Stereoselective [4 + 3] annulation of azadienes and ethyl 4-bromo-3-oxobutanoate: construction of benzindeno-fused azepine derivatives.
Shen, Jinhui; Yu, Aimin; Meng, Xiangtai; Organic & biomolecular chemistry 19 (2021) 9026–9030; doi:10.1039/d1ob01749g

data_7158323
_publ_section_title
;
 Stereoselective [4 + 3] annulation of azadienes and ethyl
 4-bromo-3-oxobutanoate: construction of benzindeno-fused azepine
 derivatives.
;
_journal_issue                   41
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9026
_journal_page_last               9030
_journal_paper_doi               10.1039/d1ob01749g
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C28 H25 N O5 S2'
_chemical_formula_sum            'C28 H25 N O5 S2'
_chemical_formula_weight         519.61
_chemical_name_systematic        ss
_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             2019-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-09-07 deposited with the CCDC.	2021-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                84.830(2)
_cell_angle_beta                 78.631(2)
_cell_angle_gamma                85.649(2)
_cell_formula_units_Z            2
_cell_length_a                   8.3217(11)
_cell_length_b                   10.3997(14)
_cell_length_c                   15.418(2)
_cell_measurement_reflns_used    5511
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      27.434
_cell_measurement_theta_min      2.473
_cell_volume                     1300.5(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0212
_diffrn_reflns_av_unetI/netI     0.0232
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            14167
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.473
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.244
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.7020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0399 before and 0.0345 after correction. The Ratio of minimum to maximum transmission is 0.9413. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_description       block
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.371
_refine_diff_density_min         -0.772
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         4576
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0742
_refine_ls_R_factor_gt           0.0615
_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^)+(0.0637P)^2^+2.0487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1495
_refine_ls_wR_factor_ref         0.1605
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3736
_reflns_number_total             4576
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01749g2.cif
_cod_data_source_block           12
_cod_depositor_comments
'Adding full bibliography for 7158322--7158326.cif.'
_cod_database_code               7158323
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.981
_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. Rigid bond restraints
 C16, C17, C18
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C8 \\sim C9 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20: within
1.7A with sigma of 0.001 and sigma for terminal atoms of 0.005
C8 \\sim C9 \\sim C10: within 1.7A with sigma of 0.001 and sigma for terminal
atoms of 0.005
4.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14)
4.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C13(H13A,H13B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C25(H25), C26(H26), C27(H27), C28(H28)
4.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              91646
_olex2_submission_special_instructions 'No special instructions were received'