Synthesis of 2,7-dioctylbiphenylenodithiophenes for use as organic semiconducting materials in solution-processed organic thin-film transistors
Watanabe, Makoto; Miyashita, Masato; Fukuda, Takashi; Oku, Shinya; CrystEngComm  (2026) –; doi:10.1039/D5CE01050K

data_7251779
_publ_section_title
;
 Synthesis of 2,7-dioctylbiphenylenodithiophenes for use as organic
 semiconducting materials in solution-processed organic thin-film
 transistors
;
_journal_issue                   14
_journal_name_full               CrystEngComm
_journal_page_first              2234
_journal_page_last               2242
_journal_paper_doi               10.1039/D5CE01050K
_journal_volume                  28
_journal_year                    2026
_chemical_formula_moiety         'C32 H40 S2'
_chemical_formula_sum            'C32 H40 S2'
_chemical_formula_weight         488.76
_chemical_melting_point          413
_chemical_name_systematic        2,7-dioctylbiphenyleno[2,3-b:6,7-b']dithiophene
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-12
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-07-31 deposited with the CCDC.	2026-03-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.015(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9056(4)
_cell_length_b                   4.7333(2)
_cell_length_c                   52.478(2)
_cell_measurement_reflns_used    4638
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.2560
_cell_measurement_theta_min      3.3580
_cell_volume                     2705.14(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.70a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.991
_diffrn_measured_fraction_theta_max 0.991
_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    -88.00 -52.00   0.50    0.11    --   25.07 178.00  90.00   72
  2  \w    -56.00 -30.00   0.50    0.11    --   25.07 150.00  21.00   52
  3  \w     78.00 161.00   0.50    0.44    --  116.06 150.00  21.00  166
  4  \w     71.00 108.00   0.50    0.11    --   25.07 178.00 120.00   74
  5  \w     91.00 151.00   0.50    0.44    --   70.56 150.00  21.00  120
  6  \w    111.00 145.00   0.50    0.44    --   70.56 111.00 -60.00   68
  7  \w    137.00 162.00   0.50    0.44    --  116.06 138.00-150.00   50
  8  \w     93.00 172.00   0.50    0.44    --  116.06 138.00-180.00  158
  9  \w    102.00 127.00   0.50    0.44    --  116.06 138.00-150.00   50
 10  \w    137.00 162.00   0.50    0.44    --  116.06 122.00-139.00   50
 11  \w    103.00 150.00   0.50    0.44    --   70.56 111.00-180.00   94
 12  \w    106.00 165.00   0.50    0.44    --  116.06 104.00 -90.00  118
 13  \w    109.00 157.00   0.50    0.44    --  116.06 104.00  60.00   96
 14  \w     65.00 112.00   0.50    0.44    --   70.56  77.00  90.00   94
 15  \w     26.00  56.00   0.50    0.44    --   70.56  77.00  90.00   60
 16  \w     25.00  68.00   0.50    0.44    --   70.56  77.00  60.00   86
 17  \w    120.00 151.00   0.50    0.44    --   70.56  77.00  90.00   62
 18  \w    102.00 128.00   0.50    0.44    --  116.06  77.00 150.00   52
 19  \w     95.00 120.00   0.50    0.44    --  116.06  77.00 120.00   50
 20  \w     59.00  90.00   0.50    0.44    --  116.06  77.00 150.00   62
 21  \w     69.00  94.00   0.50    0.44    --  116.06  77.00 120.00   50
 22  \w     60.00  93.00   0.50    0.44    --  116.06  77.00  60.00   66
 23  \w    101.00 137.00   0.50    0.44    --  116.06  77.00  60.00   72
 24  \w    153.00 178.00   0.50    0.44    --  116.06  77.00 120.00   50
 25  \w     17.00 116.00   0.50    0.44    --   70.56  63.00 150.00  198
