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_1575411
_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, 0.752(F6 P), C2.4 H1.6 Cl0.8 F0.288 P0.048'
_chemical_formula_sum            'C24.4 H13.6 Cl0.8 F4.8 P0.8 S2'
_chemical_formula_weight         515.21
_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                85.9130(10)
_cell_angle_beta                 71.4840(10)
_cell_angle_gamma                79.5210(10)
_cell_formula_units_Z            5
_cell_length_a                   13.6984(2)
_cell_length_b                   13.7841(2)
_cell_length_c                   14.6009(2)
_cell_measurement_reflns_used    20526
_cell_measurement_temperature    100
_cell_measurement_theta_max      77.2970
_cell_measurement_theta_min      3.1780
_cell_volume                     2570.36(7)
_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 0.994
_diffrn_measured_fraction_theta_max 0.973
_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    0.50    --  -47.91 130.00  67.00  138
  2  \w   -101.00 -30.00   0.50    0.50    --  -47.91 138.00-118.00  142
  3  \w   -120.00 -73.00   0.50    0.50    --  -47.91-138.00-179.00   94
  4  \w     24.00 101.00   0.50    0.50    --   47.91-138.00-179.00  154
  5  \w     20.00  95.00   0.50    0.50    --   47.91-130.00  -4.00  150
  6  \w     68.00 120.00   0.50    0.50    --   47.91 138.00-118.00  104
  7  \w   -121.00 -30.00   0.50    1.70    --  -97.00 138.00-118.00  182
  8  \w   -169.00 -73.00   0.50    1.70    --  -97.00-138.00-179.00  192
  9  \w   -115.00 -27.00   0.50    1.70    --  -97.00 130.00  67.00  176
 10  \w   -167.00 -79.00   0.50    1.70    --  -97.00-130.00  -4.00  176
 11  \w     68.00 174.00   0.50    1.70    --  106.00 138.00-118.00  212
 12  \w     34.00 121.00   0.50    1.70    --  106.00-138.00-179.00  174
 13  \w     36.00 115.00   0.50    1.70    --  106.00-130.00  -4.00  158
 14  \w     73.00 175.00   0.50    1.70    --  106.00 130.00  67.00  204
 15  \w    -31.00  26.00   0.50    0.50    --  -47.91  19.00 -90.00  114
 16  \w    -31.00  26.00   0.50    0.50    --  -47.91  19.00 -30.00  114
 17  \w     35.00 120.00   0.50    0.50    --   47.91  57.00 120.00  170
 18  \w    -24.00  27.00   0.50    0.50    --   47.91 -19.00  60.00  102
 19  \w    -24.00  27.00   0.50    0.50    --   47.91 -19.00 -30.00  102
 20  \w    -24.00  27.00   0.50    0.50    --   47.91 -19.00-150.00  102
 21  \w    -24.00  27.00   0.50    0.50    --   47.91 -19.00  90.00  102
 22  \w    -53.00 -25.00   0.50    1.70    --  -97.00  45.00 120.00   56
 23  \w   -169.00 -89.00   0.50    1.70    --  -97.00 -15.00  30.00  160
 24  \w     76.00 175.00   0.50    1.70    --  106.00 125.00  30.00  198
 25  \w     34.00  69.00   0.50    1.70    --  106.00 -61.00  60.00   70
 26  \w     37.00 112.00   0.50    1.70    --  106.00-125.00  30.00  150
 27  \w     92.00 175.00   0.50    1.70    --  106.00  61.00  30.00  166
 28  \w     76.00 175.00   0.50    1.70    --  106.00 125.00  30.00  198
 29  \w     34.00 106.00   0.50    1.70    --  106.00 -94.00-180.00  144
 30  \w     34.00  69.00   0.50    1.70    --  106.00 -61.00-180.00   70
 31  \w     37.00 112.00   0.50    1.70    --  106.00-125.00 150.00  150
 32  \w     97.00 175.00   0.50    1.70    --  106.00  45.00   0.00  156
 33  \w     34.00 106.00   0.50    1.70    --  106.00 -94.00 150.00  144
 34  \w     76.00 175.00   0.50    1.70    --  106.00 125.00-180.00  198
 35  \w     34.00 100.00   0.50    1.70    --  106.00 -77.00 -90.00  132
 36  \w     34.00 106.00   0.50    1.70    --  106.00 -94.00-150.00  144
 37  \w     37.00 112.00   0.50    1.70    --  106.00-125.00   0.00  150
 38  \w     37.00 112.00   0.50    1.70    --  106.00-125.00 -60.00  150
