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_7064099
_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         'B F4, C14 H14 N'
_chemical_formula_sum            'C14 H14 B F4 N'
_chemical_formula_weight         283.07
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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            4
_cell_length_a                   6.34650(10)
_cell_length_b                   12.68380(10)
_cell_length_c                   16.34990(10)
_cell_measurement_reflns_used    19422
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      69.3930
_cell_measurement_theta_min      4.3890
_cell_volume                     1316.13(2)
_computing_cell_refinement       'CrysAlisPro 1.171.44.85 (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.73a 64-bit (release 27-10-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.44.85 (Rigaku OD, 2024)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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    -93.00 -66.00   0.50    0.23    --  -42.24-143.00  97.00   54
  2  \w    -90.00 -36.00   0.50    0.23    --  -42.24 143.00 153.00  108
  3  \w    -57.00 -24.00   0.50    0.23    --  -42.24 127.00 -16.00   66
  4  \w     70.00 109.00   0.50    0.23    --   44.42 143.00 153.00   78
  5  \w     53.00  89.00   0.50    0.23    --   44.42-143.00  97.00   72
  6  \w     60.00  95.00   0.50    0.23    --   44.42-127.00 -92.00   70
  7  \w     17.00  43.00   0.50    0.23    --   44.42-127.00 -92.00   52
  8  \w    -86.00 -53.00   0.50    0.92    --  -97.09 127.00 -16.00   66
  9  \w   -117.00 -81.00   0.50    0.92    --  -97.09-127.00 -92.00   72
 10  \w    -79.00 -54.00   0.50    0.92    --  -97.09 143.00 153.00   50
 11  \w     90.00 115.00   0.50    0.92    --   99.28 143.00 153.00   50
 12  \w     79.00 110.00   0.50    0.92    --   99.28-143.00  97.00   62
 13  \w     74.00 100.00   0.50    0.92    --   99.28-127.00 -92.00   52
 14  \w     97.00 123.00   0.50    0.92    --   99.28 127.00 -16.00   52
 15  \w    -36.00  -7.00   0.50    0.23    --    4.00 115.00 106.29   58
 16  \w    -37.00   1.00   0.50    0.23    --   -8.00 105.00 -82.37   76
 17  \w    -16.00   9.00   0.50    0.23    --   20.00 102.00 -13.82   50
 18  \w    -15.00  10.00   0.50    0.23    --   20.00 101.00  94.88   50
 19  \w     -9.00  16.00   0.50    0.23    --   24.00  93.00-152.22   50
 20  \w      2.00  27.00   0.50    0.23    --   36.00  95.00 -34.58   50
 21  \w      2.00  27.00   0.50    0.23    --   36.00  98.00-102.61   50
 22  \w      3.00  29.00   0.50    0.23    --   36.00  97.00  15.20   52
 23  \w      2.00  27.00   0.50    0.23    --   36.00  98.00  51.53   50
 24  \w      7.00  32.00   0.50    0.23    --   40.00  93.00-160.30   50
 25  \w      6.00  31.00   0.50    0.23    --   40.00  95.00 146.35   50
 26  \w      7.00  32.00   0.50    0.23    --   40.00  93.00  89.74   50
 27  \w     10.00  35.00   0.50    0.23    --   40.00  85.00  -4.08   50
 28  \w     11.00  37.00   0.50    0.23    --   40.00  85.00 -26.18   52
 29  \w      7.00  32.00   0.50    0.23    --   40.00  93.00-140.85   50
 30  \w     10.00  35.00   0.50    0.23    --   40.00  87.00 -69.47   50
 31  \w      6.00  31.00   0.50    0.23    --   40.00  95.00 128.75   50
 32  \w    -38.00 -12.00   0.50    0.23    --  -42.24 -85.00 -34.53   52
 33  \w    -39.00 -14.00   0.50    0.23    --  -42.24 -82.00 162.66   50
 34  \w    -41.00 -16.00   0.50    0.23    --  -42.24 -75.00-107.24   50
 35  \w    -35.00  -9.00   0.50    0.23    --  -42.24 -93.00   4.42   52
 36  \w    -42.00 -15.00   0.50    0.23    --  -44.00 -83.00-146.64   54
 37  \w     14.00  39.00   0.50    0.23    --   44.00  87.00 155.60   50