 26  \w     63.00  89.00   0.50    0.44    --  116.06  77.00  30.00   52
 27  \w    120.00 152.00   0.50    0.44    --   70.56  63.00 150.00   64
 28  \w     60.00 178.00   0.50    0.44    --  116.06  54.00 120.00  236
 29  \w     92.00 167.00   0.50    0.44    --  116.06  77.00  30.00  150
 30  \w    143.00 175.00   0.50    0.44    --  116.06  54.00-150.00   64
 31  \w     87.00 113.00   0.50    0.44    --  116.06  54.00-150.00   52
 32  \w     66.00 139.00   0.50    0.44    --  116.06  54.00-180.00  146
 33  \w    153.00 178.00   0.50    0.44    --  116.06  54.00-180.00   50
 34  \w     69.00 114.00   0.50    0.44    --   70.56  63.00-180.00   90
 35  \w     37.00  63.00   0.50    0.44    --   70.56  63.00-180.00   52
 36  \w    117.00 157.00   0.50    0.44    --  116.06   0.00  60.00   80
 37  \w    111.00 138.00   0.50    0.44    --  116.06   0.00  30.00   54
 38  \w    107.00 177.00   0.50    0.44    --  116.06   0.00 150.00  140
 39  \w    121.00 151.00   0.50    0.44    --   70.56   0.00  60.00   60
 40  \w     32.00 108.00   0.50    0.11    --   25.07  19.00 150.00  152
 41  \w    -12.00  14.00   0.50    0.11    --   25.07  19.00 150.00   52
 42  \w     47.00  81.00   0.50    0.44    --  116.06 -65.00 120.00   68
 43  \w     14.00  45.00   0.50    0.44    --  116.06 -43.00 150.00   62
 44  \w     14.00  39.00   0.50    0.44    --  116.06 -43.00 120.00   50
 45  \w    -31.00  19.00   0.50    0.44    --   70.56 -37.00 120.00  100
 46  \w     10.00  49.00   0.50    0.44    --  116.06 -54.00 -30.00   78
 47  \w      5.00  30.00   0.50    0.44    --  116.06 -65.00 -60.00   50
 48  \w     15.00  47.00   0.50    0.44    --  116.06 -43.00-180.00   64
 49  \w    -29.00  12.00   0.50    0.44    --   70.56 -12.00-180.00   82
 50  \w    -34.00  24.00   0.50    0.44    --   70.56 -25.00 -90.00  116
 51  \w     37.00  74.00   0.50    0.44    --  116.06-104.00 -30.00   74
 52  \w     75.00 100.00   0.50    0.44    --  116.06-150.00 -22.00   50
 53  \w     77.00 106.00   0.50    0.44    --   70.56-122.00 138.00   58
 54  \w     41.00  69.00   0.50    0.44    --   70.56-122.00 138.00   56
 55  \w     47.00  72.00   0.50    0.44    --  116.06-122.00 138.00   50
 56  \w     79.00 105.00   0.50    0.44    --  116.06-104.00 -30.00   52
 57  \w     78.00 103.00   0.50    0.11    --   25.07-150.00 -22.00   50
 58  \w    -90.00 -65.00   0.50    0.11    --   25.07-178.00-180.00   50
 59  \w   -139.00 -79.00   0.50    0.11    --  -25.07   0.00   0.00  120
 60  \w    -79.00 -54.00   0.50    0.44    -- -106.00 122.00-139.00   50
 61  \w    -48.00 -23.00   0.50    0.44    --  -70.56 122.00-139.00   50
 62  \w    -89.00 -64.00   0.50    0.11    --  -25.07 150.00  21.00   50
 63  \w    -81.00 -45.00   0.50    0.44    -- -106.00 104.00  30.00   72
 64  \w    -17.00  30.00   0.50    0.11    --  -25.07  19.00 -30.00   94
 65  \w    -16.00  51.00   0.50    0.11    --  -25.07  19.00 -90.00  134
 66  \w    -25.00   7.00   0.50    0.44    --  -70.56  25.00-180.00   64
 67  \w    -59.00 -23.00   0.50    0.44    -- -106.00  54.00 -90.00   72
 68  \w    -25.00  12.00   0.50    0.44    --  -70.56  25.00 -60.00   74
 69  \w    -25.00   0.00   0.50    0.44    --  -70.56  25.00  30.00   50
 70  \w   -115.00 -57.00   0.50    0.44    -- -106.00 -65.00  30.00  116
 71  \w   -153.00-128.00   0.50    0.44    --  -70.56 -77.00  90.00   50
 72  \w   -113.00 -87.00   0.50    0.44    -- -106.00 -77.00 120.00   52
 73  \w    -75.00 -50.00   0.50    0.44    -- -106.00 -77.00  90.00   50
 74  \w    -53.00 -27.00   0.50    0.44    --  -70.56 -77.00  90.00   52
