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_1575412
_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, 0.8(F6 P), 0.4(C6 H4 Cl2)'
_chemical_formula_sum            'C24.4 H13.6 Cl0.8 F4.8 P0.79 S2'
_chemical_formula_weight         514.84
_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                71.394(2)
_cell_angle_beta                 86.0120(10)
_cell_angle_gamma                79.4590(10)
_cell_formula_units_Z            5
_cell_length_a                   13.7540(2)
_cell_length_b                   13.8852(2)
_cell_length_c                   14.6689(3)
_cell_measurement_reflns_used    15027
_cell_measurement_temperature    200
_cell_measurement_theta_max      74.9710
_cell_measurement_theta_min      3.2740
_cell_volume                     2610.01(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (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      200.00
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.940
_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    -96.00 -26.00   0.50    0.28    --  -48.04 131.00  33.00  140
  2  \w   -101.00 -30.00   0.50    0.28    --  -48.04 138.00-151.00  142
  3  \w   -119.00 -73.00   0.50    0.28    --  -48.04-138.00 146.00   92
  4  \w     68.00 119.00   0.50    0.28    --   48.04 138.00-151.00  102
  5  \w     21.00  96.00   0.50    0.28    --   48.04-131.00 -38.00  150
  6  \w     72.00 118.00   0.50    0.28    --   48.04 131.00  33.00   92
  7  \w     24.00 101.00   0.50    0.28    --   48.04-138.00 146.00  154
  8  \w   -169.00 -73.00   0.50    1.12    --  -97.00-138.00 146.00  192
  9  \w   -121.00 -30.00   0.50    1.12    --  -97.00 138.00-151.00  182
 10  \w   -167.00 -78.00   0.50    1.12    --  -97.00-131.00 -38.00  178
 11  \w   -116.00 -27.00   0.50    1.12    --  -97.00 131.00  33.00  178
 12  \w     68.00 174.00   0.50    1.12    --  104.77 138.00-151.00  212
 13  \w     35.00 116.00   0.50    1.12    --  104.77-131.00 -38.00  162
 14  \w     33.00 121.00   0.50    1.12    --  104.77-138.00 146.00  176
 15  \w     72.00 175.00   0.50    1.12    --  104.77 131.00  33.00  206
 16  \w    -24.00  24.00   0.50    0.28    --   48.04 -19.00  30.00   96
 17  \w    -24.00  24.00   0.50    0.28    --   48.04 -19.00-150.00   96
 18  \w    -24.00  24.00   0.50    0.28    --   48.04 -19.00 120.00   96
 19  \w    -24.00  24.00   0.50    0.28    --   48.04 -19.00-120.00   96
 20  \w    -24.00  24.00   0.50    0.28    --   48.04 -19.00 -60.00   96
 21  \w    -23.00  40.00   0.50    0.28    --   48.04 -37.00-180.00  126
 22  \w    -68.00 -25.00   0.50    1.12    --  -97.00  57.00  60.00   86
 23  \w   -169.00 -89.00   0.50    1.12    --  -97.00 -37.00 -30.00  160
 24  \w   -166.00 -82.00   0.50    1.12    --  -97.00-125.00 120.00  168
 25  \w   -169.00 -76.00   0.50    1.12    --  -97.00 -77.00  60.00  186
 26  \w   -169.00 -89.00   0.50    1.12    --  -97.00 -37.00 -30.00  160
 27  \w    -68.00 -25.00   0.50    1.12    --  -97.00  57.00   0.00   86
 28  \w    -68.00 -25.00   0.50    1.12    --  -97.00  57.00-120.00   86
 29  \w   -169.00 -87.00   0.50    1.12    --  -97.00 -49.00 163.51  164
 30  \w    -68.00 -25.00   0.50    1.12    --  -97.00  57.00-180.00   86
 31  \w   -170.00 -89.00   0.50    1.12    --  -97.00 -19.00   0.00  162
 32  \w   -111.00 -28.00   0.50    1.12    --  -97.00 125.00 -30.00  166
 33  \w   -111.00 -28.00   0.50    1.12    --  -97.00 125.00-180.00  166
 34  \w   -111.00 -28.00   0.50    1.12    --  -97.00 125.00-180.00  166
 35  \w   -169.00-140.00   0.50    1.12    --  -97.00 -49.00 163.51   58
 36  \w    -60.00 -27.00   0.50    1.12    --  -97.00  57.00-150.00   66
 37  \w    100.00 136.00   0.50    1.12    --  104.77  37.00 150.00   72
 38  \w     60.00  86.00   0.50    1.12    --  104.77 -99.00   0.00   52
 39  \w     34.00  64.00   0.50    1.12    --  104.77 -57.00 -90.00   60
 40  \w     34.00  63.00   0.50    1.12    --  104.77 -57.00   0.00   58
 41  \w     35.00 106.00   0.50    1.12    --  104.77 -99.00 -60.00  142
 42  \w     35.00 107.00   0.50    1.12    --  104.77-104.00 127.34  144
 43  \w     33.00  58.00   0.50    1.12    --  104.77 -57.00  90.00   50
 44  \w     99.00 174.00   0.50    1.12    --  104.77  19.00  90.00  150
 45  \w     46.00  99.00   0.50    1.12    --  104.77 -99.00 150.00  106
 46  \w     61.00 106.00   0.50    1.12    --  104.77 -99.00  30.00   90
 47  \w    150.00 175.00   0.50    1.12    --  104.77  37.00 150.00   50
 48  \w     56.00  83.00   0.50    1.12    --  104.77 -77.00 -60.00   54