 38  \w    -21.00  56.00   0.50    0.23    --   44.42 -54.00  30.00  154
 39  \w    -43.00 -18.00   0.50    0.23    --  -48.00 -90.00 139.33   50
 40  \w    -43.00 -17.00   0.50    0.23    --  -48.00 -90.00  69.02   52
 41  \w     24.00  50.00   0.50    0.23    --   48.00  70.00 -43.45   52
 42  \w     16.00  41.00   0.50    0.23    --   48.00  92.00 179.23   50
 43  \w    -51.00 -25.00   0.50    0.23    --  -48.00 -70.00  -3.23   52
 44  \w    -48.00 -23.00   0.50    0.23    --  -48.00 -70.00 175.79   50
 45  \w     23.00  48.00   0.50    0.23    --   48.00  70.00  45.98   50
 46  \w    -48.00 -22.00   0.50    0.23    --  -48.00 -74.00  74.90   52
 47  \w    -53.00 -28.00   0.50    0.23    --  -52.00 -67.00 153.55   50
 48  \w    -53.00 -28.00   0.50    0.23    --  -52.00 -68.00   5.18   50
 49  \w    -68.00 -27.00   0.50    0.23    --  -52.00 -70.00  73.75   82
 50  \w    -78.00 -29.00   0.50    0.23    --  -52.00 -64.00 -86.81   98
 51  \w    -58.00 -32.00   0.50    0.23    --  -56.00 -65.00  95.98   52
 52  \w    -59.00 -33.00   0.50    0.23    --  -56.00 -62.00 176.19   52
 53  \w     30.00  56.00   0.50    0.23    --   56.00  76.00 102.65   52
 54  \w     92.00 125.00   0.50    0.23    --   56.00  76.00 102.65   66
 55  \w   -119.00 -93.00   0.50    0.23    --  -56.00 -60.00 -69.72   52
 56  \w    -58.00 -33.00   0.50    0.23    --  -56.00 -64.00 131.81   50
 57  \w    -59.00 -34.00   0.50    0.23    --  -56.00 -60.00 -69.72   50
 58  \w    -59.00 -33.00   0.50    0.23    --  -56.00 -62.00 162.05   52
 59  \w    -70.00 -34.00   0.50    0.23    --  -56.00 -60.00-126.17   72
 60  \w    -76.00 -34.00   0.50    0.23    --  -56.00 -61.00 -13.51   84
 61  \w   -111.00 -85.00   0.50    0.23    --  -60.00 -71.00  -7.21   52
 62  \w   -114.00 -88.00   0.50    0.23    --  -60.00 -68.00 124.12   52
 63  \w    -61.00 -36.00   0.50    0.23    --  -60.00 -68.00 124.12   50
 64  \w    -60.00 -35.00   0.50    0.23    --  -60.00 -71.00  -7.21   50
 65  \w    -64.00 -36.00   0.50    0.23    --  -60.00 -66.00-156.98   56
 66  \w    -62.00 -37.00   0.50    0.23    --  -64.00 -75.00-115.34   50
 67  \w   -121.00 -96.00   0.50    0.23    --  -64.00 -75.00-115.34   50
 68  \w    -72.00 -46.00   0.50    0.23    --  -68.00 -73.00 178.31   52
 69  \w   -135.00 -42.00   0.50    0.23    --  -68.00 -74.00 -18.24  186
 70  \w    -77.00 -42.00   0.50    0.23    --  -68.00 -74.00  64.97   70
 71  \w   -122.00 -89.00   0.50    0.23    --  -68.00 -74.00  64.97   66
 72  \w    -80.00 -54.00   0.50    0.92    --  -72.00 -54.00-118.30   52
 73  \w    -77.00 -46.00   0.50    0.92    --  -72.00 -76.00 -51.62   62
 74  \w    -72.00 -46.00   0.50    0.92    --  -72.00 -73.00 151.98   52
 75  \w    -72.00 -46.00   0.50    0.92    --  -72.00 -74.00  88.19   52
 76  \w    -73.00 -47.00   0.50    0.92    --  -72.00 -71.00  36.61   52
 77  \w    -75.00 -50.00   0.50    0.92    --  -76.00 -73.00 109.67   50
 78  \w    -77.00 -51.00   0.50    0.92    --  -76.00 -73.00 125.32   52
 79  \w   -141.00-102.00   0.50    0.92    --  -76.00 -74.00-165.38   78
 80  \w    -78.00 -52.00   0.50    0.92    --  -76.00 -73.00  75.99   52
 81  \w    -82.00 -50.00   0.50    0.92    --  -76.00 -74.00-165.38   64
 82  \w    -79.00 -54.00   0.50    0.92    --  -80.00 -72.00  28.56   50
 83  \w   -133.00 -53.00   0.50    0.92    --  -80.00 -75.00 -63.91  160
 84  \w    -86.00 -54.00   0.50    0.92    --  -80.00 -74.00-139.10   64
 85  \w   -144.00 -97.00   0.50    0.92    --  -80.00 -74.00-139.10   94
 86  \w   -148.00 -94.00   0.50    0.92    --  -80.00 -72.00  28.56  108
 87  \w    -83.00 -57.00   0.50    0.92    --  -84.00 -75.00 112.46   52
