(Oligo-)Thiophene Functionalized Tetraazaperopyrenes: Donor-Acceptor Dyes and Ambipolar Organic Semiconductors.
Hahn, Lena; Hermannsdorfer, André; Günther, Benjamin; Wesp, Tobias; Bühler, Bastian; Zschieschang, Ute; Wadepohl, Hubert; Klauk, Hagen; Gade, Lutz H.; The Journal of organic chemistry 82 (2017) 12492–12502; doi:10.1021/acs.joc.7b02286

data_4033167
_publ_section_title
;
 (Oligo-)Thiophene Functionalized Tetraazaperopyrenes: Donor-Acceptor Dyes
 and Ambipolar Organic Semiconductors.
;
_journal_issue                   23
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12492
_journal_page_last               12502
_journal_paper_doi               10.1021/acs.joc.7b02286
_journal_volume                  82
_journal_year                    2017
_chemical_formula_sum            'C44.5 H8.75 Br8 Cl2.25 F14 N4 S4'
_chemical_formula_weight         1712.59
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_cell_setting           triclinic
_symmetry_Int_Tables_number      2
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_ah2
_audit_creation_date             2015-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
'19.10.2015 16:03:15 CEST UTC+02:00  encif 1.36'
_cell_angle_alpha                101.545(2)
_cell_angle_beta                 102.351(3)
_cell_angle_gamma                105.027(3)
_cell_formula_units_Z            4
_cell_length_a                   15.2196(7)
_cell_length_b                   15.3694(5)
_cell_length_c                   24.0731(6)
_cell_measurement_reflns_used    7487
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      64.1450
_cell_measurement_theta_min      3.9100
_cell_volume                     5114.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-15); encifer 1.5 (CCDC, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2013)'
_diffrn_ambient_environment      perfluoro
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.953
_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    -30.00  63.00   1.00    6.00    --    0.00  77.00 150.00   93
  2  \w    -11.00  24.00   1.00    6.00    --    0.00 -38.00-180.00   35
  3  \w    -72.00 -15.00   1.00    6.00    --    0.00 -38.00-180.00   57
  4  \w    -34.00  21.00   1.00    6.00    --    0.00 -57.00  60.00   55
  5  \w    -22.00  70.00   1.00    6.00    --    0.00  38.00 -60.00   92
  6  \w    -32.00   6.00   1.00    6.00    --   10.00 109.00  14.83   38
  7  \w    -37.00 -12.00   1.00    6.00    --   18.00 122.00  -7.20   25
  8  \w     -9.00  16.00   1.00   15.00    --   34.00 102.00-168.20   25
  9  \w      0.00  25.00   1.00   15.00    --   38.00  92.00 -21.37   25
 10  \w      6.00  31.00   1.00   15.00    --   42.00  88.00  87.28   25
 11  \w      5.00  30.00   1.00   15.00    --   42.00  90.00 169.92   25
 12  \w     13.00  38.00   1.00   15.00    --   46.00  83.00 -73.64   25
 13  \w     12.00  37.00   1.00   15.00    --   46.00  84.00-124.41   25
 14  \w     16.00  43.00   1.00   15.00    --   46.00  81.00-165.25   27
 15  \w     12.00  37.00   1.00   15.00    --   46.00  84.00  37.15   25
 16  \w     14.00  39.00   1.00   15.00    --   46.00  81.00 -44.82   25
 17  \w     95.00 120.00   1.00   15.00    --   50.00  75.00  28.00   25
 18  \w     18.00  43.00   1.00   15.00    --   50.00  81.00 148.38   25
 19  \w     20.00  47.00   1.00   15.00    --   50.00  77.00  93.66   27
 20  \w     22.00  49.00   1.00   15.00    --   50.00  75.00  28.00   27
 21  \w     18.00  43.00   1.00   15.00    --   50.00  81.00 -62.29   25
 22  \w     18.00  43.00   1.00   15.00    --   50.00  81.00  98.74   25
 23  \w    -14.00  13.00   1.00   15.00    --   54.00 -57.00  90.00   27
 24  \w     25.00  52.00   1.00   15.00    --   54.00  77.00-180.00   27
