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_7064096
_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 F3 O3 S, C14 H14 N'
_chemical_formula_sum            'C15 H14 F3 N O3 S'
_chemical_formula_weight         345.33
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-03-12
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-08-10 deposited with the CCDC.	2025-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                101.963(3)
_cell_angle_beta                 99.904(3)
_cell_angle_gamma                101.556(3)
_cell_formula_units_Z            2
_cell_length_a                   6.8058(3)
_cell_length_b                   10.8808(4)
_cell_length_c                   11.4591(3)
_cell_measurement_reflns_used    3763
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.9970
_cell_measurement_theta_min      4.0320
_cell_volume                     792.88(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.73a 64-bit (release 27-10-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_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_temperature      293(2)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.979
_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    -43.00  22.00   0.50    0.62    --  -42.24  44.00 -12.00  130
  2  \w    -50.00 -25.00   0.50    0.62    --  -42.24 -44.00-162.00   50
  3  \w   -106.00 -79.00   0.50    0.62    --  -42.24 -44.00-162.00   54
  4  \w     30.00  94.00   0.50    0.62    --   44.42  44.00 -12.00  128
  5  \w    127.00 153.00   0.50    2.47    --   99.28  44.00 -12.00   52
  6  \w     82.00 116.00   0.50    2.47    --   99.28  44.00 -12.00   68
  7  \w   -109.00 -77.00   0.50    0.62    --  -42.24-138.00 -90.00   64
  8  \w    -94.00 -65.00   0.50    0.62    --  -42.24-138.00   0.00   58
  9  \w    -19.00  22.00   0.50    0.62    --  -42.24  65.00  60.00   82
 10  \w    -33.00   1.00   0.50    0.62    --  -42.24 104.00 -30.00   68
 11  \w    -64.00 -29.00   0.50    0.62    --  -42.24  65.00  60.00   70
 12  \w    -58.00 -19.00   0.50    0.62    --  -42.24 -65.00 120.00   78
 13  \w    -69.00 -37.00   0.50    0.62    --  -42.24 104.00 -30.00   64
 14  \w   -104.00 -78.00   0.50    0.62    --  -42.24 -65.00 120.00   52
 15  \w     65.00 111.00   0.50    0.62    --   44.42 138.00-150.00   92
 16  \w    -31.00  21.00   0.50    0.62    --   44.42 -11.00 150.00  104
 17  \w     22.00  57.00   0.50    0.62    --   44.42 -54.00 150.00   70
 18  \w    -14.00  11.00   0.50    0.62    --   44.42 -44.00-162.00   50
 19  \w    -16.00  15.00   0.50    0.62    --   44.42 -54.00 150.00   62
 20  \w     42.00  93.00   0.50    0.62    --   44.42-138.00-150.00  102
 21  \w     17.00  43.00   0.50    0.62    --   44.42 -44.00-162.00   52
 22  \w   -164.00 -79.00   0.50    2.47    --  -97.09 -50.00-120.00  170
 23  \w    -83.00 -38.00   0.50    2.47    --  -97.09  68.00-150.00   90
 24  \w    -57.00 -31.00   0.50    2.47    --  -97.09  50.00-180.00   52
 25  \w   -137.00 -88.00   0.50    2.47    --  -97.09 -25.00 -30.00   98
 26  \w    -56.00 -31.00   0.50    2.47    --  -97.09  50.00 120.00   50
 27  \w    -57.00 -30.00   0.50    2.47    --  -97.09  50.00  90.00   54
 28  \w    -65.00 -35.00   0.50    2.47    --  -97.09  59.00  60.00   60
 29  \w    -79.00 -29.00   0.50    2.47    --  -97.09  68.00 -60.00  100
 30  \w    -57.00 -32.00   0.50    2.47    --  -97.09  50.00  30.00   50
 31  \w   -159.00 -82.00   0.50    2.47    --  -97.09 -42.00 150.00  154
 32  \w    -82.00 -31.00   0.50    2.47    --  -97.09  68.00  30.00  102
 33  \w    -57.00 -32.00   0.50    2.47    --  -97.09  50.00 -60.00   50
 34  \w    -57.00 -31.00   0.50    2.47    --  -97.09  50.00 -90.00   52
 35  \w   -164.00-138.00   0.50    2.47    --  -97.09 -44.00-162.00   52
 36  \w    -57.00 -30.00   0.50    2.47    --  -97.09  50.00   0.00   54
 37  \w   -109.00 -82.00   0.50    2.47    --  -97.09 117.00 -30.00   54
 38  \w   -120.00 -95.00   0.50    2.47    --  -97.09 -33.00 -90.00   50