 39  \w     85.00 175.00   0.50    1.70    --  106.00  77.00  60.00  180
 40  \w     92.00 175.00   0.50    1.70    --  106.00  61.00  30.00  166
 41  \w     97.00 175.00   0.50    1.70    --  106.00  45.00 -30.00  156
 42  \w     76.00 175.00   0.50    1.70    --  106.00 125.00 120.00  198
 43  \w     98.00 175.00   0.50    1.70    --  106.00  15.00-180.00  154
 44  \w     37.00 112.00   0.50    1.70    --  106.00-125.00-180.00  150
 45  \w     34.00 100.00   0.50    1.70    --  106.00 -77.00-180.00  132
 46  \w     76.00 175.00   0.50    1.70    --  106.00 125.00-180.00  198
 47  \w     37.00 112.00   0.50    1.70    --  106.00-125.00  90.00  150
 48  \w     39.00  48.50   0.50    1.70    --  106.00-125.00  90.00   19
;
_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  0.0976
_diffrn_reflns_av_unetI/netI     0.0543
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            67561
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.221
_diffrn_reflns_theta_min         3.261
_exptl_absorpt_coefficient_mu    4.402
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63821
_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    1.664
_exptl_crystal_description       plate
_exptl_crystal_F_000             1304
_refine_diff_density_max         1.109
_refine_diff_density_min         -0.858
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     892
_refine_ls_number_reflns         10732
_refine_ls_number_restraints     1198
_refine_ls_restrained_S_all      0.987
_refine_ls_R_factor_all          0.0857
_refine_ls_R_factor_gt           0.0686
_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^)+(0.1207P)^2^+2.9843P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1915
_refine_ls_wR_factor_ref         0.2038
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8281
_reflns_number_total             10732
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.7003\% 
around [0.70 -0.68 0.23] (reciprocal) or [0.72 -0.69 0.00] (direct)
;
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt-pf6-odcb-bb-100k
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_original_formula_sum        'C24.40 H13.60 Cl0.80 F4.80 P0.80 S2'
_cod_database_code               1575411
_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-C58 \\sim C59A-C58A
 with sigma of 0.02
 C59-C50 \\sim C59A-C50A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C57-C52 \\sim C57A-C52A
 with sigma of 0.02
 C57-C56 \\sim C57A-C56A
 with sigma of 0.02
 C58-H58 \\sim C58A-H58A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C52-C51 \\sim C52A-C51A
 with sigma of 0.02
 C56-H56 \\sim C56A-H56A
 with sigma of 0.02
 C56-C55 \\sim C56A-C55A
 with sigma of 0.02
 C55-H55 \\sim C55A-H55A
 with sigma of 0.02
 C55-C54 \\sim C55A-C54A
 with sigma of 0.02
 C53-H53 \\sim C53A-H53A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C54-H54 \\sim C54A-H54A
 with sigma of 0.02
 C51-H51 \\sim C51A-H51A
 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-H58 \\sim C59A-H58A
 with sigma of 0.04
 C59-C51 \\sim C59A-C51A
 with sigma of 0.04
 C57-H58 \\sim C57A-H58A
 with sigma of 0.04
 C57-H56 \\sim C57A-H56A
 with sigma of 0.04
 C57-C55 \\sim C57A-C55A
 with sigma of 0.04
 C57-C53 \\sim C57A-C53A
 with sigma of 0.04
 C57-C51 \\sim C57A-C51A
 with sigma of 0.04
 C60-C58 \\sim C60A-C58A
 with sigma of 0.04
 C60-C50 \\sim C60A-C50A
 with sigma of 0.04
 C58-C50 \\sim C58A-C50A
 with sigma of 0.04
 C58-C52 \\sim C58A-C52A
 with sigma of 0.04
 C58-C56 \\sim C58A-C56A
 with sigma of 0.04
 C50-C52 \\sim C50A-C52A
 with sigma of 0.04
 C50-H51 \\sim C50A-H51A
 with sigma of 0.04
 C52-C56 \\sim C52A-C56A
 with sigma of 0.04
 C52-H53 \\sim C52A-H53A
 with sigma of 0.04
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
