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_1575421
_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         '1(C22 H12 S2), 0.667(F6 P), 0.667(C6 H5 Cl)'
_chemical_formula_sum            'C26 H15.33 Cl0.67 F4 P0.67 S2'
_chemical_formula_weight         512.12
_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                103.036(2)
_cell_angle_beta                 105.912(3)
_cell_angle_gamma                102.613(2)
_cell_formula_units_Z            3
_cell_length_a                   10.5204(3)
_cell_length_b                   10.7353(2)
_cell_length_c                   15.7430(5)
_cell_measurement_reflns_used    9484
_cell_measurement_temperature    100
_cell_measurement_theta_max      74.8410
_cell_measurement_theta_min      3.0670
_cell_volume                     1589.57(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.950
_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    -93.00 -24.00   0.50    3.00    --  -47.91 127.00-142.00  138
  2  \w   -104.00 -32.00   0.50    3.00    --  -47.91 143.00  26.00  144
  3  \w   -120.00 -70.00   0.50    3.00    --  -47.91-143.00 -28.00  100
  4  \w     64.00 120.00   0.50    3.00    --   47.91 143.00  26.00  112
  5  \w     26.00 104.00   0.50    3.00    --   47.91-143.00 -28.00  156
  6  \w     19.00  93.00   0.50    3.00    --   47.91-127.00 141.00  148
  7  \w   -125.00 -32.00   0.50    9.00    --  -97.00 143.00  26.00  186
  8  \w   -112.00 -27.00   0.50    9.00    --  -97.00 127.00-142.00  170
  9  \w   -167.00 -81.00   0.50    9.00    --  -97.00-127.00 141.00  172
 10  \w   -169.00 -70.00   0.50    9.00    --  -97.00-143.00 -28.00  198
 11  \w     33.00 125.00   0.50    9.00    --  104.77-143.00 -28.00  184
 12  \w     64.00 171.00   0.50    9.00    --  104.77 143.00  26.00  214
 13  \w     35.00 113.00   0.50    9.00    --  104.77-127.00 141.00  156
 14  \w     75.00 175.00   0.50    9.00    --  104.77 127.00-142.00  200
 15  \w    -24.00  24.00   0.50    3.00    --   47.91 -19.00 120.00   96
 16  \w    -24.00  24.00   0.50    3.00    --   47.91 -19.00-150.00   96
 17  \w    -24.00  24.00   0.50    3.00    --   47.91 -19.00-120.00   96
 18  \w    -24.00  24.00   0.50    3.00    --   47.91 -19.00 -30.00   96
 19  \w     27.00 120.00   0.50    3.00    --   47.91  77.00  90.00  186
 20  \w    -68.00 -25.00   0.50    9.00    --  -97.00  57.00-120.00   86
 21  \w   -167.00 -91.00   0.50    9.00    --  -97.00 -99.00-180.00  152
 22  \w   -169.00 -89.00   0.50    9.00    --  -97.00 -37.00 120.00  160
 23  \w   -166.00 -82.00   0.50    9.00    --  -97.00-125.00  30.00  168
 24  \w   -109.00 -25.00   0.50    9.00    --  -97.00  77.00  60.00  168
 25  \w    -68.00 -25.00   0.50    9.00    --  -97.00  57.00-180.00   86
 26  \w   -169.00 -84.00   0.50    9.00    --  -97.00 -57.00-150.00  170
 27  \w     35.00 106.00   0.50    9.00    --  104.77 -99.00 -30.00  142
 28  \w     33.00  64.00   0.50    9.00    --  104.77 -57.00  60.00   62
 29  \w     33.00  64.00   0.50    9.00    --  104.77 -57.00 150.00   62
 30  \w     33.00  64.00   0.50    9.00    --  104.77 -57.00-180.00   62