 75  \w    -76.00 -50.00   0.50    0.44    -- -106.00 -77.00 120.00   52
 76  \w    -75.00 -50.00   0.50    0.44    -- -106.00 -77.00  60.00   50
 77  \w    -98.00 -52.00   0.50    0.44    -- -106.00 -77.00 150.00   92
 78  \w   -129.00 -83.00   0.50    0.44    -- -106.00 -77.00  90.00   92
 79  \w   -166.00-134.00   0.50    0.44    -- -106.00 -77.00  90.00   64
 80  \w   -103.00 -54.00   0.50    0.44    -- -106.00 -74.00  75.24   98
 81  \w    -88.00 -51.00   0.50    0.44    -- -106.00 -74.00  97.55   74
 82  \w   -176.00-142.00   0.50    0.44    -- -106.00 -77.00-180.00   68
 83  \w   -136.00-110.00   0.50    0.44    -- -106.00 -77.00-180.00   52
 84  \w    -99.00 -73.00   0.50    0.11    --  -25.07-150.00 -22.00   52
 85  \w    -92.00 -58.00   0.50    0.44    --  -70.56-150.00 -22.00   68
 86  \w   -144.00 -97.00   0.50    0.44    -- -106.00-150.00 -22.00   94
 87  \w   -124.00 -99.00   0.50    0.11    --  -25.07-122.00 138.00   50
 88  \w   -123.00 -98.00   0.50    0.44    --  -70.56-122.00 138.00   50
 89  \w   -147.00-122.00   0.50    0.44    -- -106.00-122.00 138.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0137669000
_diffrn_orient_matrix_UB_12      -0.0259934000
_diffrn_orient_matrix_UB_13      -0.0292757000
_diffrn_orient_matrix_UB_21      -0.1306919000
_diffrn_orient_matrix_UB_22      0.1226013000
_diffrn_orient_matrix_UB_23      0.0003234000
_diffrn_orient_matrix_UB_31      0.0521935000
_diffrn_orient_matrix_UB_32      0.3005053000
_diffrn_orient_matrix_UB_33      -0.0026850000
_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  0.0887
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       62
_diffrn_reflns_limit_l_min       -61
_diffrn_reflns_number            9144
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.484
_diffrn_reflns_theta_max         67.484
_diffrn_reflns_theta_min         3.373
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.899
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59125
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.70a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_description       plate
_exptl_crystal_F_000             1056
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.459
_refine_diff_density_min         -0.567
_refine_diff_density_rms         0.093
_refine_ls_extinction_coef       0.0006(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     156
_refine_ls_number_reflns         2423
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0594
_refine_ls_R_factor_gt           0.0572
_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^)+(0.1158P)^2^+0.8627P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1540
_refine_ls_wR_factor_ref         0.1581
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2245
_reflns_number_total             2423
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce01050k2.cif
_cod_data_source_block           mw1557_3
_cod_depositor_comments
'Adding full bibliography for 7251778--7251779.cif.'
_cod_original_cell_volume        2705.13(18)
_cod_database_code               7251779
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C32 S2'
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.600
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C13(H13A,H13B), C11(H11A,H11B), C14(H14A,H14B), C10(H10A,H10B),
 C12(H12A,H12B), C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_diffrn_reflns_filtered   314
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.874
_oxdiff_exptl_absorpt_empirical_full_min 0.434