Enantiopure 2-(2-ethylhexyl)dinaphtho[2,3-<i>b</i>:2',3'-<i>f</i>]thieno[3,2-<i>b</i>]thiophenes: synthesis, single-crystal structure and a surprising lack of influence of stereoisomerism on thin-film structure and electronic properties.
Sumitomo, Kenta; Sudo, Yuta; Kanazawa, Kiseki; Kawabata, Kohsuke; Takimiya, Kazuo; Materials horizons 9 (2022) 444–451; doi:10.1039/d1mh01119g

data_1565122
_publ_section_title
;
 Enantiopure
 2-(2-ethylhexyl)dinaphtho[2,3-<i>b</i>:2',3'-<i>f</i>]thieno[3,2-<i>b</i>]thiophenes:
 synthesis, single-crystal structure and a surprising lack of influence of
 stereoisomerism on thin-film structure and electronic properties.
;
_journal_issue                   1
_journal_name_full               'Materials horizons'
_journal_page_first              444
_journal_page_last               451
_journal_paper_doi               10.1039/d1mh01119g
_journal_volume                  9
_journal_year                    2022
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C30 H28 S2'
_chemical_formula_sum            'C30 H28 S2'
_chemical_formula_weight         452.64
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2021-01-30
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2021-06-25 deposited with the CCDC.	2021-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                98.319(2)
_cell_angle_beta                 94.455(2)
_cell_angle_gamma                92.830(2)
_cell_formula_units_Z            2
_cell_length_a                   6.0023(2)
_cell_length_b                   8.1084(2)
_cell_length_c                   24.3715(5)
_cell_measurement_reflns_used    12398
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.0910
_cell_measurement_theta_min      3.7130
_cell_volume                     1167.90(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.72a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.72a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.72a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.944
_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    112.00 175.00   0.50    0.49    --  106.76  45.00 -30.00  126
  2  \w    135.00 173.00   0.50    0.49    --  106.76  30.00   0.00   76
  3  \w     83.00 126.00   0.50    0.49    --  106.76  30.00   0.00   86
  4  \w    -33.00  -7.00   0.50    0.12    --   42.43 -19.00-180.00   52
  5  \w    -37.00  13.00   0.50    0.12    --   42.43 -19.00  30.00  100
  6  \w    -31.00   9.00   0.50    0.12    --   42.43 -19.00  60.00   80
  7  \w    -32.00  13.00   0.50    0.12    --   42.43 -19.00  90.00   90
  8  \w    -33.00   9.00   0.50    0.12    --   42.43 -37.00 150.00   84
  9  \w     64.00 107.00   0.50    0.49    --  106.76-106.00  23.76   86
 10  \w     74.00 112.00   0.50    0.49    --  106.76-125.00 -30.00   76
 11  \w     75.00 110.00   0.50    0.49    --  106.76-121.00 -18.00   70
 12  \w     43.00  69.00   0.50    0.49    --  106.76-125.00 -30.00   52
 13  \w     81.00 110.00   0.50    0.49    --  106.76-151.00-179.00   58
 14  \w     67.00 102.00   0.50    0.12    --   42.43-151.00-179.00   70
 15  \w     35.00  92.00   0.50    0.12    --   42.43-121.00 -18.00  114
 16  \w     33.00  67.00   0.50    0.49    --  106.76 -61.00  30.00   68
 17  \w     44.00 111.00   0.50    0.49    --  106.76 -77.00 150.00  134
 18  \w     79.00 116.00   0.50    0.49    --  106.76 121.00  63.00   74
 19  \w     88.00 113.00   0.50    0.49    --  106.76 151.00-135.00   50
 20  \w     78.00 103.00   0.50    0.12    --   42.43 151.00-135.00   50
 21  \w    -97.00 -72.00   0.50    0.12    --  -42.43 151.00-135.00   50