 31  \w     33.00  64.00   0.50    9.00    --  104.77 -57.00   0.00   62
 32  \w     33.00 105.00   0.50    9.00    --  104.77 -77.00 -30.00  144
 33  \w     97.00 175.00   0.50    9.00    --  104.77  37.00  30.00  156
 34  \w     33.00 105.00   0.50    9.00    --  104.77 -77.00-120.00  144
 35  \w     33.00 105.00   0.50    9.00    --  104.77 -77.00 120.00  144
 36  \w     97.00 175.00   0.50    9.00    --  104.77  19.00 -30.00  156
 37  \w     33.00  64.00   0.50    9.00    --  104.77 -57.00  30.00   62
 38  \w     35.00 106.00   0.50    9.00    --  104.77 -99.00-180.00  142
 39  \w     33.00  64.00   0.50    9.00    --  104.77 -57.00-150.00   62
 40  \w     27.00 120.00   0.50    3.00    --   47.91  77.00   0.00  186
 41  \w     27.00 120.00   0.50    3.00    --   47.91  77.00-180.00  186
 42  \w     27.00 120.00   0.50    3.00    --   47.91  77.00 -60.00  186
 43  \w     27.00 120.00   0.50    3.00    --   47.91  77.00 120.00  186
 44  \w     35.00 120.00   0.50    3.00    --   47.91  57.00 -90.00  170
;
_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      -0.0498789000
_diffrn_orient_matrix_UB_12      -0.0544894000
_diffrn_orient_matrix_UB_13      -0.1065819000
_diffrn_orient_matrix_UB_21      -0.1168488000
_diffrn_orient_matrix_UB_22      -0.1135442000
_diffrn_orient_matrix_UB_23      0.0015658000
_diffrn_orient_matrix_UB_31      -0.0965518000
_diffrn_orient_matrix_UB_32      0.0892608000
_diffrn_orient_matrix_UB_33      -0.0068897000
_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  0.0962
_diffrn_reflns_av_unetI/netI     0.0624
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            34602
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.529
_diffrn_reflns_theta_min         3.064
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.968
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71987
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light pink'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.605
_exptl_crystal_description       plate
_exptl_crystal_F_000             782
_refine_diff_density_max         1.003
_refine_diff_density_min         -0.441
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     636
_refine_ls_number_reflns         6435
_refine_ls_number_restraints     908
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0959
_refine_ls_R_factor_gt           0.0742
_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^)+(0.0559P)^2^+2.9726P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1584
_refine_ls_wR_factor_ref         0.1685
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5181
_reflns_number_total             6435
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt-pf6-100k
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_original_cell_volume        1589.57(8)
_cod_database_code               1575421
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H S P F'
_chemical_oxdiff_usercomment     ' '
_diffrn_oxdiff_digest_hkl
;
0103890cb3b8480211760cab40e24589a68926
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 S25-C24 \\sim S25A-C24A
 with sigma of 0.02
 C15-C19 \\sim C15A-C19A
 with sigma of 0.04
