Counteranion-controlled aggregation-induced emission in 10H-pyrido[1,2-a]-5-indolium salts: structure–property relationships and anion–π+ interactions
Mizuno, Shota; Suzuki, Haruka; Kato, Kunihiko; Kubota, Yasuhiro; Inuzuka, Toshiyasu; Ban, Takayuki; Funabiki, Kazumasa; New Journal of Chemistry 49 (2025) 19479–19488; doi:10.1039/D5NJ03620H

data_7064097
_publ_section_title
;
 Counteranion-controlled aggregation-induced emission in
 10H-pyrido[1,2-a]-5-indolium salts: structure--property relationships and
 anion--\p+ interactions
;
_journal_issue                   45
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              19479
_journal_page_last               19488
_journal_paper_doi               10.1039/D5NJ03620H
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C H2 Cl2, C14 H14 N, C24 H20 B'
_chemical_formula_sum            'C39 H36 B Cl2 N'
_chemical_formula_weight         600.40
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-08 deposited with the CCDC.	2025-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.5691(5)
_cell_length_b                   17.3369(5)
_cell_length_c                   20.5092(6)
_cell_measurement_reflns_used    16439
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      69.5050
_cell_measurement_theta_min      4.1450
_cell_volume                     6247.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.940
_diffrn_measured_fraction_theta_max 0.910
_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    -77.00 -51.00   0.50    0.70    --  -42.24 135.00  28.00   52
  2  \w    -43.00 -18.00   0.50    0.70    --  -42.24 135.00  28.00   50
  3  \w    -97.00 -21.00   0.50    0.70    --  -42.24 134.00-150.00  152
  4  \w     66.00 107.00   0.50    0.70    --   44.42 135.00  28.00   82
  5  \w     40.00  76.00   0.50    0.70    --   44.42-135.00 -37.00   72
  6  \w     38.00  95.00   0.50    0.70    --   44.42-134.00 142.00  114
  7  \w    -90.00 -37.00   0.50    2.78    --  -97.09 134.00-150.00  106
  8  \w     66.00 107.00   0.50    2.78    --   99.28 135.00  28.00   82
  9  \w     52.00  77.00   0.50    2.78    --   99.28-134.00 142.00   50
 10  \w   -102.00 -73.00   0.50    0.70    --  -42.24-138.00  30.00   58
 11  \w     -2.00  30.00   0.50    0.70    --  -42.24  21.00  30.00   64
 12  \w    -21.00  10.00   0.50    0.70    --  -42.24  21.00-120.00   62
 13  \w    -24.00  26.00   0.50    0.70    --  -42.24  11.00  90.00  100
 14  \w   -105.00 -77.00   0.50    0.70    --  -42.24-138.00-180.00   56
 15  \w      2.00  27.00   0.50    0.70    --  -42.24  11.00 -90.00   50
 16  \w    -20.00  15.00   0.50    0.70    --   44.42 -43.00 150.00   70
 17  \w    -24.00   1.00   0.50    0.70    --   44.42 -11.00 -60.00   50
 18  \w    -27.00  10.00   0.50    0.70    --   44.42 -11.00  90.00   74
 19  \w    -30.00  -5.00   0.50    0.70    --   44.42 -11.00 -90.00   50
 20  \w    -63.00 -29.00   0.50    2.78    --  -97.09  59.00  30.00   68
 21  \w   -123.00 -90.00   0.50    2.78    --  -97.09 -33.00-150.00   66
 22  \w    -68.00 -31.00   0.50    2.78    --  -97.09  59.00-150.00   74
 23  \w    -59.00 -34.00   0.50    2.78    --  -97.09  59.00-120.00   50
 24  \w   -165.00-135.00   0.50    2.78    --  -97.09 -33.00-150.00   60
 25  \w    -54.00 -29.00   0.50    2.78    --  -97.09  77.00-120.00   50
 26  \w    -64.00 -36.00   0.50    2.78    --  -97.09  59.00  60.00   56
 27  \w   -106.00 -80.00   0.50    2.78    --  -97.09  77.00-120.00   52
 28  \w    -99.00 -74.00   0.50    2.78    --  -97.09 135.00  28.00   50
 29  \w    -57.00 -32.00   0.50    2.78    --  -97.09  50.00  90.00   50
 30  \w    -83.00 -52.00   0.50    2.78    --  -97.09  68.00-180.00   62
 31  \w    -79.00 -52.00   0.50    2.78    --  -97.09  68.00   0.00   54
 32  \w    -56.00 -31.00   0.50    2.78    --  -97.09  50.00-180.00   50
