Azulenes exhibiting solid-state fluorescence: synthesis and photophysics of 2-aryl-6-pyrrolidinylazulenes.
Shoji, Taku; Ariga, Yukino; Ito, Daichi; Ito, Fuyuki; Hamasaki, Atom; Mori, Shigeki; Okujima, Tetsuo; Sekiguchi, Ryuta; Ito, Shunji; Chemical communications (Cambridge, England) 61 (2025) 19481–19484; doi:10.1039/d5cc05926g

data_7135299
_publ_section_title
;
 Azulenes exhibiting solid-state fluorescence: synthesis and photophysics
 of 2-aryl-6-pyrrolidinylazulenes.
;
_journal_issue                   98
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              19481
_journal_page_last               19484
_journal_paper_doi               10.1039/d5cc05926g
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C32 H29 N O4 S, 0.171(H2 O)'
_chemical_formula_sum            'C32 H29.34 N O4.17 S'
_chemical_formula_weight         526.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-16
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7308)
;
_audit_update_record
;
2025-07-16 deposited with the CCDC.	2025-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.603(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.2097(4)
_cell_length_b                   12.1202(4)
_cell_length_c                   21.9452(8)
_cell_measurement_reflns_used    22609
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.6170
_cell_measurement_theta_min      1.8690
_cell_volume                     2669.21(17)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection       'CrystalClear-SM Expert 2.1 b46 (Rigaku, 2016)'
_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-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 7.111
_diffrn_detector_type            'Rigaku Saturn724+ area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.939
_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   -105.00  75.00   0.50    2.00    --  -15.00  45.00   0.00  360
  2  \w   -105.00  75.00   0.50    2.00    --  -15.00  45.00  90.00  360
  3  \w   -105.00  75.00   0.50    2.00    --  -15.00  45.00 180.00  360
  4  \w   -105.00  75.00   0.50    2.00    --  -15.00  45.00 270.00  360
;
_diffrn_measurement_device       'AFC11 SATURN724+ Right'
_diffrn_measurement_device_type  'Rigaku Varimax with Saturn'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0611886000
_diffrn_orient_matrix_UB_12      0.0273686000
_diffrn_orient_matrix_UB_13      0.0110135000
_diffrn_orient_matrix_UB_21      -0.0324760000
_diffrn_orient_matrix_UB_22      0.0351825000
_diffrn_orient_matrix_UB_23      0.0183522000
_diffrn_orient_matrix_UB_31      0.0140249000
_diffrn_orient_matrix_UB_32      -0.0379359000
_diffrn_orient_matrix_UB_33      0.0249583000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1012
_diffrn_reflns_av_unetI/netI     0.0709
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            56326
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.872
_diffrn_reflns_theta_min         1.888
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'MicroMax 007'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.161
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89207
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1111
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.549
_refine_diff_density_min         -0.652
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     358
_refine_ls_number_reflns         7909
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1011
_refine_ls_R_factor_gt           0.0654
_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^)+(0.0689P)^2^+1.6601P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1411
_refine_ls_wR_factor_ref         0.1583
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5644
_reflns_number_total             7909
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05926g2.cif
_cod_data_source_block           shoji_b_autored
_cod_database_code               7135299
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         S1O4N1C32H29
_cell_oxdiff_angle_alpha         90.011(3)
_cell_oxdiff_angle_beta          100.611(3)
_cell_oxdiff_angle_gamma         89.998(3)
_cell_oxdiff_length_a            10.2102(3)
_cell_oxdiff_length_b            12.1182(4)
_cell_oxdiff_length_c            21.9486(7)
_cell_oxdiff_measurement_reflns_used 22607
_cell_oxdiff_volume              2669.24(15)
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Others
 Sof(O5)=Sof(H5A)=Sof(H5B)=FVAR(1)
3.a Free rotating group:
 O5(H5A,H5B)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,
 H31B), C32(H32A,H32B)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C8(H8), C9(H9), C15(H15), C16(H16), C17(H17), C20(H20),
 C21(H21), C22(H22), C23(H23)
3.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              46828
_shelx_hkl_checksum              78837
_olex2_exptl_crystal_mounting_method loop
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.571
_oxdiff_exptl_absorpt_empirical_full_min 0.656