 88  \w   -115.00 -57.00   0.50    0.92    --  -84.00 -75.00-100.30  116
 89  \w    -83.00 -58.00   0.50    0.92    --  -84.00 -73.00 170.15   50
 90  \w    -84.00 -59.00   0.50    0.92    --  -84.00 -71.00-173.81   50
 91  \w   -151.00-126.00   0.50    0.92    --  -84.00 -71.00-173.81   50
 92  \w   -110.00 -84.00   0.50    0.92    --  -84.00 -75.00 112.46   52
 93  \w   -151.00-117.00   0.50    0.92    --  -84.00 -73.00 170.15   68
 94  \w    -86.00 -58.00   0.50    0.92    --  -84.00 -73.00  19.29   56
 95  \w   -152.00-121.00   0.50    0.92    --  -84.00 -73.00  19.29   62
 96  \w    -87.00 -62.00   0.50    0.92    --  -88.00 -74.00 151.63   50
 97  \w   -155.00-115.00   0.50    0.92    --  -88.00 -74.00 151.63   80
 98  \w    -99.00 -61.00   0.50    0.92    --  -88.00 -77.00  89.70   76
 99  \w    -98.00 -63.00   0.50    0.92    --  -88.00 -72.00   6.49   70
100  \w   -106.00 -61.00   0.50    0.92    --  -88.00 -76.00  64.21   90
101  \w   -157.00-123.00   0.50    0.92    --  -88.00 -72.00   6.49   68
102  \w   -100.00 -70.00   0.50    0.92    --  -92.00 -67.00 -58.96   60
103  \w   -154.00-128.00   0.50    0.92    --  -92.00 -67.00 -58.96   52
104  \w   -112.00 -70.00   0.50    0.92    --  -96.00 -72.00 -14.55   84
105  \w   -143.00-118.00   0.50    0.92    --  -96.00 -72.00 -14.55   50
106  \w    -94.00 -69.00   0.50    0.92    --  -96.00 -77.00 -26.26   50
107  \w   -152.00-121.00   0.50    0.92    --  -96.00 -77.00 -26.26   62
108  \w   -143.00-118.00   0.50    0.92    --  -97.09 -77.00 150.00   50
109  \w   -146.00 -79.00   0.50    0.92    --  -97.09 -59.00-180.00  134
110  \w    -96.00 -70.00   0.50    0.92    --  -97.09 -77.00   0.00   52
111  \w   -152.00-126.00   0.50    0.92    --  -97.09 -77.00   0.00   52
112  \w   -131.00 -70.00   0.50    0.92    --  -97.09 -77.00-180.00  122
113  \w   -165.00-140.00   0.50    0.92    --  -97.09 -77.00-180.00   50
114  \w    -97.00 -71.00   0.50    0.92    --  -97.09 -77.00  49.85   52
115  \w   -165.00 -78.00   0.50    0.92    --  -97.09 -68.00  30.00  174
116  \w   -165.00-139.00   0.50    0.92    --  -97.09 -77.00  49.85   52
117  \w   -128.00 -75.00   0.50    0.92    --  -97.09 -59.00  90.00  106
118  \w   -134.00 -76.00   0.50    0.92    --  -97.09 -59.00   0.00  116
119  \w   -122.00 -72.00   0.50    0.92    --  -97.09 -77.00  90.00  100
120  \w   -165.00-129.00   0.50    0.92    --  -97.09 -77.00  90.00   72
121  \w    -95.00 -70.00   0.50    0.92    --  -97.09 -77.00 -90.00   50
122  \w   -165.00-120.00   0.50    0.92    --  -97.09 -77.00 -90.00   90
123  \w   -165.00 -73.00   0.50    0.92    --  -97.09 -68.00  60.00  184
124  \w   -105.00 -66.00   0.50    0.92    --  -97.09 117.00  60.00   78
125  \w   -154.00 -91.00   0.50    0.92    --  -97.09-117.00-120.00  126
126  \w   -167.00 -83.00   0.50    0.92    --  -97.09 -25.00  90.00  168
127  \w   -100.00 -71.00   0.50    0.92    --  -97.09 -77.00 129.95   58
128  \w   -164.00-126.00   0.50    0.92    --  -97.09 -77.00 129.95   76
129  \w   -152.00 -70.00   0.50    0.92    --  -97.09 -77.00-120.00  164
130  \w    -66.00 -34.00   0.50    0.92    --  -97.09  59.00 -90.00   64
131  \w    -95.00 -70.00   0.50    0.92    --  -97.09 -77.00-150.00   50
132  \w   -150.00-121.00   0.50    0.92    --  -97.09 -77.00-150.00   58
133  \w    -66.00 -33.00   0.50    0.92    --  -97.09  59.00-150.00   66
134  \w    -67.00 -41.00   0.50    0.92    --  -97.09  59.00-180.00   52
135  \w    -68.00 -31.00   0.50    0.92    --  -97.09  59.00 150.00   74
136  \w   -103.00 -71.00   0.50    0.92    --  -97.09 -77.00 150.00   64
137  \w   -108.00 -74.00   0.50    0.92    --  -97.09 117.00 150.00   68
