Synthesis of benzoazepine derivatives via Rh(iii)-catalyzed inert C(sp<sup>2</sup>)-H functionalization and [4 + 3] annulation.
Xu, Yuanshuang; Zhang, Linghua; Liu, Mengyang; Zhang, Xiaopeng; Zhang, Xinying; Fan, Xuesen; Organic & biomolecular chemistry 17 (2019) 8706–8710; doi:10.1039/c9ob01830a

data_7157083
_publ_section_title
;
 Synthesis of benzoazepine derivatives via Rh(iii)-catalyzed inert
 C(sp<sup>2</sup>)-H functionalization and [4 + 3] annulation.
;
_journal_issue                   38
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8706
_journal_page_last               8710
_journal_paper_doi               10.1039/c9ob01830a
_journal_volume                  17
_journal_year                    2019
_chemical_formula_moiety         'C21 H17 Br N2 O2, C2 H6 O S'
_chemical_formula_sum            'C23 H23 Br N2 O3 S'
_chemical_formula_weight         487.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-06-25
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_audit_update_record
;
2019-06-25 deposited with the CCDC.    2019-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.876(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.7087(6)
_cell_length_b                   24.8530(16)
_cell_length_c                   10.4060(8)
_cell_measurement_reflns_used    4880
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      28.1940
_cell_measurement_theta_min      3.8980
_cell_volume                     2104.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.868
_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    -53.00  35.00   1.00   12.22    --   15.82 -38.00 150.00   88
  2  \w     -1.00  83.00   1.00   12.22    --   15.82  57.00 -30.00   84
  3  \w    -78.00 -31.00   1.00   12.22    --  -17.23 138.00 141.00   47
  4  \w    -85.00   8.00   1.00   12.22    --  -17.23 -77.00 -30.00   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0137141000
_diffrn_orient_matrix_UB_12      -0.0103710000
_diffrn_orient_matrix_UB_13      0.0584436000
_diffrn_orient_matrix_UB_21      -0.0030509000
_diffrn_orient_matrix_UB_22      0.0265774000
_diffrn_orient_matrix_UB_23      0.0238216000
_diffrn_orient_matrix_UB_31      -0.0860816000
_diffrn_orient_matrix_UB_32      0.0007161000
_diffrn_orient_matrix_UB_33      -0.0365874000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.868
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            13912
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.868
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.184
_diffrn_reflns_theta_min         3.510
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.081
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69040
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.538
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.245
_refine_diff_density_min         -0.586
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         4931
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0532
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0353P)^2^+2.6020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0884
_refine_ls_wR_factor_ref         0.0936
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4128
_reflns_number_total             4931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01830a2.cif
_cod_data_source_block           3g
_cod_depositor_comments
'Adding full bibliography for 7157080--7157083.cif.'
_cod_database_code               7157083
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2A), C4(H4), C8(H8), C9(H9), C10(H10), C16(H16), C17(H17),
 C18(H18), C20(H20)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_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 1.422
_oxdiff_exptl_absorpt_empirical_full_min 0.772