 22  \w    -84.00 -37.00   0.50    0.49    -- -100.00 151.00-135.00   94
 23  \w    -56.00 -27.00   0.50    0.49    -- -100.00 125.00  30.00   58
 24  \w   -101.00 -60.00   0.50    0.49    -- -100.00 121.00  63.00   82
 25  \w   -112.00 -52.00   0.50    0.49    -- -100.00 125.00 150.00  120
 26  \w    -82.00 -57.00   0.50    0.12    --  -42.43 121.00  63.00   50
 27  \w    -75.00 -42.00   0.50    0.49    -- -100.00  61.00  30.00   66
 28  \w    -52.00 -25.00   0.50    0.49    -- -100.00  45.00 120.00   54
 29  \w    -52.00 -25.00   0.50    0.49    -- -100.00  45.00 150.00   54
 30  \w    -52.00 -24.00   0.50    0.49    -- -100.00  45.00  60.00   56
 31  \w    -52.00 -27.00   0.50    0.49    -- -100.00  45.00   0.00   50
 32  \w    -49.00 -24.00   0.50    0.49    -- -100.00  45.00  30.00   50
 33  \w    -51.00 -26.00   0.50    0.49    -- -100.00  45.00 -60.00   50
 34  \w    -49.00 -24.00   0.50    0.49    -- -100.00  45.00-120.00   50
 35  \w    -73.00 -36.00   0.50    0.49    -- -100.00  61.00-180.00   74
 36  \w    -50.00 -25.00   0.50    0.49    -- -100.00  45.00-180.00   50
 37  \w    -49.00 -24.00   0.50    0.49    -- -100.00  45.00-150.00   50
 38  \w    -16.00  30.00   0.50    0.12    --  -42.43  19.00-120.00   92
 39  \w    -50.00 -25.00   0.50    0.49    -- -100.00  45.00  90.00   50
 40  \w   -176.00 -93.00   0.50    0.49    -- -100.00 -45.00-120.00  166
 41  \w   -114.00 -73.00   0.50    0.12    --  -42.43-151.00-179.00   82
 42  \w   -112.00 -86.00   0.50    0.49    -- -100.00-121.00 -18.00   52
 43  \w   -165.00 -96.00   0.50    0.49    -- -100.00-125.00 120.00  138
 44  \w   -114.00 -89.00   0.50    0.12    --  -42.30-151.00-179.00   50
 45  \w      6.00  33.00   0.50    0.12    --   40.00  92.00 -54.66   54
 46  \w    -43.00 -13.00   0.50    0.12    --  -42.30 -77.00   0.00   60
 47  \w    -69.00 -22.00   0.50    0.12    --  -42.30 -37.00 -30.00   94
 48  \w    -52.00 -19.00   0.50    0.12    --  -42.30 -57.00 120.00   66
 49  \w    -48.00 -13.00   0.50    0.12    --  -42.30 -77.00 -90.00   70
 50  \w   -112.00 -54.00   0.50    0.12    --  -42.30 -57.00 120.00  116
 51  \w    -81.00 -19.00   0.50    0.12    --  -42.30 -57.00-180.00  124
 52  \w     17.00  42.00   0.50    0.12    --   42.30  77.00  60.00   50
 53  \w      9.00  34.00   0.50    0.12    --   44.00  90.00-169.52   50
 54  \w     10.00  35.00   0.50    0.12    --   44.00  88.00 130.25   50
 55  \w     24.00  73.00   0.50    0.12    --   48.00  77.00 164.69   98
 56  \w     97.00 122.00   0.50    0.12    --   48.00  77.00 164.69   50
 57  \w     29.00  55.00   0.50    0.12    --   52.00  78.00-165.73   52
 58  \w     31.00  56.00   0.50    0.12    --   60.00  79.00  -7.17   50
 59  \w    -70.00 -39.00   0.50    0.12    --  -64.00 -69.00 103.88   62
 60  \w    -58.00 -33.00   0.50    0.12    --  -64.00 -81.00 -28.14   50
 61  \w    -94.00 -39.00   0.50    0.12    --  -64.00 -67.00  67.02  110
 62  \w     36.00  62.00   0.50    0.12    --   64.00  78.00  65.84   52
 63  \w     40.00  66.00   0.50    0.12    --   64.00  75.00  41.69   52
 64  \w    -68.00 -43.00   0.50    0.12    --  -68.00 -66.00 153.68   50
 65  \w    -65.00 -39.00   0.50    0.12    --  -68.00 -81.00-135.53   52
 66  \w    -66.00 -41.00   0.50    0.12    --  -68.00 -72.00 -71.78   50
 67  \w    -67.00 -41.00   0.50    0.12    --  -68.00 -74.00-115.19   52
 68  \w    -68.00 -42.00   0.50    0.12    --  -68.00 -74.00-121.74   52
 69  \w   -121.00 -96.00   0.50    0.12    --  -68.00 -72.00 -71.78   50
 70  \w   -139.00-113.00   0.50    0.12    --  -68.00 -66.00 153.68   52
