Zipping up Tetraazaperylene: Synthesis of Tetraazacoronenes via Double Coupling in the Bay Positions
Eichelmann, Robert; Rippel, Daniel; Ballmann, Joachim; Gade, Lutz H.; Chemical Communications  (2023) –; doi:10.1039/D3CC04113A

data_7132140
_publ_section_title
;
 Zipping up Tetraazaperylene: Synthesis of Tetraazacoronenes via Double
 Coupling in the Bay Positions
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC04113A
_journal_year                    2023
_chemical_formula_moiety         'C70 H72 N8 O2'
_chemical_formula_sum            'C70 H72 N8 O2'
_chemical_formula_weight         1057.35
_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             2023-08-15
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-23 deposited with the CCDC.	2023-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                72.501(2)
_cell_angle_beta                 78.358(2)
_cell_angle_gamma                71.564(2)
_cell_formula_units_Z            4
_cell_length_a                   15.5792(4)
_cell_length_b                   18.9640(5)
_cell_length_c                   21.4149(5)
_cell_measurement_reflns_used    17074
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      67.9110
_cell_measurement_theta_min      3.4120
_cell_volume                     5684.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_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 0.982
_diffrn_measured_fraction_theta_max 0.982
_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    -26.00  67.00   1.00    1.00    --    0.00  38.00   0.00   93
  2  \w    -15.00  69.00   1.00    1.00    --    0.00  57.00-150.00   84
  3  \w    -22.00  71.00   1.00    1.00    --    0.00  38.00 120.00   93
  4  \w    -32.00  13.00   1.00    1.00    --   16.00 107.00  97.03   45
  5  \w    -30.00  -2.00   1.00    1.00    --   20.00 125.00  43.58   28
  6  \w    -17.00   8.00   1.00    4.00    --   32.00 109.00 -17.65   25
  7  \w     -2.00  24.00   1.00    4.00    --   40.00  96.00-144.54   26
  8  \w      5.00  30.00   1.00    4.00    --   44.00  90.00  18.99   25
  9  \w      7.00  32.00   1.00    4.00    --   44.00  87.00 124.65   25
 10  \w     14.00  39.00   1.00    4.00    --   48.00  81.00-127.60   25
 11  \w     14.00  39.00   1.00    4.00    --   48.00  82.00 -19.39   25
 12  \w     13.00  38.00   1.00    4.00    --   48.00  83.00 -69.62   25
 13  \w     19.00  44.00   1.00    4.00    --   52.00  80.00  83.13   25
 14  \w     18.00  43.00   1.00    4.00    --   52.00  81.00 109.13   25
 15  \w     18.00  43.00   1.00    4.00    --   52.00  82.00-101.53   25
 16  \w     18.00  43.00   1.00    4.00    --   52.00  81.00 172.46   25
 17  \w     19.00  44.00   1.00    4.00    --   52.00  80.00 -10.13   25
 18  \w     18.00  43.00   1.00    4.00    --   52.00  81.00  32.11   25
 19  \w     18.00  43.00   1.00    4.00    --   52.00  82.00 137.04   25
 20  \w    -17.00  86.00   1.00    4.00    --   54.00 -77.00   0.00  103
 21  \w     23.00  78.00   1.00    4.00    --   54.00-125.00-150.00   55
 22  \w      2.00  98.00   1.00    4.00    --   54.00 -99.00-120.00   96
 23  \w     25.00  76.00   1.00    4.00    --   56.00  75.00-136.62   51
 24  \w     28.00  82.00   1.00    4.00    --   60.00  77.00 170.41   54
 25  \w     32.00  80.00   1.00    4.00    --   64.00  77.00 -67.11   48
 26  \w     86.00 116.00   1.00    4.00    --   64.00  77.00 -67.11   30
 27  \w     32.00 134.00   1.00    4.00    --   64.00  77.00 -43.88  102
 28  \w     36.00 106.00   1.00    4.00    --   64.00  73.00  75.35   70