 C52-H51 \\sim C52A-H51A
 with sigma of 0.04
 C56-H55 \\sim C56A-H55A
 with sigma of 0.04
 C56-C54 \\sim C56A-C54A
 with sigma of 0.04
 H56-C55 \\sim H56A-C55A
 with sigma of 0.04
 C55-C53 \\sim C55A-C53A
 with sigma of 0.04
 C55-H54 \\sim C55A-H54A
 with sigma of 0.04
 H55-C54 \\sim H55A-C54A
 with sigma of 0.04
 C53-H54 \\sim C53A-H54A
 with sigma of 0.04
 C53-C51 \\sim C53A-C51A
 with sigma of 0.04
 H53-C54 \\sim H53A-C54A
 with sigma of 0.04
 P76-F80 \\sim P76A-F80A
 with sigma of 0.02
 P76-F78 \\sim P76A-F78A
 with sigma of 0.02
 P76-F77 \\sim P76A-F77A
 with sigma of 0.02
 P76-F82 \\sim P76A-F82A
 with sigma of 0.02
 P76-F79 \\sim P76A-F79A
 with sigma of 0.02
 P76-F81 \\sim P76A-F81A
 with sigma of 0.02
 F80-F78 \\sim F80A-F78A
 with sigma of 0.04
 F80-F77 \\sim F80A-F77A
 with sigma of 0.04
 F80-F82 \\sim F80A-F82A
 with sigma of 0.04
 F80-F79 \\sim F80A-F79A
 with sigma of 0.04
 F80-F81 \\sim F80A-F81A
 with sigma of 0.04
 F78-F77 \\sim F78A-F77A
 with sigma of 0.04
 F78-F82 \\sim F78A-F82A
 with sigma of 0.04
 F78-F79 \\sim F78A-F79A
 with sigma of 0.04
 F78-F81 \\sim F78A-F81A
 with sigma of 0.04
 F77-F82 \\sim F77A-F82A
 with sigma of 0.04
 F77-F79 \\sim F77A-F79A
 with sigma of 0.04
 F77-F81 \\sim F77A-F81A
 with sigma of 0.04
 F82-F79 \\sim F82A-F79A
 with sigma of 0.04
 F82-F81 \\sim F82A-F81A
 with sigma of 0.04
 F79-F81 \\sim F79A-F81A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
S49A \\sim S49 \\sim C60 \\sim C59 \\sim C50A \\sim C58 \\sim C50 \\sim C59A
\\sim C51A \\sim H58 \\sim C57 \\sim C51 \\sim C60A \\sim C58A \\sim C52A \\sim
H51A \\sim C52 \\sim C56 \\sim H51 \\sim C57A \\sim H58A \\sim C53A \\sim C53
\\sim H56 \\sim C55 \\sim C56A \\sim H53A \\sim C54A \\sim H53 \\sim C54 \\sim
H55 \\sim H56A \\sim C55A \\sim H54A \\sim H54 \\sim H55A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
F79A \\sim P76 \\sim F80 \\sim F78 \\sim F77 \\sim F82 \\sim F79 \\sim F81
\\sim F77A \\sim P76A \\sim F81A \\sim F82A \\sim F80A \\sim F78A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F77A) = Uanis(F81A) = Uanis(F80A)
Uanis(F82A) = Uanis(F79A) = Uanis(F80A)
4. Rigid body (RIGU) restrains
 S49A, C60A, C59A, C58A, C50A, C57A, H58A, C51A, C52A, C56A, H51A, C53A, H56A,
 C55A, H53A, C54A, H55A, H54A, S49, C60, C59, C58, C50, H58, C57, C51, C52, C56,
  H51, C53, H56, C55, H53, C54, H55, H54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F79A, F77A, P76A, F81A, F82A, F80A, F78A, F78, P76, F80, F77, F82, F79, F81
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: S49(0.88) P76(0.88) F80(0.88) F78(0.88) F77(0.88) F82(0.88)
 F79(0.88) F81(0.88) C59(0.88) C57(0.88) C60(0.88) C58(0.88) H58(0.88)
 C50(0.88) C52(0.88) C56(0.88) H56(0.88) C55(0.88) H55(0.88) C53(0.88)
 H53(0.88) C54(0.88) H54(0.88) C51(0.88) H51(0.88) S49A(0.12) C60A(0.12)
 C59A(0.12) C58A(0.12) H58A(0.12) C50A(0.12) C57A(0.12) C51A(0.12) H51A(0.12)
 C52A(0.12) C56A(0.12) H56A(0.12) C53A(0.12) H53A(0.12) C55A(0.12) H55A(0.12)
 C54A(0.12) H54A(0.12) F77A(0.12) F79A(0.12) F81A(0.12) F82A(0.12) F80A(0.12)
 P76A(0.12) F78A(0.12)
6.a Aromatic/amide H refined with riding coordinates:
 C31(H31), C46(H46), C2(H2), C39(H39), C18(H18), C17(H17), C28(H28), C9(H9),
 C15(H15), C35(H35), C30(H30), C42(H42), C19(H19), C32(H32), C58(H58), C20(H20),
  C43(H43), C22(H22), C56(H56), C5(H5), C69(H69), C41(H41), C33(H33), C72(H72),
 C7(H7), C55(H55), C53(H53), C70(H70), C6(H6), C54(H54), C4(H4), C51(H51),
 C44(H44), C71(H71), C58A(H58A), C51A(H51A), C56A(H56A), C53A(H53A), C55A(H55A),
  C54A(H54A)
;
_shelx_res_checksum              61966
_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 1.752
_oxdiff_exptl_absorpt_empirical_full_min 0.754
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2