 25  \w     24.00  51.00   1.00   15.00    --   54.00  77.00 -60.00   27
 26  \w     25.00  52.00   1.00   15.00    --   54.00  77.00  60.00   27
 27  \w    -15.00  74.00   1.00   15.00    --   54.00 -57.00 -90.00   89
 28  \w    -13.00  75.00   1.00   15.00    --   54.00 -57.00-180.00   88
 29  \w     28.00  55.00   1.00   15.00    --   54.00  77.00-120.00   27
 30  \w     27.00  54.00   1.00   15.00    --   54.00  77.00 -30.00   27
 31  \w     17.00  59.00   1.00   15.00    --   54.00 -57.00  90.00   42
 32  \w     25.00  52.00   1.00   15.00    --   54.00  77.00 -90.00   27
 33  \w     32.00  59.00   1.00   15.00    --   54.00  77.00  30.00   27
 34  \w     25.00  52.00   1.00   15.00    --   54.00  77.00-150.00   27
 35  \w     24.00 106.00   1.00   15.00    --   54.00-125.00 120.00   82
 36  \w     27.00  54.00   1.00   15.00    --   54.00  77.00   0.00   27
 37  \w     30.00  57.00   1.00   15.00    --   58.00  74.00 120.77   27
 38  \w     29.00  56.00   1.00   15.00    --   58.00  75.00 -83.01   27
 39  \w     28.00  55.00   1.00   15.00    --   58.00  77.00  89.89   27
 40  \w    103.00 128.00   1.00   15.00    --   58.00  76.00-135.28   25
 41  \w     29.00  55.00   1.00   15.00    --   58.00  76.00-135.28   26
 42  \w     32.00  59.00   1.00   15.00    --   58.00  74.00 -47.08   27
 43  \w     28.00  55.00   1.00   15.00    --   58.00  77.00 134.82   27
 44  \w     35.00  62.00   1.00   15.00    --   62.00  72.00  66.39   27
 45  \w     38.00  65.00   1.00   15.00    --   62.00  70.00-126.39   27
 46  \w     35.00  62.00   1.00   15.00    --   62.00  74.00   0.86   27
 47  \w     45.00  71.00   1.00   15.00    --   66.00  62.00 128.95   26
 48  \w     36.00  63.00   1.00   15.00    --   66.00  77.00 134.63   27
 49  \w     39.00  70.00   1.00   15.00    --   66.00  73.00 -61.98   31
 50  \w     47.00 125.00   1.00   15.00    --   66.00  58.00 -25.85   78
 51  \w     44.00 101.00   1.00   15.00    --   66.00  51.00  73.72   57
 52  \w     84.00 114.00   1.00   15.00    --   66.00  66.00-171.25   30
 53  \w     43.00  78.00   1.00   15.00    --   66.00  66.00-171.25   35
 54  \w     43.00  76.00   1.00   15.00    --   70.00  73.00 144.32   33
 55  \w     40.00  67.00   1.00   15.00    --   70.00  77.00  -4.72   27
 56  \w     44.00  71.00   1.00   15.00    --   70.00  72.00 -32.10   27
 57  \w     42.00  69.00   1.00   15.00    --   70.00  74.00-118.04   27
 58  \w     42.00  75.00   1.00   15.00    --   70.00  76.00 -98.53   33
 59  \w     47.00 141.00   1.00   15.00    --   74.00  74.00-150.85   94
 60  \w     51.00  78.00   1.00   15.00    --   74.00  67.00  93.36   27
 61  \w     50.00  76.00   1.00   15.00    --   74.00  69.00  13.33   26
 62  \w     55.00  82.00   1.00   15.00    --   78.00  65.00  19.70   27
 63  \w     48.00  76.00   1.00   15.00    --   78.00  77.00 125.62   28
 64  \w     49.00  75.00   1.00   15.00    --   78.00  75.00 -82.54   26
 65  \w     57.00 101.00   1.00   15.00    --   78.00  52.00  96.08   44
 66  \w    100.00 127.00   1.00   15.00    --   78.00  56.00-174.39   27
 67  \w     58.00  96.00   1.00   15.00    --   78.00  56.00-174.39   38
 68  \w     59.00 113.00   1.00   22.00    --   82.00  64.00 -80.74   54
 69  \w     64.00 100.00   1.00   22.00    --   86.00  61.00 -60.89   36
 70  \w     65.00 102.00   1.00   22.00    --   86.00  62.00  86.19   37
 71  \w     56.00  83.00   1.00   22.00    --   86.00  77.00 -68.99   27
 72  \w     69.00  99.00   1.00   22.00    --   90.00  66.00 -82.57   30
 73  \w     68.00  95.00   1.00   22.00    --   90.00  63.00  11.78   27
 74  \w    109.00 155.00   1.00   22.00    --   90.00  63.00 142.33   46
 75  \w     68.00 105.00   1.00   22.00    --   90.00  63.00 142.33   37
 76  \w    132.00 157.00   1.00   22.00    --   90.00  71.00  15.71   25
