Synthesis of a novel twisted π-conjugated macrocycle <i>via</i> double Friedel-Crafts reaction and its physical properties.
Jiang, Zhiyan; Kuninobu, Yoichiro; Chemical communications (Cambridge, England) 60 (2024) 7642–7645; doi:10.1039/d4cc00890a

data_7133263
_publ_section_title
;
 Synthesis of a novel twisted &#x3c0;-conjugated macrocycle <i>via</i>
 double Friedel-Crafts reaction and its physical properties.
;
_journal_issue                   59
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7642
_journal_page_last               7645
_journal_paper_doi               10.1039/d4cc00890a
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C50 H48 N4, 2[C7H8]'
_chemical_formula_sum            'C64 H64 N4'
_chemical_formula_weight         889.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-06-18
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-18 deposited with the CCDC.	2024-06-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.162(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6774(4)
_cell_length_b                   23.2733(8)
_cell_length_c                   17.2556(5)
_cell_measurement_reflns_used    18511
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.1440
_cell_measurement_theta_min      3.1590
_cell_volume                     5087.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.960
_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     44.00  84.00   0.50    0.06    --   44.63-118.00  71.00   80
  2  \w     43.00  68.00   0.50    0.20    --  107.43-118.00  71.00   50
  3  \w     66.00  92.00   0.50    0.20    --  107.43 -94.00  60.00   52
  4  \w     35.00  93.00   0.50    0.20    --  107.43 -94.00  90.00  116
  5  \w     34.00  63.00   0.50    0.20    --  107.43 -94.00 120.00   58
  6  \w     67.00  93.00   0.50    0.20    --  107.43 -94.00 120.00   52
  7  \w     34.00  93.00   0.50    0.20    --  107.43 -94.00 150.00  118
  8  \w    110.00 136.00   0.50    0.20    --  107.43  15.00 120.00   52
  9  \w     42.00  71.00   0.50    0.20    --  107.43 -77.00 -90.00   58
 10  \w    101.00 172.00   0.50    0.20    --  107.43 118.00 157.00  142
 11  \w    -16.00  10.00   0.50    0.06    --  -44.63  38.00  60.00   52
 12  \w    -11.00  28.00   0.50    0.06    --  -44.63  38.00  30.00   78
 13  \w    -17.00  30.00   0.50    0.06    --  -44.63  38.00 -30.00   94
 14  \w     -9.00  31.00   0.50    0.06    --  -44.63  38.00 -90.00   80
 15  \w    -42.00  29.00   0.50    0.06    --  -44.63  57.00-120.00  142
 16  \w    -13.00  24.00   0.50    0.06    --  -44.63  38.00 -60.00   74
 17  \w    -71.00 -31.00   0.50    0.20    -- -104.00  77.00-180.00   80
 18  \w    -43.00 -17.00   0.50    0.06    --  -44.63 118.00 157.00   52
 19  \w    -83.00 -53.00   0.50    0.06    --  -44.63 118.00 157.00   60
 20  \w    -98.00 -61.00   0.50    0.20    -- -104.00 118.00 157.00   74
 21  \w    -66.00 -30.00   0.50    0.20    -- -104.00  77.00  90.00   72
 22  \w   -134.00 -95.00   0.50    0.20    -- -104.00 -15.00 120.00   78
 23  \w   -128.00-102.00   0.50    0.20    -- -104.00 -15.00  30.00   52
 24  \w   -166.00-140.00   0.50    0.20    -- -104.00 -61.00 -90.00   52
 25  \w   -126.00-101.00   0.50    0.20    -- -104.00 -61.00 -90.00   50
 26  \w   -125.00 -99.00   0.50    0.20    -- -104.00 -30.00-120.00   52
 27  \w   -134.00 -96.00   0.50    0.20    -- -104.00 -15.00-150.00   76
 28  \w   -163.00-128.00   0.50    0.20    -- -104.00 -30.00-120.00   70
 29  \w   -132.00-100.00   0.50    0.20    -- -104.00 -15.00 -90.00   64
 30  \w   -134.00 -95.00   0.50    0.20    -- -104.00 -15.00  60.00   78
 31  \w   -146.00-100.00   0.50    0.20    -- -104.00-118.00  71.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0094229000
_diffrn_orient_matrix_UB_12      0.0269590000
_diffrn_orient_matrix_UB_13      0.0816367000
_diffrn_orient_matrix_UB_21      0.0226887000
_diffrn_orient_matrix_UB_22      -0.0597349000
_diffrn_orient_matrix_UB_23      0.0353099000
_diffrn_orient_matrix_UB_31      0.1188964000
_diffrn_orient_matrix_UB_32      0.0093022000
_diffrn_orient_matrix_UB_33      -0.0098410000
_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  0.0322
_diffrn_reflns_av_unetI/netI     0.0313
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            36578
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.566
_diffrn_reflns_theta_min         3.190
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.510
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.518
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_description       prism
_exptl_crystal_F_000             1904
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene/hexane'
_exptl_crystal_size_max          0.248
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.148
_refine_diff_density_max         0.327
_refine_diff_density_min         -0.292
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     495
_refine_ls_number_reflns         10141
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0667
_refine_ls_R_factor_gt           0.0609
_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^)+(0.1046P)^2^+2.5469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1909
_refine_ls_wR_factor_ref         0.1965
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8729
_reflns_number_total             10141
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00890a2.cif
_cod_data_source_block           molecule_3
_cod_depositor_comments          'Adding full bibliography for 7133263.cif.'
_cod_database_code               7133263
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.884
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C16(H16), C1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C29(H29), C26(H26), C21(H21), C3(H3), C4(H4), C28(H28), C18(H18),
 C19(H19), C11(H11), C36(H36), C14(H14), C13(H13), C42(H42), C35(H35), C38(H38),
  C34(H34), C41(H41), C40(H40), C39(H39), C32(H32), C33(H33)
2.c Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C47(H47A,H47B,H47C), C51(H51A,H51B,H51C), C50(H50A,H50B,
 H50C), C54(H54A,H54B,H54C), C45(H45A,H45B,H45C), C44(H44A,H44B,H44C), C53(H53A,
 H53B,H53C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 436 electrons were 
found in a volume of 1674\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C7H8] per formula unit 
which account for 400 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              82007
_shelx_hkl_checksum              9108
_shelx_fab_checksum              2866
_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 1.242
_oxdiff_exptl_absorpt_empirical_full_min 0.848