 29  \w     36.00  70.00   1.00    4.00    --   68.00  77.00 -94.98   34
 30  \w     40.00  71.00   1.00    4.00    --   68.00  70.00 135.01   31
 31  \w     36.00  64.00   1.00    4.00    --   68.00  77.00-157.91   28
 32  \w     37.00  64.00   1.00    4.00    --   68.00  75.00 -11.66   27
 33  \w     37.00  90.00   1.00    4.00    --   68.00  76.00  91.56   53
 34  \w     93.00 136.00   1.00    4.00    --   68.00  76.00  91.56   43
 35  \w     38.00  65.00   1.00    4.00    --   68.00  75.00  41.69   27
 36  \w     94.00 119.00   1.00    4.00    --   68.00  75.00  14.29   25
 37  \w     37.00  63.00   1.00    4.00    --   68.00  75.00  14.29   26
 38  \w     89.00 116.00   1.00    4.00    --   68.00  77.00 -94.98   27
 39  \w    107.00 134.00   1.00    4.00    --   72.00  75.00 -36.70   27
 40  \w     41.00 117.00   1.00    4.00    --   72.00  75.00-129.31   76
 41  \w     42.00  74.00   1.00    4.00    --   72.00  75.00 -36.70   32
 42  \w     47.00 108.00   1.00    4.00    --   76.00  73.00 139.41   61
 43  \w     77.00 145.00   1.00    4.00    --   76.00  72.00  66.23   68
 44  \w     48.00  73.00   1.00    4.00    --   76.00  72.00  66.23   25
 45  \w     47.00  75.00   1.00    4.00    --   76.00  74.00-105.81   28
 46  \w     45.00  90.00   1.00    4.00    --   76.00  75.00 -62.37   45
 47  \w     48.00  75.00   1.00    4.00    --   76.00  72.00  97.33   27
 48  \w     48.00 138.00   1.00    4.00    --   76.00  72.00  36.27   90
 49  \w     45.00  82.00   1.00    4.00    --   76.00  75.00 164.80   37
 50  \w     58.00  94.00   1.00    4.00    --   80.00  70.00 166.68   36
 51  \w     59.00  86.00   1.00    4.00    --   80.00  57.00 -31.64   27
 52  \w     56.00  84.00   1.00    4.00    --   80.00  64.00  25.26   28
 53  \w     49.00  75.00   1.00    4.00    --   80.00  75.00  -9.79   26
 54  \w     60.00 147.00   1.00    4.00    --   80.00  61.00-126.46   87
 55  \w     53.00 133.00   1.00   10.00    --   84.00  75.00-163.33   80
 56  \w     53.00 104.00   1.00   10.00    --   84.00  76.00 141.11   51
 57  \w     60.00  86.00   1.00   10.00    --   84.00  48.00  70.87   26
 58  \w     58.00  83.00   1.00   10.00    --   84.00  69.00 -84.19   25
 59  \w    126.00 153.00   1.00   10.00    --   88.00  63.00  83.38   27
 60  \w     64.00  90.00   1.00   10.00    --   88.00  63.00  83.38   26
 61  \w     56.00  82.00   1.00   10.00    --   88.00  77.00 103.12   26
 62  \w    112.00 158.00   1.00   10.00    --   88.00  73.00-113.41   46
 63  \w     59.00  88.00   1.00   10.00    --   88.00  73.00-113.41   29
 64  \w     61.00  88.00   1.00   10.00    --   92.00  76.00 107.72   27
 65  \w     66.00  91.00   1.00   10.00    --   96.00  75.00 -28.94   25
 66  \w     76.00 173.00   1.00   10.00    --  104.00  71.00 156.45   97
 67  \w     50.00 112.00   1.00   10.00    --  108.00-111.00 -90.00   62
 68  \w     76.00 169.00   1.00   10.00    --  108.00  77.00  60.00   93
 69  \w     40.00 110.00   1.00   10.00    --  108.00 -64.00   0.00   70
 70  \w    107.00 167.00   1.00   10.00    --  108.00  77.00-180.00   60
 71  \w     76.00 103.00   1.00   10.00    --  108.00  77.00-180.00   27
 72  \w     84.00 169.00   1.00   10.00    --  108.00  64.00  30.00   85
 73  \w     76.00 178.00   1.00   10.00    --  108.00  77.00 120.00  102
 74  \w     50.00 131.00   1.00   10.00    --  108.00 -50.00 120.00   81
 75  \w     76.00 169.00   1.00   10.00    --  108.00  77.00  90.00   93
 76  \w     76.00 178.00   1.00   10.00    --  108.00  77.00-120.00  102