 C22-C14 \\sim C22A-C14A
 with sigma of 0.04
 S25-C13 \\sim S25A-C13A
 with sigma of 0.02
 C24-C35 \\sim C24A-C35A
 with sigma of 0.04
 C28-C34 \\sim C28A-C34A
 with sigma of 0.04
 S36-C23 \\sim S36A-C23A
 with sigma of 0.02
 C31-C33 \\sim C31A-C33A
 with sigma of 0.04
 S36-C35 \\sim S36A-C35A
 with sigma of 0.02
 C26-C23 \\sim C26A-C23A
 with sigma of 0.04
 C20-C16 \\sim C20A-C16A
 with sigma of 0.04
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 C27-C35 \\sim C27A-C35A
 with sigma of 0.04
 C26-C24 \\sim C26A-C24A
 with sigma of 0.02
 C21-C13 \\sim C21A-C13A
 with sigma of 0.04
 C26-C35 \\sim C26A-C35A
 with sigma of 0.02
 C23-C13 \\sim C23A-C13A
 with sigma of 0.04
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 C22-C13 \\sim C22A-C13A
 with sigma of 0.02
 C20-C15 \\sim C20A-C15A
 with sigma of 0.02
 C28-C30 \\sim C28A-C30A
 with sigma of 0.04
 C20-C21 \\sim C20A-C21A
 with sigma of 0.02
 C27-C33 \\sim C27A-C33A
 with sigma of 0.04
 C20-C19 \\sim C20A-C19A
 with sigma of 0.02
 C15-C21 \\sim C15A-C21A
 with sigma of 0.04
 C28-C27 \\sim C28A-C27A
 with sigma of 0.02
 C21-C19 \\sim C21A-C19A
 with sigma of 0.04
 C28-C29 \\sim C28A-C29A
 with sigma of 0.02
 C30-C32 \\sim C30A-C32A
 with sigma of 0.04
 C28-C33 \\sim C28A-C33A
 with sigma of 0.02
 C29-C33 \\sim C29A-C33A
 with sigma of 0.04
 C14-C15 \\sim C14A-C15A
 with sigma of 0.02
 C14-C13 \\sim C14A-C13A
 with sigma of 0.02
 C15-C16 \\sim C15A-C16A
 with sigma of 0.02
 C32-C34 \\sim C32A-C34A
 with sigma of 0.04
 C17-C16 \\sim C17A-C16A
 with sigma of 0.02
 C26-C34 \\sim C26A-C34A
 with sigma of 0.04
 C17-C18 \\sim C17A-C18A
 with sigma of 0.02
 C22-C20 \\sim C22A-C20A
 with sigma of 0.04
 C30-C31 \\sim C30A-C31A
 with sigma of 0.02
 C22-C24 \\sim C22A-C24A
 with sigma of 0.04
 C30-C29 \\sim C30A-C29A
 with sigma of 0.02
 C20-C14 \\sim C20A-C14A
 with sigma of 0.04
 C31-C32 \\sim C31A-C32A
 with sigma of 0.02
 C20-C18 \\sim C20A-C18A
 with sigma of 0.04
 C19-C18 \\sim C19A-C18A
 with sigma of 0.02
 C28-C32 \\sim C28A-C32A
 with sigma of 0.04
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C27-C29 \\sim C27A-C29A
 with sigma of 0.04
 C27-C24 \\sim C27A-C24A
 with sigma of 0.04
 C33-C32 \\sim C33A-C32A
 with sigma of 0.02
 C14-C16 \\sim C14A-C16A
 with sigma of 0.04
 C33-C34 \\sim C33A-C34A
 with sigma of 0.02
 C15-C17 \\sim C15A-C17A
 with sigma of 0.04
 C15-C13 \\sim C15A-C13A
 with sigma of 0.04
 C35-C34 \\sim C35A-C34A
 with sigma of 0.02
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 S25-C26 \\sim S25A-C26A
 with sigma of 0.04
 C17-C19 \\sim C17A-C19A
 with sigma of 0.04
 S25-C22 \\sim S25A-C22A
 with sigma of 0.04
 C31-C29 \\sim C31A-C29A
 with sigma of 0.04
 S25-C14 \\sim S25A-C14A
 with sigma of 0.04
 C16-C18 \\sim C16A-C18A
 with sigma of 0.04
 S25-C23 \\sim S25A-C23A
 with sigma of 0.04
 C23-C35 \\sim C23A-C35A
 with sigma of 0.04
 S36-C26 \\sim S36A-C26A
 with sigma of 0.04
 C33-C35 \\sim C33A-C35A
 with sigma of 0.04
 S36-C22 \\sim S36A-C22A
 with sigma of 0.04
 C24-C13 \\sim C24A-C13A
 with sigma of 0.04
 S36-C24 \\sim S36A-C24A
 with sigma of 0.04
 S36-C34 \\sim S36A-C34A
