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_7064095
_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         'C14 H14 N, C7 H7 O3 S'
_chemical_formula_sum            'C21 H21 N O3 S'
_chemical_formula_weight         367.45
_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     direct
_audit_creation_date             2025-06-26
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-06-28 deposited with the CCDC.	2025-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                73.514(3)
_cell_angle_beta                 80.003(3)
_cell_angle_gamma                83.314(3)
_cell_formula_units_Z            2
_cell_length_a                   6.6646(3)
_cell_length_b                   11.2132(4)
_cell_length_c                   12.7701(5)
_cell_measurement_reflns_used    3928
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      69.4090
_cell_measurement_theta_min      3.4820
_cell_volume                     898.92(6)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.988
_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     28.00  62.00   0.40    0.20    --   44.42 -65.00 -30.00   85
  2  \w    -20.00   6.00   0.40    0.20    --   44.42 -65.00 -30.00   65
  3  \w    -27.00  27.00   0.40    0.20    --   44.42 -21.00 -90.00  135
  4  \w    -31.00  -5.00   0.40    0.20    --   44.42 -11.00 -30.00   65
  5  \w    -28.00  21.20   0.40    0.20    --   44.42 -11.00  30.00  123
  6  \w     78.00 138.00   0.40    0.59    --   99.28 117.00 -90.00  150
  7  \w     93.00 118.20   0.40    0.59    --   99.28 131.00  39.00   63
  8  \w    -29.00  23.00   0.40    0.20    --   44.42 -11.00-180.00  130
  9  \w     55.00  81.00   0.40    0.20    --   44.42-131.00 -31.00   65
 10  \w     23.00  50.20   0.40    0.20    --   44.42-131.00 -31.00   68
 11  \w     31.00 105.00   0.40    0.59    --   99.28 -77.00 -60.00  185
 12  \w     31.00  59.00   0.40    0.59    --   99.28 -59.00-180.00   70
 13  \w     31.00  63.00   0.40    0.59    --   99.28 -59.00-150.00   80
 14  \w     51.00  82.20   0.40    0.59    --   99.28 -68.00   0.00   78
 15  \w     46.00  89.20   0.40    0.20    --   44.42-138.00 153.00  108
 16  \w     38.00 104.00   0.40    0.59    --   99.28 -77.00 150.00  165
 17  \w     30.00  88.00   0.40    0.59    --   99.28 -96.00 150.00  145
 18  \w     67.00  92.20   0.40    0.59    --   99.28-138.00 153.00   63
 19  \w     35.00 108.20   0.40    0.59    --   99.28-117.00 150.00  183
 20  \w     52.00  77.20   0.40    0.59    --   99.28-131.00 -31.00   63
 21  \w     84.00 134.00   0.40    0.59    --   99.28  25.00  60.00  125
 22  \w    141.00 169.00   0.40    0.59    --   99.28  25.00  60.00   70
 23  \w     92.00 156.00   0.40    0.59    --   99.28  33.00  90.00  160
 24  \w     76.00 108.00   0.40    0.59    --   99.28  68.00   0.00   80
 25  \w     64.00 100.00   0.40    0.20    --   44.42 138.00 -60.00   90
 26  \w     71.00 101.00   0.40    0.20    --   44.42 138.00-144.00   75
 27  \w     67.00 110.20   0.40    0.20    --   44.42 138.00-120.00  108
 28  \w     64.00  89.20   0.40    0.20    --   44.42 138.00  60.00   63
 29  \w    -61.00  10.20   0.40    0.20    --  -42.24  54.00-120.00  178
 30  \w   -122.00 -80.00   0.40    0.59    --  -97.09 138.00-144.00  105
 31  \w   -125.00 -75.00   0.40    0.59    --  -97.09 144.00-120.00  125
 32  \w   -110.00 -62.00   0.40    0.59    --  -97.09 117.00-150.00  120
 33  \w    -65.00 -40.20   0.40    0.59    --  -97.09 138.00-144.00   62
 34  \w     -2.00  24.00   0.40    0.20    --  -42.24  32.00  60.00   65
 35  \w    -30.00  -4.00   0.40    0.20    --  -42.24  32.00  60.00   65
 36  \w   -105.00 -35.00   0.40    0.59    --  -97.09 117.00  30.00  175
 37  \w    -98.00 -72.80   0.40    0.59    --  -97.09 131.00  39.00   63
 38  \w    -61.00 -23.00   0.40    0.20    --  -42.24 131.00  39.00   95