 77  \w     63.00  92.00   1.00   22.00    --   90.00  71.00  15.71   29
 78  \w     66.00  95.00   1.00   22.00    --   90.00  67.00 -37.85   29
 79  \w     68.00 158.00   1.00   22.00    --   90.00  62.00-126.25   90
 80  \w     67.00 110.00   1.00   22.00    --   94.00  74.00  96.39   43
 81  \w     74.00 106.00   1.00   22.00    --   94.00  53.00 -56.48   32
 82  \w    133.00 163.00   1.00   22.00    --   98.00  71.00 157.34   30
 83  \w     72.00 102.00   1.00   22.00    --   98.00  71.00 157.34   30
 84  \w     41.00  87.00   1.00   22.00    --  108.00 -64.00 -60.00   46
 85  \w     37.00  77.00   1.00   22.00    --  108.00 -92.00  60.00   40
 86  \w     37.00 116.00   1.00   22.00    --  108.00-111.00 -60.00   79
 87  \w     85.00 112.00   1.00   22.00    --  108.00  38.00-150.00   27
 88  \w     87.00 171.00   1.00   22.00    --  108.00  64.00  90.00   84
 89  \w    142.00 177.00   1.00   22.00    --  108.00  51.00 -17.18   35
 90  \w     86.00 114.00   1.00   22.00    --  108.00  64.00-120.00   28
 91  \w     86.00 141.00   1.00   22.00    --  108.00  51.00 -17.18   55
 92  \w    120.00 177.00   1.00   22.00    --  108.00  76.00-123.31   57
 93  \w    127.00 174.00   1.00   22.00    --  108.00 111.00  60.00   47
 94  \w     81.00 106.00   1.00   22.00    --  108.00  76.00-123.31   25
 95  \w     86.00 125.00   1.00   22.00    --  108.00  50.00-106.50   39
 96  \w     86.00 175.00   1.00   22.00    --  108.00  64.00 120.00   89
 97  \w     86.00 175.00   1.00   22.00    --  108.00  64.00   0.00   89
 98  \w     88.00 115.00   1.00   22.00    --  108.00  64.00 -30.00   27
 99  \w     85.00 155.00   1.00   22.00    --  108.00  64.00-150.00   70
100  \w     78.00 105.00   1.00   22.00    --  108.00  77.00-120.00   27
101  \w     86.00 152.00   1.00   22.00    --  108.00  64.00  60.00   66
102  \w     81.00 106.00   1.00   22.00    --  108.00-111.00-120.00   25
103  \w     81.00 109.00   1.00   22.00    --  108.00  77.00  90.00   28
104  \w     78.00 105.00   1.00   22.00    --  108.00  77.00-180.00   27
105  \w     78.00 176.00   1.00   22.00    --  108.00  77.00 -60.00   98
106  \w     79.00 106.00   1.00   22.00    --  108.00  77.00 120.00   27
107  \w     78.00 105.00   1.00   22.00    --  108.00  77.00  30.00   27
108  \w     79.00 106.00   1.00   22.00    --  108.00  77.00 -30.00   27
109  \w     49.00 144.00   1.00   22.00    --  108.00 -92.00   0.00   95
110  \w    112.00 178.00   1.00   22.00    --  108.00  77.00-150.00   66
111  \w     80.00 107.00   1.00   22.00    --  108.00  77.00-150.00   27
112  \w     79.00 107.00   1.00   22.00    --  108.00  77.00 -90.00   28
113  \w    124.00 167.00   1.00   22.00    --  108.00  64.00-180.00   43
114  \w     85.00 112.00   1.00   22.00    --  108.00  64.00-180.00   27
115  \w     78.00 105.00   1.00   22.00    --  108.00  77.00  60.00   27
116  \w     86.00 173.00   1.00   22.00    --  108.00  64.00 -90.00   87
117  \w     89.00  92.00   1.00   22.00    --  108.00  64.00  30.00    3
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0827313000
_diffrn_orient_matrix_UB_12      -0.0210515000
_diffrn_orient_matrix_UB_13      0.0277887000
_diffrn_orient_matrix_UB_21      -0.0602893000
_diffrn_orient_matrix_UB_22      -0.0778721000
_diffrn_orient_matrix_UB_23      -0.0565894000
_diffrn_orient_matrix_UB_31      0.0380264000
_diffrn_orient_matrix_UB_32      -0.0715358000
_diffrn_orient_matrix_UB_33      0.0256345000
_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  0.1438
_diffrn_reflns_av_unetI/netI     0.1211
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            101070
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.224
_diffrn_reflns_theta_min         3.642
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    10.950
