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_1575420
_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, 0.667(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                103.313(2)
_cell_angle_beta                 105.912(3)
_cell_angle_gamma                102.660(3)
_cell_formula_units_Z            3
_cell_length_a                   10.5925(3)
_cell_length_b                   10.7783(3)
_cell_length_c                   15.8611(5)
_cell_measurement_reflns_used    10734
_cell_measurement_temperature    200
_cell_measurement_theta_max      77.1320
_cell_measurement_theta_min      4.3850
_cell_volume                     1615.72(10)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      200
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.945
_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   -110.00 -36.00   0.50    5.00    --  -47.91 153.00-158.00  148
  2  \w    -89.00 -20.00   0.50    5.00    --  -47.91 120.00  42.00  138
  3  \w   -120.00 -63.00   0.50    5.00    --  -47.91-153.00 160.00  114
  4  \w     15.00  89.00   0.50    5.00    --   47.91-120.00 -40.00  148
  5  \w     30.00 111.00   0.50    5.00    --   47.91-153.00 160.00  162
  6  \w     57.00 120.00   0.50    5.00    --   47.91 153.00-158.00  126
  7  \w   -163.00 -63.00   0.50   11.00    --  -97.00-153.00 160.00  200
  8  \w   -131.00 -36.00   0.50   11.00    --  -97.00 153.00-158.00  190
  9  \w   -166.00 -85.00   0.50   11.00    --  -97.00-120.00 -40.00  162
 10  \w   -109.00 -28.00   0.50   11.00    --  -97.00 120.00  42.00  162
 11  \w     80.00 174.00   0.50   11.00    --  104.77 120.00  42.00  188
 12  \w     33.00 131.00   0.50   11.00    --  104.77-153.00 160.00  196
 13  \w     36.00 110.00   0.50   11.00    --  104.77-120.00 -40.00  148
 14  \w   -120.00 -35.00   0.50    5.00    --  -47.91 -57.00-150.00  170
 15  \w    -28.00  26.00   0.50    5.00    --  -47.91  19.00 150.00  108
 16  \w   -120.00 -35.00   0.50    5.00    --  -47.91 -57.00 150.00  170
 17  \w    -24.00  24.00   0.50    5.00    --   47.91 -19.00 -30.00   96
 18  \w    -24.00  24.00   0.50    5.00    --   47.91 -19.00  60.00   96
 19  \w   -167.00 -91.00   0.50   11.00    --  -97.00 -99.00   0.00  152
 20  \w    -68.00 -25.00   0.50   11.00    --  -97.00  57.00   0.00   86
 21  \w   -169.00 -76.00   0.50   11.00    --  -97.00 -77.00-120.00  186
 22  \w   -109.00 -25.00   0.50   11.00    --  -97.00  77.00 -90.00  168
 23  \w   -167.00 -91.00   0.50   11.00    --  -97.00 -99.00 -90.00  152
 24  \w   -169.00 -76.00   0.50   11.00    --  -97.00 -77.00   0.00  186
 25  \w   -169.00 -84.00   0.50   11.00    --  -97.00 -57.00  30.00  170
 26  \w     36.00  61.00   0.50   11.00    --  104.77-125.00-120.00   50
 27  \w     37.00 105.00   0.50   11.00    --  104.77 -99.00-180.00  136
 28  \w     99.00 139.00   0.50   11.00    --  104.77  37.00 -30.00   80
 29  \w     33.00  63.00   0.50   11.00    --  104.77 -57.00 -90.00   60
 30  \w     35.00  60.00   0.50   11.00    --  104.77 -57.00-180.00   50
 31  \w     33.00  64.00   0.50   11.00    --  104.77 -57.00  90.00   62
 32  \w     33.00  63.00   0.50   11.00    --  104.77 -57.00  30.00   60
 33  \w     33.00  58.00   0.50   11.00    --  104.77 -57.00   0.00   50