 39  \w   -114.00 -88.00   0.50    2.47    --  -97.09 -33.00  30.00   52
 40  \w   -159.00-132.00   0.50    2.47    --  -97.09 -33.00  30.00   54
 41  \w   -162.00-125.00   0.50    2.47    --  -97.09 -33.00 -90.00   74
 42  \w    -60.00 -34.00   0.50    2.47    --  -97.09 117.00 -30.00   52
 43  \w   -118.00 -86.00   0.50    2.47    --  -97.09 -44.00-162.00   64
 44  \w     68.00 109.00   0.50    2.47    --   99.28-117.00-180.00   82
 45  \w     38.00  63.00   0.50    2.47    --   99.28-117.00-180.00   50
 46  \w     35.00 109.00   0.50    2.47    --   99.28-117.00-120.00  148
 47  \w     40.00  67.00   0.50    2.47    --   99.28 -59.00 120.00   54
 48  \w     43.00  81.00   0.50    2.47    --   99.28 -96.00-120.00   76
 49  \w     69.00  94.00   0.50    2.47    --   99.28 -77.00 120.00   50
 50  \w     76.00 122.00   0.50    2.47    --   99.28-144.00 150.00   92
 51  \w    140.00 166.00   0.50    2.47    --   99.28 144.00  30.00   52
 52  \w     32.00  66.00   0.50    2.47    --   99.28-144.00 150.00   68
 53  \w     70.00 112.00   0.50    2.47    --   99.28 144.00  30.00   84
 54  \w    116.00 165.00   0.50    2.47    --   99.28  59.00 -90.00   98
 55  \w     32.00  66.00   0.50    2.47    --   99.28 -59.00 -90.00   68
 56  \w     39.00  64.00   0.50    2.47    --   99.28 -59.00  30.00   50
 57  \w     43.00  68.00   0.50    2.47    --   99.28 -59.00 -60.00   50
 58  \w     44.00 107.00   0.50    2.47    --   99.28-144.00-180.00  126
 59  \w     85.00 110.00   0.50    2.47    --   99.28-117.00 -30.00   50
 60  \w    142.00 167.00   0.50    2.47    --   99.28  33.00-150.00   50
 61  \w     50.00 129.00   0.50    2.47    --   99.28 -86.00 -60.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0462
_diffrn_reflns_av_unetI/netI     0.0612
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            6836
_diffrn_reflns_point_group_measured_fraction_full 0.633
_diffrn_reflns_point_group_measured_fraction_max 0.625
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.624
_diffrn_reflns_theta_min         4.045
_exptl_absorpt_coefficient_mu    2.247
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86527
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
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    1.446
_exptl_crystal_description       plate
_exptl_crystal_F_000             356
_refine_diff_density_max         0.649
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.08(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     382
_refine_ls_number_reflns         3724
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0798
_refine_ls_R_factor_gt           0.0645
_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^)+(0.1337P)^2^+0.0818P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1879
_refine_ls_wR_factor_ref         0.2156
_reflns_Friedel_coverage         0.276
_reflns_Friedel_fraction_full    0.278
_reflns_Friedel_fraction_max     0.270
_reflns_number_gt                2811
_reflns_number_total             3724
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03620h2.cif
_cod_data_source_block           2b
_cod_depositor_comments
'Adding full bibliography for 7064095--7064099.cif.'
_cod_database_code               7064096
_shelx_shelxl_version_number     2019/3
_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 Me refined with riding coordinates:
 C00H(H00A,H00B,H00C), C00V(H00D,H00E,H00F), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C)
2.b Aromatic/amide H refined with riding coordinates:
 C003(H003), C00K(H00K), C00R(H00R), C00O(H00O), C016(H016), C00J(H00J),
 C00X(H00X), C00C(H00G), C00L(H00L), C017(H017), C00T(H00T), C014(H014), C3(H3),
  C4(H4), C5(H5), C6(H6)
2.c Fitted pentagon refined as free rotating group:
 N00A(C01A,C00N,C012,C00W)
2.d Fitted hexagon refined as free rotating group:
 N008(C00P,C00R,C00O,C016,C00J), C007(C00D,C00X,C00C,C00L,C017)
;
_shelx_res_checksum              47693
_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
;