.00 112.00   0.50    0.40    --  106.00-125.00  60.00  150
 16  \w     37.00 112.00   0.50    0.40    --  106.00-125.00 120.00  150
 17  \w     38.00 109.00   0.50    0.40    --  106.00-115.00 118.00  142
 18  \w     34.00 106.00   0.50    0.40    --  106.00 -94.00 150.00  144
 19  \w     34.00 106.00   0.50    0.40    --  106.00 -94.00 120.00  144
 20  \w     34.00 106.00   0.50    0.40    --  106.00 -94.00 120.00  144
 21  \w     11.00  85.00   0.50    0.10    --   47.91-115.00 118.00  148
 22  \w     34.00 106.00   0.50    0.40    --  106.00 -94.00-120.00  144
 23  \w     34.00 106.00   0.50    0.40    --  106.00 -94.00 -90.00  144
 24  \w     36.00  65.00   0.50    0.40    --  106.00 -61.00 -30.00   58
 25  \w     34.00 100.00   0.50    0.40    --  106.00 -77.00 -60.00  132
 26  \w     34.00  88.00   0.50    0.40    --  106.00 -77.00 -90.00  108
 27  \w     34.00  69.00   0.50    0.40    --  106.00 -61.00-180.00   70
 28  \w     34.00 100.00   0.50    0.40    --  106.00 -77.00 -30.00  132
 29  \w     55.00  81.00   0.50    0.40    --  106.00 -77.00  30.00   52
 30  \w     34.00  69.00   0.50    0.40    --  106.00 -61.00  30.00   70
 31  \w     54.00  93.00   0.50    0.40    --  106.00 -77.00  90.00   78
 32  \w     34.00 100.00   0.50    0.40    --  106.00 -77.00 150.00  132
 33  \w     34.00  69.00   0.50    0.40    --  106.00 -61.00 120.00   70
 34  \w     34.00  69.00   0.50    0.40    --  106.00 -61.00   0.00   70
 35  \w     98.00 175.00   0.50    0.40    --  106.00  15.00-150.00  154
 36  \w     98.00 175.00   0.50    0.40    --  106.00  30.00 -30.00  154
 37  \w     97.00 175.00   0.50    0.40    --  106.00  45.00   0.00  156
 38  \w     99.00 175.00   0.50    0.40    --  106.00  30.00 -60.00  152
 39  \w     27.00 120.00   0.50    0.10    --   47.91  77.00 -60.00  186
 40  \w     98.00 175.00   0.50    0.40    --  106.00  15.00-150.00  154
 41  \w     98.00 175.00   0.50    0.40    --  106.00  15.00 -90.00  154
 42  \w     98.00 175.00   0.50    0.40    --  106.00  30.00  60.00  154
 43  \w     98.00 175.00   0.50    0.40    --  106.00  30.00  90.00  154
 44  \w    116.00 150.00   0.50    0.40    --  106.00  45.00 120.00   68
 45  \w     48.00 120.00   0.50    0.10    --   47.91 167.00  -7.00  144
 46  \w     76.00 175.00   0.50    0.40    --  106.00 125.00 150.00  198
 47  \w     48.00 153.00   0.50    0.40    --  106.00 167.00  -7.00  210
 48  \w     82.00 174.00   0.50    0.40    --  106.00 115.00-152.00  184
 49  \w    -31.00  26.00   0.50    0.10    --  -47.91  19.00-180.00  114
 50  \w   -121.00 -42.00   0.50    0.10    --  -47.91 167.00  -7.00  158
 51  \w    -53.00 -25.00   0.50    0.40    --  -97.00  45.00 150.00   56
 52  \w   -140.00 -42.00   0.50    0.40    --  -97.00 167.00  -7.00  196
 53  \w   -108.00 -29.00   0.50    0.40    --  -97.00 115.00-152.00  158
 54  \w    -85.00 -17.00   0.50    0.10    --  -47.91 115.00-152.00  136
 55  \w   -169.00 -84.00   0.50    0.40    --  -97.00 -58.00-166.76  170
 56  \w   -120.00 -54.00   0.50    0.10    --  -47.91-167.00 -27.00  132
 57  \w   -153.00 -54.00   0.50    0.40    --  -97.00-167.00 -27.00  198
 58  \w   -165.00 -88.00   0.50    0.40    --  -97.00-115.00 118.00  154
;
_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_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19964
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.264
_diffrn_reflns_theta_min         3.198
_exptl_absorpt_coefficient_mu    4.372
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91216
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (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    1.686
_exptl_crystal_description       needle
_exptl_crystal_F_000             1308
_refine_diff_density_max         2.139
_refine_diff_density_min         -0.655
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     787
_refine_ls_number_reflns         19964
_refine_ls_number_restraints     300
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0594
_refine_ls_R_factor_gt           0.0487
_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^)+(0.0949P)^2^+0.1331P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1295
_refine_ls_wR_factor_ref         0.1375
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16359
_reflns_number_total             19964
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9953\% 
around [-0.00 0.00 1.00] (reciprocal) or [-0.01 -0.32 0.95] (direct)
;
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt-pf6-bb-100k
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_original_formula_sum        'C24.40 H14 Br0.40 F4.80 P0.80 S2'
_cod_database_code               1575418
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H S Br P F'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5723(7)
 0.4277(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 P68-F72 \\sim P68-F72A
 with sigma of 0.02
 P68-F69 \\sim P68-F69A
 with sigma of 0.02
 P68-F74 \\sim P68-F74A
 with sigma of 0.02
 P68-F73 \\sim P68-F73A
 with sigma of 0.02
 P68-F70 \\sim P68-F70A
 with sigma of 0.02
 P68-F71 \\sim P68-F71A
 with sigma of 0.02
 F71-F74A \\sim F71A-F74A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
F69 \\sim P68 \\sim F73 \\sim F73A \\sim F71 \\sim F72 \\sim F70 \\sim F69A
\\sim F72A \\sim F74A \\sim F74: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
F74A \\sim P68 \\sim F73 \\sim F71A \\sim F71 \\sim F69A \\sim F70 \\sim F72
\\sim F72A \\sim F70A \\sim F69 \\sim F74 \\sim F73A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 F71, P68, F73, F73A, F72, F70, F69A, F72A, F74A, F69, F74
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F74A, P68, F73, F71A, F71, F69A, F70, F72, F72A, F70A, F69, F74, F73A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F69A)=Sof(F73A)=Sof(F72A)=Sof(F74A)=1-FVAR(1)
 Sof(F72)=Sof(F69)=Sof(F74)=Sof(F73)=FVAR(1)
 Sof(F71A)=Sof(F70A)=1-FVAR(2)
 Sof(F70)=Sof(F71)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C35(H35), C24(H24), C46(H46), C53(H53), C29(H29), C18(H18), C37(H37), C2(H2),
 C27(H27), C38(H38), C11(H11), C22(H22), C26(H26), C42(H42), C48(H48), C13(H13),
  C51(H51), C16(H16), C63(H63), C40(H40), C60(H60), C50(H50), C5(H5), C62(H62),
 C3(H3), C14(H14), C39(H39), C25(H25), C15(H15), C58(H58), C61(H61), C65(H65),
 C49(H49), C6(H6), C4(H4)
;
_shelx_res_checksum              63225
_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 1.315
_oxdiff_exptl_absorpt_empirical_full_min 0.671
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2