 34  \w    109.00 171.00   0.50   11.00    --  104.77  19.00  90.00  124
 35  \w     44.00  94.00   0.50   11.00    --  104.77 -77.00 -30.00  100
 36  \w     33.00  63.00   0.50   11.00    --  104.77 -57.00 150.00   60
 37  \w     36.00 102.00   0.50   11.00    --  104.77 -99.00 120.00  132
 38  \w     34.00  63.00   0.50   11.00    --  104.77 -57.00-150.00   58
 39  \w    146.00 174.00   0.50   11.00    --  104.77  37.00 -30.00   56
 40  \w     38.00  99.00   0.50   11.00    --  104.77 -99.00 -30.00  122
 41  \w    105.00 117.50   0.50   11.00    --  104.77 153.00-158.00   25
;
_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      0.0414228000
_diffrn_orient_matrix_UB_12      0.0554332000
_diffrn_orient_matrix_UB_13      0.1055371000
_diffrn_orient_matrix_UB_21      0.1175847000
_diffrn_orient_matrix_UB_22      0.1150376000
_diffrn_orient_matrix_UB_23      0.0019827000
_diffrn_orient_matrix_UB_31      -0.0980768000
_diffrn_orient_matrix_UB_32      0.0861757000
_diffrn_orient_matrix_UB_33      -0.0117799000
_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  0.0527
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            30073
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.637
_diffrn_reflns_theta_min         3.047
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.904
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51823
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.579
_exptl_crystal_description       plate
_exptl_crystal_F_000             782
_refine_diff_density_max         0.920
_refine_diff_density_min         -0.396
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     714
_refine_ls_number_reflns         6506
_refine_ls_number_restraints     1489
_refine_ls_restrained_S_all      0.951
_refine_ls_R_factor_all          0.0746
_refine_ls_R_factor_gt           0.0606
_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^)+(0.0868P)^2^+1.3265P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1578
_refine_ls_wR_factor_ref         0.1672
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5244
_reflns_number_total             6506
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00680e2.cif
_cod_data_source_block           dntt-pf6-200k
_cod_depositor_comments
'Adding full bibliography for 1575411--1575428.cif.'
_cod_original_cell_volume        1615.72(9)
_cod_database_code               1575420
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H S P F'
_diffrn_oxdiff_digest_hkl
;
01cc0ffe069f3b2014b1cf79e04f56841dd4b0
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 S002-C00S \\sim S0-C1
 with sigma of 0.02
 C00L-C00S \\sim C6-C1
 with sigma of 0.04
 S002-C00Z \\sim S0-C00{
 with sigma of 0.02
 S003-C00H \\sim S1-C3
 with sigma of 0.02
 C00G-C00P \\sim C12-C5
 with sigma of 0.04
 S003-C00X \\sim S1-C7
 with sigma of 0.02
 C00D-C00L \\sim C2-C6
 with sigma of 0.02
 C00D-C00S \\sim C2-C1
 with sigma of 0.02
 C00F-C00S \\sim C4-C1
 with sigma of 0.04
 C00D-C00X \\sim C2-C7
 with sigma of 0.02
 C00I-C014 \\sim C10-C11
 with sigma of 0.04
 C00F-C00H \\sim C4-C3
 with sigma of 0.02
 C00K-C010 \\sim C9-C0
 with sigma of 0.04
 C00F-C00Q \\sim C4-C8
 with sigma of 0.02
 C00F-C00Z \\sim C4-C00{
 with sigma of 0.02
