Synthesis of naphth[2,1-<i>a</i>]azulenes <i>via</i> [8 + 2] cycloaddition of 2<i>H</i>-cyclohepta[<i>b</i>]furan-2-ones, and their reactivity, optical, and structural properties.
Shoji, Taku; Yamazaki, Akari; Yoshida, Miku; Yasunami Deceased, Masafumi; Mori, Shigeki; Okujima, Tetsuo; Kamayachi, Takumi; Uchiyama, Ikumi; Sekiguchi, Ryuta; Ito, Shunji; Organic & biomolecular chemistry 23 (2025) 10088–10099; doi:10.1039/d5ob01492a

data_7160795
_publ_section_title
;
 Synthesis of naphth[2,1-<i>a</i>]azulenes <i>via</i> [8 + 2]
 cycloaddition of 2<i>H</i>-cyclohepta[<i>b</i>]furan-2-ones, and their
 reactivity, optical, and structural properties.
;
_journal_issue                   44
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10088
_journal_page_last               10099
_journal_paper_doi               10.1039/d5ob01492a
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C31 H20 Cl2 N2'
_chemical_formula_sum            'C31 H20 Cl2 N2'
_chemical_formula_weight         491.39
_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             2025-09-13
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-16 deposited with the CCDC.	2025-10-13 downloaded from the CCDC.
;
_cell_angle_alpha                102.566(3)
_cell_angle_beta                 96.090(3)
_cell_angle_gamma                96.304(3)
_cell_formula_units_Z            2
_cell_length_a                   6.1306(2)
_cell_length_b                   10.2833(4)
_cell_length_c                   19.6907(8)
_cell_measurement_reflns_used    13233
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.4810
_cell_measurement_theta_min      2.0180
_cell_volume                     1193.44(8)
_computing_cell_refinement       'CrysAlisPro 1.171.44.85 (Rigaku OD, 2024)'
_computing_data_collection       'CrystalClear-SM Expert 2.1 b46 (Rigaku, 2016)'
_computing_data_reduction        'CrysAlisPro 1.171.44.85 (Rigaku OD, 2024)'
_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 0.908
_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      -0.0530422000
_diffrn_orient_matrix_UB_12      0.0549204000
_diffrn_orient_matrix_UB_13      -0.0063905000
_diffrn_orient_matrix_UB_21      0.0188612000
_diffrn_orient_matrix_UB_22      -0.0165558000
_diffrn_orient_matrix_UB_23      -0.0355915000
_diffrn_orient_matrix_UB_31      -0.1030911000
_diffrn_orient_matrix_UB_32      -0.0424165000
_diffrn_orient_matrix_UB_33      -0.0089088000
_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  0.0792
_diffrn_reflns_av_unetI/netI     0.0681
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.908
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            24960
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.908
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.762
_diffrn_reflns_theta_min         2.048
_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    0.296
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69381
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.85 (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.505
_refine_diff_density_min         -0.838
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     329
_refine_ls_number_reflns         6765
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0864
_refine_ls_R_factor_gt           0.0604
_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^)+(0.0772P)^2^+0.1567P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1374
_refine_ls_wR_factor_ref         0.1507
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5006
_reflns_number_total             6765
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01492a2.cif
_cod_data_source_block           shoji_6_autored
_cod_depositor_comments
'Adding full bibliography for 7160792--7160797.cif.'
_cod_database_code               7160795
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Cl2N2C31H20
_cell_oxdiff_angle_alpha         102.566(3)
_cell_oxdiff_angle_beta          96.090(3)
_cell_oxdiff_angle_gamma         96.304(3)
_cell_oxdiff_length_a            6.1306(2)
_cell_oxdiff_length_b            10.2833(4)
_cell_oxdiff_length_c            19.6907(8)
_cell_oxdiff_measurement_reflns_used 13233
_cell_oxdiff_volume              1193.44(8)
_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
2. Others
 Sof(H25A)=Sof(C126)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(1)
 Sof(H25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C25(H25A), C25(H25)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C10(H10), C11(H11), C12(H12),
 C14(H14), C20(H20), C23(H23), C24(H24), C28(H28)
3.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C126(H12A,H12B,H12C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              42755
_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 1.734
_oxdiff_exptl_absorpt_empirical_full_min 0.470