Synthesis of 6-Amino- and 6-Arylazoazulenes via Nucleophilic Aromatic Substitution and Their Reactivity and Properties.
Shoji, Taku; Sugiyama, Shuhei; Takeuchi, Mutsumi; Ohta, Akira; Sekiguchi, Ryuta; Ito, Shunji; Yatsu, Tomoaki; Okujima, Tetsuo; Yasunami, Masafumi; The Journal of organic chemistry 84 (2019) 1257–1275; doi:10.1021/acs.joc.8b02648

data_4037542
_publ_section_title
;
 Synthesis of 6-Amino- and 6-Arylazoazulenes via Nucleophilic Aromatic
 Substitution and Their Reactivity and Properties.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1257
_journal_page_last               1275
_journal_paper_doi               10.1021/acs.joc.8b02648
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C21 H23 Br2 N O4'
_chemical_formula_sum            'C21 H23 Br2 N O4'
_chemical_formula_weight         513.22
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2016/6
_cell_angle_alpha                90
_cell_angle_beta                 94.933(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.84176(19)
_cell_length_b                   18.7757(5)
_cell_length_c                   21.9789(9)
_cell_measurement_reflns_used    13524
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.31
_cell_measurement_theta_min      2.12
_cell_volume                     1990.64(13)
_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 4.2.4 (Rigaku, 2016)'
_computing_publication_material  'CrystalStructure 4.2.4'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 7.111
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0547
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            33794
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.999
_diffrn_reflns_theta_min         1.860
_diffrn_source                   'Varimax 50 kV 24 mA Rotating anode'
_exptl_absorpt_coefficient_mu    4.100
_exptl_absorpt_correction_T_max  0.960
_exptl_absorpt_correction_T_min  0.636
_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    1.712
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1032
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.010
_refine_diff_density_max         0.588
_refine_diff_density_min         -0.875
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         4820
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0331
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0267P)^2^+2.8188P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0665
_refine_ls_wR_factor_ref         0.0708
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4043
_reflns_number_total             4820
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02648_si_002.cif
_cod_data_source_block           shelxl
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4037542
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_min   0.373
_shelx_estimated_absorpt_t_max   0.960
_shelx_res_checksum              88762
_shelx_hkl_checksum              13434