 33  \w   -153.00-104.00   0.50    2.78    --  -97.09-117.00-150.00   98
 34  \w   -106.00 -80.00   0.50    2.78    --  -97.09  77.00  60.00   52
 35  \w    -81.00 -29.00   0.50    2.78    --  -97.09  68.00-120.00  104
 36  \w   -137.00 -86.00   0.50    2.78    --  -97.09-117.00  30.00  102
 37  \w    126.00 158.00   0.50    2.78    --   99.28  33.00 -30.00   64
 38  \w     50.00  75.00   0.50    2.78    --   99.28 -68.00 -60.00   50
 39  \w     78.00 153.00   0.50    2.78    --   99.28 117.00-120.00  150
 40  \w     78.00 163.00   0.50    2.78    --   99.28 117.00  60.00  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0063636000
_diffrn_orient_matrix_UB_12      -0.0001231000
_diffrn_orient_matrix_UB_13      -0.0749200000
_diffrn_orient_matrix_UB_21      0.0872268000
_diffrn_orient_matrix_UB_22      -0.0052779000
_diffrn_orient_matrix_UB_23      0.0055021000
_diffrn_orient_matrix_UB_31      -0.0051669000
_diffrn_orient_matrix_UB_32      -0.0887744000
_diffrn_orient_matrix_UB_33      -0.0002372000
_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  0.0848
_diffrn_reflns_av_unetI/netI     0.0548
_diffrn_reflns_Laue_measured_fraction_full 0.940
_diffrn_reflns_Laue_measured_fraction_max 0.910
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            31810
_diffrn_reflns_point_group_measured_fraction_full 0.940
_diffrn_reflns_point_group_measured_fraction_max 0.910
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.800
_diffrn_reflns_theta_min         4.181
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.078
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24669
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (Rigaku Oxford Diffraction, 2022)
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    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             2528
_exptl_crystal_preparation       DCM/Hexane
_exptl_crystal_size_max          0.487
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.067
_refine_diff_density_max         0.453
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     390
_refine_ls_number_reflns         5469
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0801P)^2^+1.9859P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1307
_refine_ls_wR_factor_ref         0.1415
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4601
_reflns_number_total             5469
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03620h2.cif
_cod_data_source_block           2d
_cod_depositor_comments
'Adding full bibliography for 7064095--7064099.cif.'
_cod_database_code               7064097
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H B N'
_cell_oxdiff_angle_alpha         90.0115(16)
_cell_oxdiff_angle_beta          90.040(2)
_cell_oxdiff_angle_gamma         89.9814(17)
_cell_oxdiff_length_a            17.5845(4)
_cell_oxdiff_length_b            17.3231(3)
_cell_oxdiff_length_c            20.5075(5)
_cell_oxdiff_measurement_reflns_used 16438
_cell_oxdiff_volume              6247.0(2)
_shelx_estimated_absorpt_t_max   0.873
_shelx_estimated_absorpt_t_min   0.431
_diffrn_oxdiff_digest_hkl
;
0129c6fd168e8975aafa65dddb644bbcb0db25
;
_olex2_refinement_description
;
1.a Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B)
1.b Aromatic/amide H refined with riding coordinates:
 C24(H24), C22(H22), C4(H4), C15(H15), C16(H16), C38(H38), C1(H1), C19(H19),
 C32(H32), C18(H18), C8(H8), C34(H34), C28(H28), C26(H26), C17(H17), C25(H25),
 C10(H10), C31(H31), C11(H11), C21(H21), C29(H29), C30(H30), C2(H2), C37(H37),
 C35(H35), C3(H3), C36(H36), C9(H9)
1.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              53388
_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 4.022
_oxdiff_exptl_absorpt_empirical_full_min 0.358