 71  \w    -71.00 -45.00   0.50    0.49    --  -72.00 -71.00 -20.40   52
 72  \w    -70.00 -45.00   0.50    0.49    --  -72.00 -73.00-127.56   50
 73  \w    -68.00 -42.00   0.50    0.49    --  -72.00 -80.00 164.27   52
 74  \w    -72.00 -47.00   0.50    0.49    --  -72.00 -68.00-102.57   50
 75  \w    -80.00 -54.00   0.50    0.49    --  -76.00 -63.00 101.26   52
 76  \w    -77.00 -51.00   0.50    0.49    --  -76.00 -66.00 -86.50   52
 77  \w    -77.00 -51.00   0.50    0.49    --  -76.00 -68.00-112.65   52
 78  \w    -80.00 -53.00   0.50    0.49    --  -76.00 -61.00  60.13   54
 79  \w    -78.00 -52.00   0.50    0.49    --  -80.00 -77.00-146.19   52
 80  \w    -74.00 -49.00   0.50    0.49    --  -80.00 -81.00 -16.59   50
 81  \w    -90.00 -64.00   0.50    0.49    --  -80.00 -59.00  61.73   52
 82  \w   -129.00-103.00   0.50    0.49    --  -80.00 -81.00 -16.59   52
 83  \w    -83.00 -57.00   0.50    0.49    --  -80.00 -63.00 112.03   52
 84  \w    -76.00 -51.00   0.50    0.49    --  -80.00 -77.00 162.17   50
 85  \w    -79.00 -53.00   0.50    0.49    --  -80.00 -73.00  29.09   52
 86  \w    -83.00 -57.00   0.50    0.49    --  -80.00 -67.00-116.39   52
 87  \w    -93.00 -57.00   0.50    0.49    --  -80.00 -57.00  38.10   72
 88  \w    -82.00 -57.00   0.50    0.49    --  -84.00 -71.00  12.33   50
 89  \w    -83.00 -57.00   0.50    0.49    --  -84.00 -71.00-115.23   52
 90  \w    -87.00 -61.00   0.50    0.49    --  -84.00 -64.00 -10.56   52
 91  \w    -90.00 -65.00   0.50    0.49    --  -88.00 -60.00  83.61   50
 92  \w    -91.00 -65.00   0.50    0.49    --  -88.00 -62.00 -95.56   52
 93  \w    -92.00 -66.00   0.50    0.49    --  -88.00 -62.00 125.61   52
 94  \w    -87.00 -61.00   0.50    0.49    --  -88.00 -72.00-118.52   52
 95  \w    -90.00 -63.00   0.50    0.49    --  -88.00 -67.00 104.61   54
 96  \w    -99.00 -65.00   0.50    0.49    --  -88.00 -63.00-103.58   68
 97  \w   -102.00 -64.00   0.50    0.49    --  -88.00 -61.00 -78.93   76
 98  \w   -122.00 -65.00   0.50    0.49    --  -92.00 -73.00-123.76  114
 99  \w   -145.00 -71.00   0.50    0.49    -- -100.00 -81.00  72.20  148
100  \w   -169.00-143.00   0.50    0.49    -- -100.00 -77.00   0.00   52
101  \w   -108.00 -71.00   0.50    0.49    -- -100.00 -77.00-150.00   74
102  \w   -105.00 -78.00   0.50    0.49    -- -100.00 -59.00 -48.06   54
103  \w   -146.00 -74.00   0.50    0.49    -- -100.00 -70.00 133.25  144
104  \w   -106.00 -76.00   0.50    0.49    -- -100.00 -61.00  -8.24   60
105  \w    -50.00 -25.00   0.50    0.49    -- -100.00  45.00 -90.00   50
106  \w   -131.00 -74.00   0.50    0.49    -- -100.00 -77.00-180.00  114
107  \w   -147.00 -71.00   0.50    0.49    -- -100.00 -77.00  90.00  152
108  \w   -100.00 -74.00   0.50    0.49    -- -100.00 -71.00  27.06   52
109  \w   -100.00 -75.00   0.50    0.49    -- -100.00 -77.00 120.00   50
110  \w   -152.00-126.00   0.50    0.49    -- -100.00 -77.00 120.00   52
111  \w   -104.00 -73.00   0.50    0.49    -- -100.00 -71.00 -93.28   62
112  \w    -96.00 -71.00   0.50    0.49    -- -100.00 -77.00 -30.00   50
113  \w   -126.00 -75.00   0.50    0.49    -- -100.00 -69.00-178.45  102
114  \w   -147.00-121.00   0.50    0.49    -- -100.00 -71.00 -93.28   52
115  \w   -152.00-126.00   0.50    0.49    -- -100.00 -77.00 -30.00   52
116  \w   -159.00-132.00   0.50    0.49    -- -100.00 -69.00-178.45   54
117  \w    -98.00 -73.00   0.50    0.49    -- -100.00 -75.00  42.10   50
118  \w   -105.00 -73.00   0.50    0.49    -- -100.00 -72.00-134.59   64
119  \w   -100.00 -75.00   0.50    0.49    -- -100.00 -69.00  15.11   50