 C00S-C00X \\sim C1-C7
 with sigma of 0.04
 C00G-C00K \\sim C12-C9
 with sigma of 0.02
 C00G-C00Q \\sim C12-C8
 with sigma of 0.02
 C00G-C00Y \\sim C12-C16
 with sigma of 0.02
 C00H-C00S \\sim C3-C1
 with sigma of 0.02
 C00G-C013 \\sim C12-C19
 with sigma of 0.04
 C00H-C00X \\sim C3-C7
 with sigma of 0.04
 C00I-C00L \\sim C10-C6
 with sigma of 0.02
 C00I-C00T \\sim C10-C14
 with sigma of 0.02
 C00I-C011 \\sim C10-C15
 with sigma of 0.02
 C00K-C00Y \\sim C9-C16
 with sigma of 0.04
 C00L-C00X \\sim C6-C7
 with sigma of 0.04
 C00K-C00P \\sim C9-C5
 with sigma of 0.02
 C00K-C00V \\sim C9-C13
 with sigma of 0.02
 C00Q-C00Z \\sim C8-C00{
 with sigma of 0.04
 C00T-C011 \\sim C14-C15
 with sigma of 0.04
 C00P-C00Z \\sim C5-C00{
 with sigma of 0.02
 C00Y-C010 \\sim C16-C0
 with sigma of 0.04
 C012-C016 \\sim C18-C17
 with sigma of 0.04
 C00T-C014 \\sim C14-C11
 with sigma of 0.02
 C00T-C016 \\sim C14-C17
 with sigma of 0.02
 C00V-C010 \\sim C13-C0
 with sigma of 0.02
 C00G-C00V \\sim C12-C13
 with sigma of 0.04
 C00X-C014 \\sim C7-C11
 with sigma of 0.02
 C00H-C00Q \\sim C3-C8
 with sigma of 0.04
 C00Y-C013 \\sim C16-C19
 with sigma of 0.02
 C00H-C00Z \\sim C3-C00{
 with sigma of 0.04
 C00I-C012 \\sim C10-C18
 with sigma of 0.04
 C010-C013 \\sim C0-C19
 with sigma of 0.02
 C00I-C016 \\sim C10-C17
 with sigma of 0.04
 C011-C012 \\sim C15-C18
 with sigma of 0.02
 C00K-C00Q \\sim C9-C8
 with sigma of 0.04
 C012-C017 \\sim C18-C1A
 with sigma of 0.02
 C00K-C00Z \\sim C9-C00{
 with sigma of 0.04
 C016-C017 \\sim C17-C1A
 with sigma of 0.02
 C00L-C00T \\sim C6-C14
 with sigma of 0.04
 S002-C00D \\sim S0-C2
 with sigma of 0.04
 C00L-C011 \\sim C6-C15
 with sigma of 0.04
 S002-C00F \\sim S0-C4
 with sigma of 0.04
 S002-C00H \\sim S0-C3
 with sigma of 0.04
 C00P-C00V \\sim C5-C13
 with sigma of 0.04
 S002-C00P \\sim S0-C5
 with sigma of 0.04
 C00Q-C00Y \\sim C8-C16
 with sigma of 0.04
 C00S-C00Z \\sim C1-C00{
 with sigma of 0.04
 S003-C00D \\sim S1-C2
 with sigma of 0.04
 C00T-C00X \\sim C14-C7
 with sigma of 0.04
 S003-C00F \\sim S1-C4
 with sigma of 0.04
 C00T-C017 \\sim C14-C1A
 with sigma of 0.04
 S003-C00S \\sim S1-C1
 with sigma of 0.04
 S003-C014 \\sim S1-C11
 with sigma of 0.04
 C00V-C013 \\sim C13-C19
 with sigma of 0.04
 C00D-C00H \\sim C2-C3
 with sigma of 0.04
 C00D-C00I \\sim C2-C10
 with sigma of 0.04
 C00D-C014 \\sim C2-C11
 with sigma of 0.04
 C011-C017 \\sim C15-C1A
 with sigma of 0.04
 C014-C016 \\sim C11-C17
 with sigma of 0.04
 C00F-C00G \\sim C4-C12
 with sigma of 0.04
 C00F-C00P \\sim C4-C5
 with sigma of 0.04
 Cl00-C018 \\sim Cl-C1B
 with sigma of 0.02
 C018-C01C \\sim C1B-C1C
 with sigma of 0.02
 C018-C01B \\sim C1B-C20
 with sigma of 0.02
 C01B-C01C \\sim C20-C1C
 with sigma of 0.04
 C01A-C01B \\sim C1D-C20
 with sigma of 0.02
 C01A-C01D \\sim C1D-C1E
 with sigma of 0.02
 C01C-C01D \\sim C1C-C1E
 with sigma of 0.04
 C01A-C01E \\sim C1D-C01F
 with sigma of 0.04
 C01C-C01E \\sim C1C-C01F
 with sigma of 0.02
 C01D-C01E \\sim C1E-C01F
 with sigma of 0.02
 C01B-C01D \\sim C20-C1E
 with sigma of 0.04
 Cl00-C01B \\sim Cl-C20
 with sigma of 0.04
 Cl00-C01C \\sim Cl-C1C
 with sigma of 0.04
 C018-C01A \\sim C1B-C1D
 with sigma of 0.04
 C018-C01E \\sim C1B-C01F
 with sigma of 0.04
