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_7064098
_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         '2(C24 B F20), 2(C14 H14 N), C H Cl3'
_chemical_formula_sum            'C77 H29 B2 Cl3 F40 N2'
_chemical_formula_weight         1869.99
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-06-28 deposited with the CCDC.	2025-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                98.570(2)
_cell_angle_beta                 101.164(2)
_cell_angle_gamma                112.216(2)
_cell_formula_units_Z            1
_cell_length_a                   10.1711(2)
_cell_length_b                   12.3512(3)
_cell_length_c                   16.3633(3)
_cell_measurement_reflns_used    9577
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      69.3980
_cell_measurement_theta_min      2.8370
_cell_volume                     1810.28(8)
_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      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 0.990
_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    -10.00  47.00   0.50    0.20    --   44.42 -43.00 120.00  114
  2  \w      0.00  37.00   0.50    0.20    --   44.42 -32.00 -90.00   74
  3  \w     37.00  63.00   0.50    0.20    --   44.42 -67.00-133.00   52
  4  \w    -21.00  28.00   0.50    0.20    --   44.42 -67.00-133.00   98
  5  \w     -5.00  20.00   0.50    0.20    --   44.42 -11.00-180.00   50
  6  \w    -30.00  24.00   0.50    0.20    --   44.42 -11.00-120.00  108
  7  \w     36.00  81.00   0.50    0.20    --   44.42-104.00 -30.00   90
  8  \w     22.00  60.00   0.50    0.20    --   44.42-104.00  90.00   76
  9  \w     37.00  78.00   0.50    0.20    --   44.42-138.00-120.00   82
 10  \w     76.00 104.00   0.50    0.74    --   99.28 -77.00-180.00   56
 11  \w     31.00  64.00   0.50    0.74    --   99.28 -77.00-180.00   66
 12  \w     32.00  58.00   0.50    0.74    --   99.28 -67.00-133.00   52
 13  \w     43.00  74.00   0.50    0.74    --   99.28 -96.00-180.00   62
 14  \w     73.00  98.00   0.50    0.74    --   99.28-117.00-180.00   50
 15  \w     85.00 110.00   0.50    0.74    --   99.28-117.00-120.00   50
 16  \w     39.00  64.00   0.50    0.74    --   99.28-117.00-120.00   50
 17  \w     77.00 110.00   0.50    0.74    --   99.28-117.00  60.00   66
 18  \w     90.00 142.00   0.50    0.74    --   99.28  96.00 -30.00  104
 19  \w     84.00 109.00   0.50    0.20    --   44.42 138.00-150.00   50
 20  \w     65.00 109.00   0.50    0.20    --   44.42 138.00 -90.00   88
 21  \w     97.00 123.00   0.50    0.74    --   99.28  67.00   0.00   52
 22  \w     86.00 154.00   0.50    0.74    --   99.28  33.00 120.00  136
 23  \w     21.00 108.00   0.50    0.20    --   44.42  67.00   0.00  174
 24  \w    -64.00 -14.00   0.50    0.20    --  -42.24  67.00   0.00  100
 25  \w    -11.00  30.00   0.50    0.20    --  -42.24  21.00  90.00   82
 26  \w    -24.00  30.00   0.50    0.20    --  -42.24  11.00 150.00  108
 27  \w      0.00  27.00   0.50    0.20    --  -42.24  67.00   0.00   54
 28  \w    -12.00  27.00   0.50    0.20    --  -42.24  11.00-180.00   78
 29  \w   -100.00 -24.00   0.50    0.74    --  -97.09  96.00-150.00  152
 30  \w    -55.00 -30.00   0.50    0.74    --  -97.09 144.00-150.00   50
 31  \w   -126.00 -77.00   0.50    0.74    --  -97.09 144.00-150.00   98
 32  \w   -101.00 -75.00   0.50    0.20    --  -42.24 138.00   0.00   52
 33  \w    -72.00 -46.00   0.50    0.20    --  -42.24 138.00   0.00   52
 34  \w    -71.00 -42.00   0.50    0.74    --  -97.09 144.00  90.00   58
 35  \w    -80.00 -24.00   0.50    0.74    --  -97.09  96.00  60.00  112
 36  \w    -54.00 -29.00   0.50    0.74    --  -97.09 144.00  30.00   50
 37  \w    -78.00 -33.00   0.50    0.74    --  -97.09 117.00   0.00   90
 38  \w   -126.00 -73.00   0.50    0.74    --  -97.09 144.00  30.00  106
 39  \w   -101.00 -24.00   0.50    0.74    --  -97.09  96.00   0.00  154
 40  \w    -56.00 -30.00   0.50    0.74    --  -97.09  50.00-120.00   52
 41  \w    -81.00 -31.00   0.50    0.74    --  -97.09  68.00   0.00  100
 42  \w    -79.00 -54.00   0.50    0.74    --  -97.09  67.00   0.00   50