 77  \w     83.00 176.00   1.00   10.00    --  108.00  64.00-150.00   93
 78  \w     69.00 109.00   1.00   10.00    --  108.00 -92.00 -30.00   40
 79  \w     35.00 109.00   1.00   10.00    --  108.00 -92.00 150.00   74
 80  \w     83.00 109.00   1.00   10.00    --  108.00  64.00   0.00   26
 81  \w     79.00 155.00   1.00   10.00    --  108.00  72.00 -77.63   76
 82  \w     41.00  66.00   1.00   10.00    --  108.00 -64.00-120.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0903616000
_diffrn_orient_matrix_UB_12      -0.0052445000
_diffrn_orient_matrix_UB_13      -0.0460171000
_diffrn_orient_matrix_UB_21      -0.0290635000
_diffrn_orient_matrix_UB_22      -0.0455858000
_diffrn_orient_matrix_UB_23      -0.0367720000
_diffrn_orient_matrix_UB_31      -0.0448132000
_diffrn_orient_matrix_UB_32      0.0757413000
_diffrn_orient_matrix_UB_33      -0.0479597000
_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  0.0993
_diffrn_reflns_av_unetI/netI     0.1005
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            91456
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        66.598
_diffrn_reflns_theta_max         66.598
_diffrn_reflns_theta_min         3.011
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.586
_exptl_absorpt_correction_T_max  0.80447
_exptl_absorpt_correction_T_min  0.79645
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.51a (Rigaku Oxford Diffraction, 2022)
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_colour_primary    orange
_exptl_crystal_density_diffrn    1.235
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2256
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_crystal_size_rad          0.400
_refine_diff_density_max         0.669
_refine_diff_density_min         -0.479
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.951
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1472
_refine_ls_number_reflns         19732
_refine_ls_number_restraints     315
_refine_ls_restrained_S_all      0.957
_refine_ls_R_factor_all          0.1746
_refine_ls_R_factor_gt           0.0905
_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^)+(0.1750P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2339
_refine_ls_wR_factor_ref         0.2852
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9732
_reflns_number_total             19732
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04113a2.cif
_cod_data_source_block           compd_2a_ga_re26
_cod_database_code               7132140
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C70H72N8O2
_chemical_oxdiff_usercomment     re331c
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.944
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C43-C44A \\sim C43-C44B
 with sigma of 0.02
 C44A-C46A \\sim C44B-C46B
 with sigma of 0.02
 C44A-C45A \\sim C44B-C45B
 with sigma of 0.02
 C45A-C46A \\sim C45B-C46B
 with sigma of 0.02
 C43-C45A \\sim C43-C45B
 with sigma of 0.02
 C95A-C94 \\sim C95B-C94
 with sigma of 0.02
 C46B-C45B \\sim C45B-C44B
 with sigma of 0.01
 C46A-C45A \\sim C45A-C44A
 with sigma of 0.01
 C1-C29A \\sim C1-C29B
 with sigma of 0.02
 N2A-C1 \\sim N2B-C1
 with sigma of 0.02
 N2A-C29A \\sim N2B-C29B
 with sigma of 0.02
 N2A-C30A \\sim N2B-C30B
 with sigma of 0.02
 N2A-C3 \\sim N2B-C3
 with sigma of 0.02
 C3-C29A \\sim C3-C29B
 with sigma of 0.02
 C29A-C31A \\sim C29B-C31B
 with sigma of 0.02
 C31A-C30A \\sim C31B-C30B
 with sigma of 0.02
 C29A-C30A \\sim C29B-C30B
 with sigma of 0.02
 C31B-C32 \\sim C32-C31A
