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_7135297
_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         'C26 H21 N S, 0.25(C H Cl3)'
_chemical_formula_sum            'C26.25 H21.25 Cl0.75 N S'
_chemical_formula_weight         409.34
_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     dual
_audit_creation_date             2022-01-31
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-01-31 deposited with the CCDC.	2025-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                101.038(3)
_cell_angle_beta                 95.116(3)
_cell_angle_gamma                97.429(3)
_cell_formula_units_Z            4
_cell_length_a                   9.4521(4)
_cell_length_b                   14.7452(6)
_cell_length_c                   14.7989(5)
_cell_measurement_reflns_used    20798
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.8480
_cell_measurement_theta_min      1.7790
_cell_volume                     1993.62(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrystalClear-SM Expert 2.1 b46 (Rigaku, 2016)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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 0.888
_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    1.00    --  -15.00  45.00   0.00  360
  2  \w   -105.00  75.00   0.50    1.00    --  -15.00  45.00  90.00  360
  3  \w   -105.00  75.00   0.50    1.00    --  -15.00  45.00 180.00  360
  4  \w   -105.00  75.00   0.50    1.00    --  -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      0.0467053000
_diffrn_orient_matrix_UB_12      0.0177910000
_diffrn_orient_matrix_UB_13      -0.0295343000
_diffrn_orient_matrix_UB_21      -0.0341084000
_diffrn_orient_matrix_UB_22      -0.0354563000
_diffrn_orient_matrix_UB_23      -0.0378509000
_diffrn_orient_matrix_UB_31      -0.0496161000
_diffrn_orient_matrix_UB_32      0.0297226000
_diffrn_orient_matrix_UB_33      -0.0106208000
_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  0.0651
_diffrn_reflns_av_unetI/netI     0.0722
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.888
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            41468
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.888
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.833
_diffrn_reflns_theta_min         1.787
_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    0.276
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91252
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.364
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             858
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.457
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     560
_refine_ls_number_reflns         11137
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0942
_refine_ls_R_factor_gt           0.0600
_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^)+(0.0501P)^2^+1.0567P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1223
_refine_ls_wR_factor_ref         0.1383
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7793
_reflns_number_total             11137
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05926g2.cif
_cod_data_source_block           shoji_autored
_cod_database_code               7135297
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         S1N1C26H21
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.944
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{C49, C149}
{C52, C152}
3. Restrained distances
 Cl1-C53 = Cl2-C53 = Cl3-C53
 1.79 with sigma of 0.02
 Cl1-Cl2 = Cl2-Cl3 = Cl3-Cl1
 2.85 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl2 \\sim Cl3 \\sim C53: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(C53)
\\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C49) = Uanis(C149)
Uanis(C52) = Uanis(C152)
5. Rigid body (RIGU) restrains
 Cl1, Cl2, Cl3, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C149)=Sof(H14A)=Sof(H14B)=Sof(C150)=Sof(H15A)=Sof(H15B)=Sof(C151)=
 Sof(H15C)=Sof(H15D)=Sof(C152)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51A)=
 Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=FVAR(1)
 Fixed Sof: Cl1(0.5) Cl2(0.5) Cl3(0.5) C53(0.5) H53(0.5)
7.a Ternary CH refined with riding coordinates:
 C53(H53)
7.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C49(H49A,
 H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C149(H14A,H14B),
 C150(H15A,H15B), C151(H15C,H15D), C152(H15E,H15F)
7.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C12(H12), C13(H13), C14(H14),
 C17(H17), C18(H18), C19(H19), C20(H20), C27(H27), C29(H29), C31(H31), C32(H32),
  C34(H34), C35(H35), C38(H38), C39(H39), C40(H40), C43(H43), C44(H44),
 C45(H45), C46(H46)
;
_shelx_res_checksum              17336
_shelx_hkl_checksum              37794
_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 1.201
_oxdiff_exptl_absorpt_empirical_full_min 0.740