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_7158324
_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 H29 N O5 S'
_chemical_formula_sum            'C29 H29 N O5 S'
_chemical_formula_weight         503.59
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-23
_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                90
_cell_angle_beta                 102.3890(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.04250(10)
_cell_length_b                   16.36150(10)
_cell_length_c                   14.86460(10)
_cell_measurement_reflns_used    16036
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.9560
_cell_measurement_theta_min      3.0480
_cell_volume                     2623.08(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 0.998
_diffrn_measured_fraction_theta_max 0.995
_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    -39.00   3.00   0.50    1.00    --   42.30 -82.00-150.00   84
  2  \w     38.00  70.00   0.50    1.00    --   42.30 -82.00 -60.00   64
  3  \w    -47.00   3.00   0.50    1.00    --   42.30 -77.00-180.00  100
  4  \w     27.00  70.00   0.50    1.00    --   42.30 -82.00-150.00   86
  5  \w     -2.00  71.00   0.50    1.00    --   42.30 -54.00-150.00  146
  6  \w     82.00 131.00   0.50    1.00    --   42.30  11.00 -90.00   98
  7  \w     15.00  69.00   0.50    1.00    --   42.30 -82.00  60.00  108
  8  \w     11.00  59.00   0.50    1.00    --   42.30 -77.00-180.00   96
  9  \w     33.00  64.00   0.50    1.00    --   42.30 -65.00 -90.00   62
 10  \w    -47.00  23.00   0.50    1.00    --   42.30 -82.00   0.00  140
 11  \w     29.00  70.00   0.50    1.00    --   42.30 -82.00 120.00   82
 12  \w    -39.00  14.00   0.50    1.00    --   42.30 -77.00  60.00  106
 13  \w     26.00  58.00   0.50    1.00    --   42.30 -77.00  60.00   64
 14  \w    -28.00  16.00   0.50    1.00    --   42.30 -82.00 120.00   88
 15  \w     21.00  70.00   0.50    1.00    --   42.30  11.00 -90.00   98
 16  \w    -46.00  -7.00   0.50    1.00    --   42.30  11.00 -90.00   78
 17  \w    -45.00   7.00   0.50    1.00    --   42.30 -82.00  60.00  104
 18  \w     -1.00  25.00   0.50    1.00    --   42.30 -82.00 -60.00   52
 19  \w     77.00 103.00   0.50    1.00    --   42.30  82.00 -90.00   52
 20  \w     15.00  65.00   0.50    1.00    --   42.30  82.00 -90.00  100
 21  \w    -45.00 -19.00   0.50    1.00    --   42.30 -65.00 -90.00   52
 22  \w     37.00  68.00   0.50    1.00    --   42.30 -82.00   0.00   62
 23  \w     86.00 112.00   0.50    2.46    --   93.70 -50.00  60.00   52
 24  \w     11.00  86.00   0.50    2.46    --   93.70 -33.00 120.00  150
 25  \w     12.00 120.00   0.50    2.46    --   93.70 -82.00-150.00  216
 26  \w      5.00  42.00   0.50    2.46    --   93.70 -50.00  60.00   74
 27  \w     35.00 102.00   0.50    2.46    --   93.70 -82.00 -90.00  134
 28  \w     42.00 121.00   0.50    2.46    --   93.70 -82.00  90.00  158
 29  \w     13.00  96.00   0.50    2.46    --   93.70 -82.00  30.00  166
 30  \w     70.00  96.00   0.50    2.46    --   93.70 -82.00   0.00   52
 31  \w     12.00 121.00   0.50    2.46    --   93.70 -33.00 -60.00  218
 32  \w     66.00  92.00   0.50    2.46    --   93.70 -82.00-180.00   52
 33  \w    138.00 168.00   0.50    2.46    --   93.70  59.00  30.00   60
 34  \w    106.00 132.00   0.50    2.46    --   93.70  59.00  30.00   52
 35  \w     69.00  95.00   0.50    2.46    --   93.70 -82.00 -60.00   52
 36  \w      4.00  98.00   0.50    2.46    --   93.70 -82.00 150.00  188
 37  \w      4.00  70.00   0.50    2.46    --   93.70 -82.00-120.00  132
 38  \w     11.00  60.00   0.50    2.46    --   93.70 -77.00 120.00   98
 39  \w      4.00  98.00   0.50    2.46    --   93.70 -82.00 -30.00  188
 40  \w     80.00 106.00   0.50    2.46    --   93.70 -82.00 120.00   52
 41  \w     89.00 114.00   0.50    2.46    --   93.70 -59.00  90.00   50
 42  \w    108.00 153.00   0.50    2.46    --   93.70  50.00   0.00   90
 43  \w     37.00  93.00   0.50    2.46    --   93.70 -82.00  60.00  112
 44  \w      6.00  32.00   0.50    2.46    --   93.70 -59.00  90.00   52
 45  \w      4.00  49.00   0.50    2.46    --   93.70 -68.00 -90.00   90
 46  \w     35.00  68.00   0.50    2.46    --   93.70 -82.00   0.00   66
 47  \w      4.00 182.00   0.50    2.46    --   93.70   0.00-150.00  356
 48  \w      6.00  54.00   0.50    2.46    --   93.70 -77.00 -60.00   96
;
_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      -0.0343416000
_diffrn_orient_matrix_UB_12      0.0912621000
_diffrn_orient_matrix_UB_13      -0.0107981000
_diffrn_orient_matrix_UB_21      -0.0734180000
_diffrn_orient_matrix_UB_22      -0.0076877000
_diffrn_orient_matrix_UB_23      0.0767486000
_diffrn_orient_matrix_UB_31      0.1176766000
_diffrn_orient_matrix_UB_32      0.0218556000
_diffrn_orient_matrix_UB_33      0.0724402000
_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  0.0225
_diffrn_reflns_av_unetI/netI     0.0148
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            26154
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.227
_diffrn_reflns_theta_min         4.071
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.417
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91025
_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    1.275
_exptl_crystal_description       block
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.324
_refine_diff_density_rms         0.028
_refine_ls_extinction_coef       0.00116(14)
_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   1.077
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     337
_refine_ls_number_reflns         4776
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0393
_refine_ls_R_factor_gt           0.0354
_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^)+(0.0553P)^2^+0.3641P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1036
_refine_ls_wR_factor_ref         0.1069
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4210
_reflns_number_total             4776
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob01749g2.cif
_cod_data_source_block           exp_1164_auto
_cod_depositor_comments
'Adding full bibliography for 7158322--7158326.cif.'
_cod_database_code               7158324
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.765
_shelx_estimated_absorpt_t_min   0.676
_reflns_odcompleteness_completeness 99.65
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C8(H8), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C26(H26A,H26B)
2.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C35(H35), C12(H12), C15(H15), C31(H31), C34(H34), C14(H14),
 C17(H17), C32(H32), C13(H13), C20(H20), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C36(H36A,H36B,H36C)
2.e Idealised tetrahedral OH refined as rotating group:
 O29(H29)
;
_shelx_res_checksum              61391
_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 2.084
_oxdiff_exptl_absorpt_empirical_full_min 0.749