 with sigma of 0.04
 C26-C28 \\sim C26A-C28A
 with sigma of 0.04
 C44-C46 \\sim C44A-C46A
 with sigma of 0.04
 Cl50-C44 \\sim Cl-C44A
 with sigma of 0.02
 C44-C49 \\sim C44A-C49A
 with sigma of 0.02
 C47-C45 \\sim C47A-C45A
 with sigma of 0.04
 C48-C47 \\sim C48A-C47A
 with sigma of 0.02
 C44-C48 \\sim C44A-C48A
 with sigma of 0.04
 C48-C49 \\sim C48A-C49A
 with sigma of 0.02
 C47-C46 \\sim C47A-C46A
 with sigma of 0.02
 C48-C46 \\sim C48A-C46A
 with sigma of 0.04
 C47-C49 \\sim C47A-C49A
 with sigma of 0.04
 C45-C46 \\sim C45A-C46A
 with sigma of 0.02
 C49-C45 \\sim C49A-C45A
 with sigma of 0.04
 Cl50-C49 \\sim Cl-C49A
 with sigma of 0.04
 Cl50-C45 \\sim Cl-C45A
 with sigma of 0.04
 C44-C45 \\sim C44A-C45A
 with sigma of 0.02
3. Restrained planarity
 C35A, S25A, C24A, C13A, C26A, C23A, C22A, C14A, C27A, S36A, C21A, C15A, C28A,
 C34A, C20A, C16A, C29A, C33A, C19A, C17A, C30A, C32A, C18A, C31A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C23A \\sim C35A \\sim C26A \\sim S36A \\sim C34A \\sim C24A \\sim C27A \\sim
C33A \\sim S25A \\sim C28A \\sim C22A \\sim C32A \\sim C13A \\sim C29A \\sim
C21A \\sim C31A \\sim C14A \\sim C30A \\sim C20A \\sim C15A \\sim C19A \\sim
C16A \\sim C18A \\sim C17A: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
Uanis(C32A) = Uanis(C35A) = Uanis(C26A) = Uanis(C23A) = Uanis(C22A) =
Uanis(C13A) = Uanis(C14A) = Uanis(C21A) = Uanis(C20A) = Uanis(C15A) =
Uanis(C16A) = Uanis(C17A) = Uanis(C18A) = Uanis(C19A) = Uanis(C27A) =
Uanis(C33A) = Uanis(C34A)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C35A)=Sof(S25A)=Sof(C24A)=Sof(C13A)=Sof(C26A)=Sof(C23A)=Sof(C22A)=
 Sof(C14A)=Sof(H14A)=Sof(C27A)=Sof(H27A)=Sof(S36A)=Sof(C21A)=Sof(H21A)=
 Sof(C15A)=Sof(C28A)=Sof(C34A)=Sof(H34A)=Sof(C20A)=Sof(C16A)=Sof(H16A)=
 Sof(C29A)=Sof(H29A)=Sof(C33A)=Sof(C19A)=Sof(H19A)=Sof(C17A)=Sof(H17A)=
 Sof(C30A)=Sof(H30A)=Sof(C32A)=Sof(H32A)=Sof(C18A)=Sof(H18A)=Sof(C31A)=
 Sof(H31A)=1-FVAR(1)
 Sof(S25)=Sof(S36)=Sof(C26)=Sof(C22)=Sof(C20)=Sof(C28)=Sof(C27)=Sof(H27)=
 Sof(C14)=Sof(H14)=Sof(C15)=Sof(C21)=Sof(H21)=Sof(C17)=Sof(H17)=Sof(C30)=
 Sof(H30)=Sof(C31)=Sof(H31)=Sof(C19)=Sof(H19)=Sof(C16)=Sof(H16)=Sof(C29)=
 Sof(H29)=Sof(C18)=Sof(H18)=Sof(C23)=Sof(C33)=Sof(C24)=Sof(C35)=Sof(C13)=
 Sof(C32)=Sof(H32)=Sof(C34)=Sof(H34)=FVAR(1)
 Sof(C44A)=Sof(Cl)=Sof(C49A)=Sof(H49A)=Sof(C45A)=Sof(H45A)=Sof(C48A)=Sof(H48A)=
 Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(H47A)=1-FVAR(2)
 Sof(Cl50)=Sof(C44)=Sof(C48)=Sof(H48)=Sof(C47)=Sof(H47)=Sof(C49)=Sof(H49)=
 Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C27(H27), C10(H10), C14(H14), C21(H21), C3(H3), C17(H17), C7(H7), C8(H8),
 C5(H5), C30(H30), C31(H31), C19(H19), C16(H16), C29(H29), C18(H18), C6(H6),
 C32(H32), C34(H34), C48(H48), C47(H47), C49(H49), C45(H45), C46(H46),
 C14A(H14A), C27A(H27A), C21A(H21A), C34A(H34A), C16A(H16A), C29A(H29A),
 C19A(H19A), C17A(H17A), C30A(H30A), C32A(H32A), C18A(H18A), C31A(H31A),
 C49A(H49A), C45A(H45A), C48A(H48A), C46A(H46A), C47A(H47A)
;
_shelx_res_checksum              98018
_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 2.445
_oxdiff_exptl_absorpt_empirical_full_min 0.406