Synthesis and crystal structure of pH-sensitive fluorescent pyrene-based double aza- and diaza[4]helicenes
Tonkoglazova, Daria; Oryabinskaya, Lyubov M.; Shcherbatykh, Aleksandr; Gulevskaya, Anna V.; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB00204C

data_7158566
_publ_section_title
;
 Synthesis and crystal structure of pH-sensitive fluorescent pyrene-based
 double aza- and diaza[4]helicenes
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB00204C
_journal_year                    2022
_chemical_formula_moiety         'C38 H23 N, C D Cl3 '
_chemical_formula_sum            'C39 H23 Cl3 D N'
_chemical_formula_weight         613.95
_chemical_melting_point          519.0(10)
_chemical_name_systematic        5-(p-Tolyl)naphtho[2,1-f]pyreno[2,1-h]quinoline
_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             2021-12-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-01-28 deposited with the CCDC.	2022-03-09 downloaded from the CCDC.
;
_cell_angle_alpha                100.434(2)
_cell_angle_beta                 109.813(2)
_cell_angle_gamma                94.308(2)
_cell_formula_units_Z            2
_cell_length_a                   9.9654(2)
_cell_length_b                   10.8736(2)
_cell_length_c                   14.6459(3)
_cell_measurement_reflns_used    14001
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.7750
_cell_measurement_theta_min      3.2910
_cell_volume                     1452.32(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_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_environment      N~2~
_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 0.998
_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    -89.00 -34.00   0.50    0.45    --  -47.44 115.00 119.00  110
  2  \w   -117.00 -77.00   0.50    0.45    --  -47.44-167.00-115.00   80
  3  \w   -110.00 -85.00   0.50    0.45    --  -47.44 167.00 -94.00   50
  4  \w     49.00 119.00   0.50    0.45    --   47.44 167.00 -94.00  140
  5  \w     12.00  38.00   0.50    0.45    --   47.44-115.00  30.00   52
  6  \w     54.00  79.00   0.50    0.45    --   47.44-167.00-115.00   50
  7  \w   -137.00 -54.00   0.50    1.80    -- -106.00 167.00 -94.00  166
  8  \w   -108.00 -40.00   0.50    1.80    -- -106.00 115.00 119.00  136
  9  \w   -153.00-128.00   0.50    1.80    -- -106.00-115.00  30.00   50
 10  \w   -123.00 -98.00   0.50    1.80    -- -106.00-167.00-115.00   50
 11  \w     86.00 121.00   0.50    1.80    --  113.25-167.00-115.00   70
 12  \w     65.00 101.00   0.50    1.80    --  113.25 167.00 -94.00   72
 13  \w     51.00 109.00   0.50    1.80    --  113.25-115.00  30.00  116
 14  \w    105.00 130.00   0.50    1.80    --  113.25 115.00 119.00   50
 15  \w   -113.00 -75.00   0.50    0.45    --  -47.44-125.00  60.00   76
 16  \w    -24.00  24.00   0.50    0.45    --  -47.44  19.00-150.00   96
 17  \w   -114.00 -25.00   0.50    0.45    --  -47.44 -77.00  60.00  178
 18  \w     78.00 119.00   0.50    0.45    --   47.44 125.00  60.00   82
 19  \w    -17.00  20.00   0.50    0.45    --   47.44 -19.00-180.00   74
 20  \w     74.00 119.00   0.50    0.45    --   47.44 125.00  30.00   90
 21  \w   -177.00-119.00   0.50    1.80    -- -106.00 -15.00  60.00  116
 22  \w    -96.00 -70.00   0.50    1.80    -- -106.00  77.00 -30.00   52
 23  \w   -177.00 -93.00   0.50    1.80    -- -106.00 -45.00  30.00  168
 24  \w   -107.00 -82.00   0.50    1.80    -- -106.00 111.00  55.10   50
 25  \w    -68.00 -42.00   0.50    1.80    -- -106.00  77.00 -30.00   52
 26  \w   -112.00 -39.00   0.50    1.80    -- -106.00 125.00-150.00  146
 27  \w    -64.00 -39.00   0.50    1.80    -- -106.00  61.00 -60.00   50
 28  \w   -166.00-126.00   0.50    1.80    -- -106.00 -15.00  90.00   80
 29  \w   -112.00 -80.00   0.50    1.80    -- -106.00 125.00-180.00   64
 30  \w   -112.00 -35.00   0.50    1.80    -- -106.00 125.00 120.00  154
 31  \w   -175.00-150.00   0.50    1.80    -- -106.00-125.00   0.00   50