;
_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  0.0944
_diffrn_reflns_av_unetI/netI     0.0520
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            60064
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.600
_diffrn_reflns_theta_min         3.269
_exptl_absorpt_coefficient_mu    4.326
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89363
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (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    1.638
_exptl_crystal_description       plate
_exptl_crystal_F_000             1303
_refine_diff_density_max         0.999
_refine_diff_density_min         -0.697
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     847
_refine_ls_number_reflns         10445
_refine_ls_number_restraints     578
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1079
_refine_ls_R_factor_gt           0.0837
_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^)+(0.1606P)^2^+2.0393P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2374
_refine_ls_wR_factor_ref         0.2592
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7320
_reflns_number_total             10445
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9419\% 
around [0.67 -0.71 -0.23] (reciprocal) or [0.70 -0.72 -0.00] (direct)
;
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt-pf6-odcb-bb-200K
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_original_formula_sum        'C24.40 H13.60 Cl0.80 F4.80 P0.79 S2'
_cod_database_code               1575412
_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
 S49-C60 \\sim S49A-C60A
 with sigma of 0.02
 C59-C60 \\sim C59A-C60A
 with sigma of 0.02
 C59-C50 \\sim C59A-C50A
 with sigma of 0.02
 C59-C58 \\sim C59A-C58A
 with sigma of 0.02
 C52-C57 \\sim C52A-C57A
 with sigma of 0.02
 C52-C51 \\sim C52A-C51A
 with sigma of 0.02
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C57-C56 \\sim C57A-C56A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
 C55-C56 \\sim C55A-C56A
 with sigma of 0.02
 C55-C54 \\sim C55A-C54A
 with sigma of 0.02
 C54-C53 \\sim C54A-C53A
 with sigma of 0.02
 S49-C59 \\sim S49A-C59A
 with sigma of 0.04
 C59-C57 \\sim C59A-C57A
 with sigma of 0.04
 C59-C51 \\sim C59A-C51A
 with sigma of 0.04
 C60-C50 \\sim C60A-C50A
 with sigma of 0.04
 C60-C58 \\sim C60A-C58A
 with sigma of 0.04
 C52-C50 \\sim C52A-C50A
 with sigma of 0.04
 C52-C58 \\sim C52A-C58A
 with sigma of 0.04
 C52-C56 \\sim C52A-C56A
 with sigma of 0.04
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
 C57-C55 \\sim C57A-C55A
 with sigma of 0.04
 C57-C51 \\sim C57A-C51A
 with sigma of 0.04
 C57-C53 \\sim C57A-C53A
 with sigma of 0.04
 C50-C58 \\sim C50A-C58A
 with sigma of 0.04
 C58-C56 \\sim C58A-C56A
 with sigma of 0.04
 C55-C53 \\sim C55A-C53A
 with sigma of 0.04
 C56-C54 \\sim C56A-C54A
 with sigma of 0.04
 C51-C53 \\sim C51A-C53A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
S49A \\sim C60A \\sim C59A \\sim C50A \\sim C58A \\sim C51A \\sim C57A \\sim
C52A \\sim C56A \\sim C53A \\sim C55A \\sim C54A \\sim S49 \\sim C60 \\sim C59
\\sim C50 \\sim C58 \\sim C51 \\sim C57 \\sim C52 \\sim C56 \\sim C53 \\sim C55
\\sim C54: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
4. Rigid body (RIGU) restrains
 S49, C60, C59, C50, C58, C51, C57, C52, C56, C53, C55, C54, S49A, C60A, C59A,
 C50A, C58A, C51A, C57A, C52A, C56A, C53A, C55A, C54A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: S49(0.9) C59(0.9) C60(0.9) C52(0.9) C57(0.9) C50(0.9) C58(0.9)
 H58(0.9) C55(0.9) H55(0.9) C56(0.9) H56(0.9) C54(0.9) H54(0.9) C51(0.9)
 H51(0.9) C53(0.9) H53(0.9) S49A(0.1) C60A(0.1) C59A(0.1) C50A(0.1) C58A(0.1)
 H58A(0.1) C51A(0.1) H51A(0.1) C57A(0.1) C52A(0.1) C56A(0.1) H56A(0.1)
 C53A(0.1) H53A(0.1) C55A(0.1) H55A(0.1) C54A(0.1) H54A(0.1)
6.a Aromatic/amide H refined with riding coordinates:
 C39(H39), C35(H35), C15(H15), C18(H18), C4(H4), C11(H11), C17(H17), C28(H28),
 C42(H42), C22(H22), C46(H46), C41(H41), C19(H19), C43(H43), C20(H20), C58(H58),
  C31(H31), C30(H30), C55(H55), C56(H56), C54(H54), C32(H32), C9(H9), C44(H44),
 C6(H6), C51(H51), C53(H53), C33(H33), C76(H76), C7(H7), C8(H8), C79(H79),
 C78(H78), C77(H77), C58A(H58A), C51A(H51A), C56A(H56A), C53A(H53A), C55A(H55A),
  C54A(H54A)
;
_shelx_res_checksum              86456
_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 1.322
_oxdiff_exptl_absorpt_empirical_full_min 0.828
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2