 with sigma of 0.02
 C33-C32 \\sim C32-C31B
 with sigma of 0.01
 C30B-C31B \\sim C31B-C32
 with sigma of 0.01
3. Restrained planarity
 N2A, C1, N6, C5, C4, C3
 with sigma of 0.1
 N2B, C1, N6, C5, C4, C3
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C44B \\sim C44A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 2A
C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C90 \\sim C91 \\sim
C92 \\sim C93 \\sim C94 \\sim C95B \\sim C95A \\sim C129 \\sim C130 \\sim C131
\\sim C132 \\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138
\\sim C139 \\sim C140 \\sim C147 \\sim C148 \\sim C149 \\sim C150 \\sim C151
\\sim C152: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
within 2A
N2B \\sim N2A \\sim C29B \\sim C29A \\sim C30B \\sim C30A \\sim C31B \\sim C31A
\\sim C32 \\sim C33 \\sim C34: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01 within 2A
Uanis(C46B) = Uanis(C46A) = Uanis(C45B) = Uanis(C45A)
Uanis(N2A) = Uanis(N2B)
Uanis(C29A) = Uanis(C30B) = Uanis(C29B) = Uanis(C30A) = Uanis(C31B) =
Uanis(C31A)
5. Others
 Sof(H43C)=Sof(H43D)=Sof(C44B)=Sof(H44A)=Sof(H44B)=Sof(C45B)=Sof(H45C)=
 Sof(H45D)=Sof(C46B)=Sof(H46A)=Sof(H46B)=Sof(H46C)=1-FVAR(1)
 Sof(H43A)=Sof(H43B)=Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C45A)=Sof(H45A)=
 Sof(H45B)=Sof(C46A)=Sof(H46D)=Sof(H46E)=Sof(H46F)=FVAR(1)
 Sof(H94C)=Sof(H94D)=Sof(C95B)=Sof(H95A)=Sof(H95B)=Sof(H95C)=1-FVAR(2)
 Sof(H94A)=Sof(H94B)=Sof(C95A)=Sof(H95D)=Sof(H95E)=Sof(H95F)=FVAR(2)
 Sof(N2B)=Sof(C29B)=Sof(H29A)=Sof(H29B)=Sof(C30B)=Sof(H30A)=Sof(H30B)=
 Sof(C31B)=Sof(H31A)=Sof(H31B)=Sof(H32C)=Sof(H32D)=1-FVAR(3)
 Sof(N2A)=Sof(C29A)=Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=
 Sof(C31A)=Sof(H31C)=Sof(H31D)=Sof(H32A)=Sof(H32B)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C29B(H29A,H29B), C29A(H29C,H29D), C30B(H30A,H30B), C30A(H30C,H30D), C31B(H31A,
 H31B), C31A(H31C,H31D), C32(H32A,H32B), C32(H32C,H32D), C33(H33A,H33B),
 C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B),
  C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C43(H43C,H43D), C44B(H44A,
 H44B), C44A(H44C,H44D), C45A(H45A,H45B), C45B(H45C,H45D), C47(H47A,H47B),
 C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C90(H90A,H90B),
  C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B), C94(H94C,
 H94D), C129(H12A,H12B), C130(H13A,H13B), C131(H13C,H13D), C132(H13E,H13F),
 C133(H13G,H13H), C135(H13L,H13M), C136(H13N,H13O), C137(H13P,H13Q), C138(H13R,
 H13S), C139(H13T,H13U), C147(H14D,H14E), C148(H14F,H14G), C149(H14H,H14I),
 C150(H15A,H15B), C151(H15C,H15D)
6.b Aromatic/amide H refined with riding coordinates:
 C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C62(H62), C63(H63),
 C64(H64), C65(H65), C66(H66), C69(H69), C70(H70), C71(H71), C72(H72), C73(H73),
  C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C155(H155), C156(H156),
 C157(H157), C158(H158), C159(H159), C162(H162), C163(H163), C164(H164),
 C165(H165), C166(H166), C169(H169), C170(H170), C171(H171), C172(H172),
 C173(H173), C176(H176), C177(H177), C178(H178), C179(H179), C180(H180)
6.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C40(H40A,H40B,H40C), C46B(H46A,H46B,H46C), C46A(H46D,
 H46E,H46F), C52(H52A,H52B,H52C), C95B(H95A,H95B,H95C), C95A(H95D,H95E,H95F),
 C134(H13I,H13J,H13K), C140(H14A,H14B,H14C), C152(H15E,H15F,H15G)
;
_shelx_res_checksum              65564
_shelx_hkl_checksum              87141
_olex2_date_sample_data_collection 2022-10-07
_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
- B-factor correction
;