 32  \w    -68.00 -34.00   0.50    1.80    -- -106.00  61.00 150.00   68
 33  \w   -121.00 -96.00   0.50    1.80    -- -106.00 138.00 155.21   50
 34  \w    -78.00 -34.00   0.50    1.80    -- -106.00 138.00 155.21   88
 35  \w    -69.00 -33.00   0.50    1.80    -- -106.00  61.00-120.00   72
 36  \w    -69.00 -44.00   0.50    1.80    -- -106.00 111.00  55.10   50
 37  \w   -112.00 -85.00   0.50    1.80    -- -106.00 125.00 -90.00   54
 38  \w   -113.00 -75.00   0.50    1.80    -- -106.00-125.00   0.00   76
 39  \w    101.00 176.00   0.50    1.80    --  113.25  61.00 120.00  150
 40  \w     62.00  88.00   0.50    1.80    --  113.25 -77.00   0.00   52
 41  \w     58.00 106.00   0.50    1.80    --  113.25 -94.00  60.00   96
 42  \w     42.00 108.00   0.50    1.80    --  113.25-125.00 -30.00  132
 43  \w     43.00  69.00   0.50    1.80    --  113.25 -61.00  60.00   52
 44  \w     71.00 101.00   0.50    1.80    --  113.25-125.00   0.00   60
 45  \w     42.00  69.00   0.50    1.80    --  113.25 -61.00  30.00   54
 46  \w    133.00 170.00   0.50    1.80    --  113.25  77.00  90.00   74
 47  \w     44.00 111.00   0.50    1.80    --  113.25-125.00  60.00  134
 48  \w     91.00 130.00   0.50    1.80    --  113.25  77.00  90.00   78
 49  \w     71.00  96.00   0.50    1.80    --  113.25 -94.00-120.00   50
 50  \w    105.00 169.00   0.50    1.80    --  113.25  15.00 -90.00  128
 51  \w     45.00  77.00   0.50    1.80    --  113.25 -94.00-150.00   64
 52  \w    106.00 172.00   0.50    1.80    --  113.25  30.00-150.00  132
 53  \w     44.00  69.00   0.50    1.80    --  113.25 -61.00   0.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0690745000
_diffrn_orient_matrix_UB_12      0.1146180000
_diffrn_orient_matrix_UB_13      0.0313147000
_diffrn_orient_matrix_UB_21      0.1005519000
_diffrn_orient_matrix_UB_22      0.0148119000
_diffrn_orient_matrix_UB_23      0.1089052000
_diffrn_orient_matrix_UB_31      0.1127795000
_diffrn_orient_matrix_UB_32      0.0886491000
_diffrn_orient_matrix_UB_33      -0.0172187000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            20770
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.991
_diffrn_reflns_theta_min         3.288
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.087
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92133
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (Rigaku Oxford Diffraction, 2021)
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    1.404
_exptl_crystal_description       prism
_exptl_crystal_F_000             632
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.352
_refine_diff_density_min         -0.421
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         5497
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0389
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0512P)^2^+0.5541P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0951
_refine_ls_wR_factor_ref         0.0980
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4949
_reflns_number_total             5497
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob00204c2.cif
_cod_data_source_block           19381_sp-66
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '518-520' was changed to
'519.0(10)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_original_cell_volume        1452.32(5)
_cod_original_formula_sum        'C39 H23 D Cl3 N'
_cod_database_code               7158566
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C39 H23 D Cl3 N'
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.690
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_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:
 C39(D39)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C29(H29),
  C33(H33), C34(H34), C36(H36), C37(H37)
2.c Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C)
;
_shelx_res_checksum              28924
_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 1.345
_oxdiff_exptl_absorpt_empirical_full_min 0.712