 43  \w    -68.00 -29.00   0.50    0.74    --  -97.09  59.00 -30.00   78
 44  \w    -57.00 -30.00   0.50    0.74    --  -97.09  50.00 -60.00   54
 45  \w   -106.00 -40.00   0.50    0.74    --  -97.09  77.00 150.00  132
 46  \w    -56.00 -31.00   0.50    0.74    --  -97.09  50.00 150.00   50
 47  \w    -57.00 -31.00   0.50    0.74    --  -97.09  50.00 120.00   52
 48  \w    -68.00 -32.00   0.50    0.74    --  -97.09  59.00  90.00   72
 49  \w    -57.00 -32.00   0.50    0.74    --  -97.09  50.00  90.00   50
 50  \w   -159.00 -87.00   0.50    0.74    --  -97.09 -42.00-120.00  144
 51  \w   -125.00 -76.00   0.50    0.74    --  -97.09 -67.00-133.00   98
 52  \w   -166.00-130.00   0.50    0.74    --  -97.09 -67.00-133.00   72
 53  \w   -162.00 -78.00   0.50    0.74    --  -97.09 -50.00 -90.00  168
 54  \w    -47.00 -18.00   0.50    0.20    --  -42.24 -67.00-133.00   58
 55  \w   -110.00 -60.00   0.50    0.20    --  -42.24 -67.00-133.00  100
 56  \w   -165.00 -89.00   0.50    0.74    --  -97.09 -59.00-180.00  152
 57  \w   -109.00 -66.00   0.50    0.20    --  -42.24-138.00 -60.00   86
 58  \w   -134.00 -83.00   0.50    0.74    --  -97.09 -96.00 -30.00  102
 59  \w   -108.00 -78.00   0.50    0.74    --  -97.09 -86.00   0.00   60
 60  \w   -157.00-113.00   0.50    0.74    --  -97.09 -86.00   0.00   88
;
_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      0.1652151000
_diffrn_orient_matrix_UB_12      0.0285163000
_diffrn_orient_matrix_UB_13      0.0307796000
_diffrn_orient_matrix_UB_21      -0.0233983000
_diffrn_orient_matrix_UB_22      -0.1100803000
_diffrn_orient_matrix_UB_23      -0.0689849000
_diffrn_orient_matrix_UB_31      0.0328898000
_diffrn_orient_matrix_UB_32      0.0798597000
_diffrn_orient_matrix_UB_33      -0.0639455000
_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  0.0631
_diffrn_reflns_av_unetI/netI     0.0847
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            17751
_diffrn_reflns_point_group_measured_fraction_full 0.664
_diffrn_reflns_point_group_measured_fraction_max 0.655
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.593
_diffrn_reflns_theta_min         2.839
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.542
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45978
_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_density_diffrn    1.715
_exptl_crystal_description       block
_exptl_crystal_F_000             926
_refine_diff_density_max         0.339
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_coef       0.0008(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1145
_refine_ls_number_reflns         8938
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0544
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0420P)^2^+0.1758P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1118
_refine_ls_wR_factor_ref         0.1171
_reflns_Friedel_coverage         0.324
_reflns_Friedel_fraction_full    0.328
_reflns_Friedel_fraction_max     0.321
_reflns_number_gt                7923
_reflns_number_total             8938
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03620h2.cif
_cod_data_source_block           exp_945_auto
_cod_depositor_comments
'Adding full bibliography for 7064095--7064099.cif.'
_cod_original_cell_volume        1810.28(7)
_cod_database_code               7064098
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N B F'
_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. Restrained distances
 Cl2-C5 \\sim Cl2A-C5
 with sigma of 0.02
 Cl3-C5 \\sim Cl3A-C5
 with sigma of 0.02
3. Others
 Sof(Cl3A)=Sof(Cl2A)=1-FVAR(1)
 Sof(Cl2)=Sof(Cl3)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C025(H025), C02C(H02C), C02F(H02F), C02I(H02I), C02K(H02K), C02N(H02N),
 C02T(H02T), C02W(H02W), C031(H031), C032(H032), C033(H033), C034(H034),
 C035(H035), C036(H036), C037(H037), C03B(H03J)
4.b Idealised Me refined as rotating group:
 C02O(H02A,H02B,H02D), C03A(H03G,H03H,H03I), C03F(H03A,H03B,H03C), C03G(H03D,
 H03E,H03F)
;
_shelx_res_checksum              8632
_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 1.909
_oxdiff_exptl_absorpt_empirical_full_min 0.522