120  \w   -162.00-117.00   0.50    0.49    -- -100.00 -72.00-134.59   90
121  \w   -111.00 -77.00   0.50    0.49    -- -100.00 -64.00 143.82   68
122  \w    -98.00 -73.00   0.50    0.49    -- -100.00 -77.00   0.00   50
123  \w    139.00 174.00   0.50    0.49    --  106.76  77.00  90.00   70
124  \w     78.00 111.00   0.50    0.49    --  106.76  77.00  90.00   66
;
_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      -0.0220350000
_diffrn_orient_matrix_UB_12      -0.0413974000
_diffrn_orient_matrix_UB_13      0.0591469000
_diffrn_orient_matrix_UB_21      0.0434865000
_diffrn_orient_matrix_UB_22      0.1863894000
_diffrn_orient_matrix_UB_23      0.0238488000
_diffrn_orient_matrix_UB_31      -0.2532781000
_diffrn_orient_matrix_UB_32      0.0235662000
_diffrn_orient_matrix_UB_33      -0.0066558000
_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  0.1115
_diffrn_reflns_av_unetI/netI     0.0841
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            29803
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.889
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.209
_diffrn_reflns_theta_min         1.839
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.167
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49293
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.72a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       plate
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.446
_refine_diff_density_min         -0.617
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Flack x determined using 2888 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     581
_refine_ls_number_reflns         8577
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0722
_refine_ls_R_factor_gt           0.0598
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1172P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1628
_refine_ls_wR_factor_ref         0.1748
_reflns_Friedel_coverage         0.883
_reflns_Friedel_fraction_full    0.924
_reflns_Friedel_fraction_max     0.834
_reflns_number_gt                7330
_reflns_number_total             8577
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1mh01119g2.cif
_cod_data_source_block           s-eh-dntt
_cod_depositor_comments
;
Adding full bibliography for 1565122--1565123.cif.

2022-05-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C60 H56 S4'
_cod_original_formula_weight         905.28
_cod_original_formula_moiety         '2(C30 H28 S2)'
_cod_original_formula_units_Z            1
_cod_database_code               1565122
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H S'
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.563
_diffrn_oxdiff_digest_frames
;
012145e888a15575069c05e815fb166abd0323460ad
;
_diffrn_oxdiff_digest_hkl
;
01dec0e362f8494c4b4ee0a7a979d29d1f49ee
;
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C26(H26), C58(H58)
2.b Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C25(H25A,H25B), C27(H27A,H27B), C28(H28A,H28B), C59(H59A,
 H59B), C31(H31A,H31B), C60(H60A,H60B), C63(H63A,H63B), C61(H61A,H61B),
 C29(H29A,H29B)
2.c Aromatic/amide H refined with riding coordinates:
 C44(H44), C15(H15), C42(H42), C17(H17), C22(H22), C6(H6), C49(H49), C37(H37),
 C4(H4), C47(H47), C50(H50), C7(H7), C9(H9), C39(H39), C40(H40), C18(H18),
 C52(H52), C19(H19), C11(H11), C51(H51), C54(H54), C20(H20)
2.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C62(H62A,H62B,H62C), C30(H30A,H30B,H30C), C64(H64A,H64B,
 H64C)
;
_shelx_res_checksum              13945
_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 5.032
_oxdiff_exptl_absorpt_empirical_full_min 0.370