138  \w   -137.00-112.00   0.50    0.92    --  -97.09-143.00  97.00   50
139  \w     51.00 101.00   0.50    0.92    --   99.28 -77.00-180.00  100
140  \w     72.00 148.00   0.50    0.92    --   99.28  77.00 -60.00  152
141  \w     72.00 157.00   0.50    0.92    --   99.28  77.00 -90.00  170
142  \w     32.00 123.00   0.50    0.92    --   99.28 -86.00  60.00  182
143  \w     35.00  67.00   0.50    0.92    --   99.28 -59.00  90.00   64
144  \w     37.00 108.00   0.50    0.92    --   99.28-144.00  30.00  142
145  \w     86.00 173.00   0.50    0.92    --   99.28  96.00-150.00  174
146  \w     88.00 124.00   0.50    0.92    --   99.28-144.00   0.00   72
147  \w     52.00  80.00   0.50    0.92    --   99.28-144.00   0.00   56
148  \w     31.00  83.00   0.50    0.92    --   99.28 -68.00-120.00  104
149  \w     73.00 161.00   0.50    0.92    --   99.28  77.00-120.00  176
150  \w     71.00  99.00   0.50    0.92    --   99.28-117.00  30.00   56
151  \w     36.00  67.00   0.50    0.92    --   99.28-117.00  30.00   62
;
_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      -0.0054453000
_diffrn_orient_matrix_UB_12      -0.0988795000
_diffrn_orient_matrix_UB_13      -0.0547418000
_diffrn_orient_matrix_UB_21      0.0139177000
_diffrn_orient_matrix_UB_22      -0.0706233000
_diffrn_orient_matrix_UB_23      0.0765358000
_diffrn_orient_matrix_UB_31      -0.2420372000
_diffrn_orient_matrix_UB_32      -0.0017862000
_diffrn_orient_matrix_UB_33      0.0056748000
_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  0.0459
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            28449
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.522
_diffrn_reflns_theta_min         4.412
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.056
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49492
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.85 (Rigaku Oxford Diffraction, 2024)
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    1.429
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_preparation       DCM/Hexane
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.230
_refine_diff_density_min         -0.169
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 994 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         2475
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0258
_refine_ls_R_factor_gt           0.0252
_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^)+(0.0297P)^2^+0.3433P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0624
_refine_ls_wR_factor_ref         0.0627
_reflns_Friedel_coverage         0.701
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                2427
_reflns_number_total             2475
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03620h2.cif
_cod_data_source_block           2e
_cod_depositor_comments
'Adding full bibliography for 7064095--7064099.cif.'
_cod_database_code               7064099
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H B N F'
_cell_oxdiff_angle_alpha         89.9875(15)
_cell_oxdiff_angle_beta          89.9743(15)
_cell_oxdiff_angle_gamma         89.9763(16)
_cell_oxdiff_length_a            6.35288(13)
_cell_oxdiff_length_b            12.6771(2)
_cell_oxdiff_length_c            16.3422(3)
_cell_oxdiff_measurement_reflns_used 19422
_cell_oxdiff_volume              1316.14(4)
_shelx_estimated_absorpt_t_max   0.920
_shelx_estimated_absorpt_t_min   0.849
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C11(H11), C3(H3), C1(H1), C9(H9), C8(H8), C4(H4), C10(H10)
1.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              13984
_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 1.921
_oxdiff_exptl_absorpt_empirical_full_min 0.638