 39  \w    -65.00 -39.00   0.40    0.59    --  -97.09  59.00  30.00   65
 40  \w    -66.00 -30.00   0.40    0.59    --  -97.09  59.00-120.00   90
 41  \w    -56.00 -30.00   0.40    0.59    --  -97.09  50.00-150.00   65
 42  \w    -88.00 -62.00   0.40    0.20    --  -42.24 138.00-144.00   65
 43  \w    -51.00 -19.00   0.40    0.20    --  -42.24 138.00-144.00   80
 44  \w    -56.00 -31.20   0.40    0.59    --  -97.09  50.00   0.00   62
 45  \w    -56.00 -32.00   0.40    0.59    --  -97.09  50.00  60.00   60
 46  \w    -56.00 -32.00   0.40    0.59    --  -97.09  50.00 120.00   60
 47  \w   -108.00 -78.00   0.40    0.20    --  -42.24 -54.00 -60.00   75
 48  \w    -65.00 -25.00   0.40    0.20    --  -42.24 -54.00 -60.00  100
 49  \w   -120.00 -80.00   0.40    0.59    --  -97.09 -50.00 -30.00  100
 50  \w   -126.00 -86.00   0.40    0.59    --  -97.09 -33.00-150.00  100
 51  \w   -163.20 -80.00   0.40    0.59    --  -97.09 -42.00-180.00  208
 52  \w   -165.00-129.00   0.40    0.59    --  -97.09 -33.00-150.00   90
 53  \w   -164.00-138.00   0.40    0.59    --  -97.09 -50.00 -30.00   65
 54  \w   -164.00-138.00   0.40    0.59    --  -97.09 -50.00 150.00   65
 55  \w   -125.00 -85.00   0.40    0.59    --  -97.09 -50.00 150.00  100
 56  \w   -138.00-112.80   0.40    0.59    --  -97.09-138.00 153.00   63
 57  \w   -105.00 -79.00   0.40    0.20    --  -42.24-138.00  60.00   65
 58  \w    -96.00 -70.00   0.40    0.20    --  -42.24-138.00  30.00   65
 59  \w   -134.00-108.00   0.40    0.59    --  -97.09-131.00 -31.00   65
 60  \w   -156.00 -78.80   0.40    0.59    --  -97.09 -86.00 -90.00  193
;
_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      0.0392851000
_diffrn_orient_matrix_UB_12      0.0480458000
_diffrn_orient_matrix_UB_13      -0.1268559000
_diffrn_orient_matrix_UB_21      -0.1202903000
_diffrn_orient_matrix_UB_22      -0.1050780000
_diffrn_orient_matrix_UB_23      -0.0090212000
_diffrn_orient_matrix_UB_31      -0.1983948000
_diffrn_orient_matrix_UB_32      0.0853416000
_diffrn_orient_matrix_UB_33      0.0026184000
_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  0.0566
_diffrn_reflns_av_unetI/netI     0.0790
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            8077
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.712
_diffrn_reflns_theta_min         3.650
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.770
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.641
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (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            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.358
_exptl_crystal_description       block
_exptl_crystal_F_000             388
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.432
_refine_diff_density_min         -0.621
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         3348
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0769P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1341
_refine_ls_wR_factor_ref         0.1429
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2742
_reflns_number_total             3348
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03620h2.cif
_cod_data_source_block           exp_940_auto
_cod_depositor_comments
'Adding full bibliography for 7064095--7064099.cif.'
_cod_database_code               7064095
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N S O'
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.656
_olex2_refinement_description
;
1.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15),
 C17(H17), C18(H18), C20(H20), C21(H21)
1.b Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              40366
_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 3.196
_oxdiff_exptl_absorpt_empirical_full_min 0.397