_exptl_absorpt_correction_T_max  0.75005
_exptl_absorpt_correction_T_min  0.73592
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    2.224
_exptl_crystal_description       plate
_exptl_crystal_F_000             3248
_exptl_crystal_size_max          0.112
_exptl_crystal_size_mid          0.041
_exptl_crystal_size_min          0.007
_refine_diff_density_max         1.403
_refine_diff_density_min         -1.309
_refine_diff_density_rms         0.172
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1396
_refine_ls_number_reflns         18912
_refine_ls_number_restraints     476
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.1579
_refine_ls_R_factor_gt           0.0783
_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^)+(0.0934P)^2^+15.1697P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1761
_refine_ls_wR_factor_ref         0.2191
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10069
_reflns_number_total             18912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02286_si_002.cif
_cod_data_source_block           ga_ah2
_cod_depositor_comments
'Adding full bibliography for 4033164--4033168.cif.'
_cod_original_cell_volume        5113.9(3)
_cod_original_formula_sum        'C44.50 H8.75 Br8 Cl2.25 F14 N4 S4'
_cod_database_code               4033167
_audit_block_refno               2556
_audit_block_usercomment         'AH-029 orange plate'
_chemical_oxdiff_formula         'C44.5 H8.8 Br8 Cl2.2 F14 N4 S4'
_chemical_oxdiff_usercomment     'AH-029 orange plate'
_shelx_estimated_absorpt_t_max   0.407
_shelx_estimated_absorpt_t_min   0.407
_reflns_odcompleteness_completeness 97.29
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelxl_version_number           2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C102-Cl21 \\sim C102-Cl22
 with sigma of 0.001
 C101-Cl11 \\sim C101-Cl12 \\sim C101-Cl13 \\sim C102-Cl21 \\sim C102-Cl22
 with sigma of 0.02
 Cl11-Cl12 \\sim Cl11-Cl13 \\sim Cl12-Cl13 \\sim Cl21-Cl22
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C23, C24, C25, F1, F2, F3, F4, F5, F6, F7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C27, C28, F8, F9, F10, F11, F12, F13, F14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C73, C74, C75, F51, F52, F53, F54, F55, F56, F57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C76, C77, C78, F58, F59, F60, F61, F62, F63, F64
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C101, C102, Cl11, Cl12, Cl13, Cl21, Cl22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C23, C24, C25, F1, F2, F3, F4, F5, F6, F7} sigma for 1-2: 0.02, 1-3: 0.04
as
{C26, C27, C28, F8, F9, F10, F11, F12, F13, F14}
{C23, C24, C25, F1, F2, F3, F4, F5, F6, F7} sigma for 1-2: 0.02, 1-3: 0.04
as
{C73, C74, C75, F51, F52, F53, F54, F55, F56, F57}
{C23, C24, C25, F1, F2, F3, F4, F5, F6, F7} sigma for 1-2: 0.02, 1-3: 0.04
as
{C76, C77, C78, F58, F59, F60, F61, F62, F63, F64}
5. Others
 Fixed Sof: C78(0.5) Cl21(0.5) C102(0.5) H102(0.5)
6.a Ternary CH refined with riding coordinates:
 C101(H101), C102(H102)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C9(H9), C12(H12), C18(H18), C32(H32), C36(H36), C40(H40), C44(H44),
 C53(H53), C59(H59), C62(H62), C68(H68), C82(H82), C86(H86), C90(H90), C94(H94)
;
_shelx_res_checksum              46648
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.288
_oxdiff_exptl_absorpt_empirical_full_min 0.673
_cell_oxdiff_length_a            15.2196(7)
_cell_oxdiff_length_b            15.3694(5)
_cell_oxdiff_length_c            24.0731(6)
_cell_oxdiff_angle_alpha         101.545(2)
_cell_oxdiff_angle_beta          102.351(3)
_cell_oxdiff_angle_gamma         105.027(3)
_cell_oxdiff_volume              5113.9(3)
_cell_oxdiff_measurement_reflns_used 7487