3. Restrained planarity
 C15, C0, C13, C19, C9, C16, C12, C5, C8, C00{, C4, S0, C3, C1, S1, C2, C7, C6,
  C11, C10, C14, C17, C18, C1A, C016, S002, C00S, C00Z, C00H, C00D, C00P, C00F,
 S003, C00L, C00X, C00K, C00Q, C00I, C014, C00V, C00G, C00T, C011, C010, C00Y,
 C012, C013, C017
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
S1 \\sim C0 \\sim C13 \\sim C19 \\sim C9 \\sim C16 \\sim C5 \\sim C12 \\sim
C00{ \\sim C8 \\sim C4 \\sim S0 \\sim C3 \\sim C1 \\sim C2 \\sim C7 \\sim C6
\\sim C11 \\sim C10 \\sim C14 \\sim C15 \\sim C17 \\sim C18 \\sim C1A \\sim
S002 \\sim C00S \\sim C00Z \\sim C00H \\sim C00D \\sim C00F \\sim C00P \\sim
S003 \\sim C00L \\sim C00X \\sim C00Q \\sim C00K \\sim C00I \\sim C014 \\sim
C00G \\sim C00V \\sim C00T \\sim C011 \\sim C00Y \\sim C010 \\sim C016 \\sim
C012 \\sim C013 \\sim C017: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
Cl00 \\sim C018 \\sim C01A \\sim C01B \\sim C01C \\sim C01D \\sim C01E \\sim
C20 \\sim Cl \\sim C1B \\sim C1C \\sim C1D \\sim C01F \\sim C1E: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
Uanis(C16) = Uanis(C19) = Uanis(C00Y)
Uanis(C2) = Uanis(C7)
5. Rigid body (RIGU) restrains
 C00P, S002, C00S, C00Z, C00H, C00D, C00F, S003, C00L, C00X, C00Q, C00K, C00I,
 C014, C00G, C00V, C00T, C011, C00Y, C010, C016, C012, C013, C017, C8, C0, C13,
 C19, C9, C16, C5, C12, C00{, C4, S0, C3, C1, S1, C2, C7, C6, C11, C10, C14,
 C15, C17, C18, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl00, C018, C01A, C01B, C01C, C01D, C01E, C20, Cl, C1B, C1C, C1D, C01F, C1E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C0)=Sof(H0)=Sof(S0)=Sof(C1)=Sof(C00{)=Sof(C2)=Sof(C3)=Sof(C4)=Sof(C5)=
 Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(S1)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(C10)=
 Sof(C11)=Sof(H11)=Sof(C12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(C15)=Sof(H15)=
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=
 Sof(C1A)=Sof(H1A)=1-FVAR(1)
 Sof(S002)=Sof(S003)=Sof(C00D)=Sof(C00F)=Sof(C00G)=Sof(C00H)=Sof(C00I)=
 Sof(C00K)=Sof(C00L)=Sof(H00L)=Sof(C00P)=Sof(H00P)=Sof(C00Q)=Sof(H00Q)=
 Sof(C00S)=Sof(C00T)=Sof(C00V)=Sof(H00V)=Sof(C00X)=Sof(C00Y)=Sof(H00Y)=
 Sof(C00Z)=Sof(C010)=Sof(H010)=Sof(C011)=Sof(H011)=Sof(C012)=Sof(H012)=
 Sof(C013)=Sof(H013)=Sof(C014)=Sof(H014)=Sof(C016)=Sof(H016)=Sof(C017)=
 Sof(H017)=FVAR(1)
 Sof(C20)=Sof(H20)=Sof(Cl)=Sof(C1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=
 Sof(C01F)=Sof(H01F)=Sof(C1E)=Sof(H1E)=1-FVAR(2)
 Sof(Cl00)=Sof(C018)=Sof(C01A)=Sof(H01A)=Sof(C01B)=Sof(H01B)=Sof(C01C)=
 Sof(H01C)=Sof(C01D)=Sof(H01D)=Sof(C01E)=Sof(H01E)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00L(H00L), C00P(H00P), C00Q(H00Q), C00R(H00R), C00U(H00U),
 C00V(H00V), C00W(H00W), C00Y(H00Y), C010(H010), C011(H011), C012(H012),
 C013(H013), C014(H014), C015(H015), C016(H016), C017(H017), C019(H019),
 C01A(H01A), C01B(H01B), C01C(H01C), C01D(H01D), C01E(H01E), C0(H0), C5(H5),
 C6(H6), C8(H8), C11(H11), C13(H13), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19), C1A(H1A), C20(H20), C1C(H1C), C1D(H1D), C01F(H01F), C1E(H1E)
;
_shelx_res_checksum              37844
_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 1.876
_oxdiff_exptl_absorpt_empirical_full_min 0.601