Synthesis of 2-amino- and 2-arylazoazulenes via nucleophilic aromatic substitution of 2-chloroazulenes with amines and arylhydrazines
Shoji, Taku; Sugiyama, Shuhei; Araki, Takanori; Ohta, Akira; Sekiguchi, Ryuta; Ito, Shunji; Mori, Shigeki; Okujima, Tetsuo; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB00691H

data_7155580
_publ_section_title
;
 Synthesis of 2-amino- and 2-arylazoazulenes via nucleophilic aromatic
 substitution of 2-chloroazulenes with amines and arylhydrazines
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB00691H
_journal_year                    2017
_chemical_formula_moiety         'C23 H22 N2 O4'
_chemical_formula_sum            'C23 H22 N2 O4'
_chemical_formula_weight         390.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_audit_update_record
;
2016-11-24 deposited with the CCDC.
2017-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.085(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.5798(6)
_cell_length_b                   15.4279(8)
_cell_length_c                   16.6633(7)
_cell_measurement_reflns_used    20362
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.28
_cell_measurement_theta_min      1.82
_cell_volume                     4005.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'CrystalStructure 4.2.2 (Rigaku, 2016)'
_computing_publication_material  'CrystalStructure 4.2.2 (Rigaku, 2016)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 7.111
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Rigaku Saturn724'
_diffrn_measurement_method       \w
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0682
_diffrn_reflns_av_unetI/netI     0.0886
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            68739
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.996
_diffrn_reflns_theta_min         1.788
_diffrn_source                   'Varimax 50 kV 24 mA Rotating anode'
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  0.998
_exptl_absorpt_correction_T_min  0.750
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.295
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1648
_exptl_crystal_size_max          0.120
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.020
_refine_diff_density_max         0.369
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 3696 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.4(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1272
_refine_ls_number_reflns         19261
_refine_ls_number_restraints     1351
_refine_ls_restrained_S_all      0.984
_refine_ls_R_factor_all          0.1309
_refine_ls_R_factor_gt           0.0647
_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^)+(0.0600P)^2^+0.3032P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1216
_refine_ls_wR_factor_ref         0.1448
_reflns_Friedel_coverage         0.925
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                11246
_reflns_number_total             19261
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob00691h2.cif
_cod_data_source_block           shelxl
_cod_database_code               7155580
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.989
_shelx_estimated_absorpt_t_max   0.998
_shelx_res_checksum              60117