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_7158325
_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         'C29 H27 N O7 S'
_chemical_formula_sum            'C29 H27 N O7 S'
_chemical_formula_weight         533.57
_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             2021-08-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-09-07 deposited with the CCDC.	2021-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                112.119(2)
_cell_angle_beta                 96.2310(10)
_cell_angle_gamma                100.0470(10)
_cell_formula_units_Z            2
_cell_length_a                   8.19470(10)
_cell_length_b                   13.0078(2)
_cell_length_c                   13.8955(2)
_cell_measurement_reflns_used    6931
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.9720
_cell_measurement_theta_min      3.4920
_cell_volume                     1326.27(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.964
_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    -15.00  68.00   0.50    0.50    --   42.30 -82.00 150.00  166
  2  \w    -43.00 -15.00   0.50    0.50    --   42.30 -82.00 -60.00   56
  3  \w    -29.00  15.00   0.50    0.50    --   42.30 -54.00-150.00   88
  4  \w    -43.00  -9.00   0.50    0.50    --   42.30 -82.00-150.00   68
  5  \w      9.00  38.00   0.50    0.50    --   42.30 -82.00  60.00   58
  6  \w     -1.00  70.00   0.50    0.50    --   42.30 -82.00 -60.00  142
  7  \w     41.00  66.00   0.50    0.50    --   42.30  82.00 -30.00   50
  8  \w     16.00  73.00   0.50    0.50    --   42.30  82.00 -60.00  114
  9  \w     11.00  64.00   0.50    0.50    --   42.30 -65.00 -30.00  106
 10  \w      0.00  48.00   0.50    0.50    --   42.30 -82.00-150.00   96
 11  \w    -23.00  35.00   0.50    0.50    --   42.30 -77.00  60.00  116
 12  \w     42.00  69.00   0.50    0.50    --   42.30 -82.00  60.00   54
 13  \w     27.00  52.00   0.50    0.50    --   42.30  82.00-120.00   50
 14  \w    -45.00 -19.00   0.50    0.50    --   42.30 -82.00  60.00   52
 15  \w     62.00 130.00   0.50    0.50    --   42.30  82.00-120.00  136
 16  \w     78.00 132.00   0.50    0.50    --   42.30  82.00 -60.00  108
 17  \w     19.00  44.00   0.50    0.50    --   42.30 -77.00 -30.00   50
 18  \w    -43.00  14.00   0.50    0.50    --   42.30 -77.00 -30.00  114
 19  \w     68.00 175.00   0.50    0.50    --   93.70  50.00-150.00  214
 20  \w     57.00 109.00   0.50    0.50    --   93.70 -82.00-180.00  104
 21  \w      4.00  52.00   0.50    0.50    --   93.70 -82.00-180.00   96
 22  \w    129.00 183.00   0.50    0.50    --   93.70  59.00 150.00  108
 23  \w     72.00 169.00   0.50    0.50    --   93.70  68.00 120.00  194
 24  \w     44.00  97.00   0.50    0.50    --   93.70 -82.00  30.00  106
 25  \w     17.00  73.00   0.50    0.50    --   93.70 -82.00 150.00  112
 26  \w     99.00 183.00   0.50    0.50    --   93.70  68.00  60.00  168
 27  \w      7.00 101.00   0.50    0.50    --   93.70 -82.00 -90.00  188
 28  \w     32.00  93.00   0.50    0.50    --   93.70 -82.00-120.00  122
 29  \w     27.00  58.00   0.50    0.50    --   93.70 -82.00  60.00   62
 30  \w     76.00 106.00   0.50    0.50    --   93.70 -82.00  60.00   60
 31  \w     10.00  35.00   0.50    0.50    --   93.70 -82.00 120.00   50
 32  \w     17.00  86.00   0.50    0.50    --   93.70 -82.00 -30.00  138
 33  \w     36.00 121.00   0.50    0.50    --   93.70 -82.00   0.00  170
 34  \w     64.00 126.00   0.50    0.50    --   93.70  50.00-120.00  124
 35  \w     71.00 152.00   0.50    0.50    --   93.70  68.00  90.00  162
 36  \w     45.00 118.00   0.50    0.50    --   93.70 -82.00 120.00  146
 37  \w     77.00 102.00   0.50    0.50    --   93.70  68.00 -30.00   50
 38  \w     50.00  95.00   0.50    0.50    --   93.70 -82.00 -60.00   90
 39  \w     83.00 183.00   0.50    0.50    --   93.70  33.00-180.00  200
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0742620000
_diffrn_orient_matrix_UB_12      -0.0752831000
_diffrn_orient_matrix_UB_13      -0.0910975000
_diffrn_orient_matrix_UB_21      0.0811829000
_diffrn_orient_matrix_UB_22      -0.0480929000
_diffrn_orient_matrix_UB_23      0.0740274000
_diffrn_orient_matrix_UB_31      -0.1603940000
_diffrn_orient_matrix_UB_32      -0.0964792000
_diffrn_orient_matrix_UB_33      -0.0329463000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11874
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.274
_diffrn_reflns_theta_min         3.498
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.492
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44856
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.336
_exptl_crystal_description       block
_exptl_crystal_F_000             560
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.044
_refine_ls_extinction_coef       0.0134(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         4682
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0410
_refine_ls_shift/su_max          0.013
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0624P)^2^+0.1890P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1140
_refine_ls_wR_factor_ref         0.1183
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4128
_reflns_number_total             4682
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01749g2.cif
_cod_data_source_block           exp_1161_auto
_cod_depositor_comments
'Adding full bibliography for 7158322--7158326.cif.'
_cod_original_cell_volume        1326.26(4)
_cod_database_code               7158325
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 97.36
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C6(H6), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C20(H20), C37(H37), C19(H19), C17(H17), C11(H11), C14(H14),
 C36(H36), C33(H33), C34(H34), C13(H13), C12(H12)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C38(H38A,H38B,H38C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              30284
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.685
_oxdiff_exptl_absorpt_empirical_full_min 0.523