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_7157080
_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         '2(C25 H26 N2 O2)'
_chemical_formula_sum            'C50 H52 N4 O4'
_chemical_formula_weight         772.95
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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                92.305(2)
_cell_angle_beta                 111.817(3)
_cell_angle_gamma                103.594(3)
_cell_formula_units_Z            2
_cell_length_a                   12.8963(5)
_cell_length_b                   13.1501(3)
_cell_length_c                   17.1010(5)
_cell_measurement_reflns_used    10524
_cell_measurement_temperature    289(3)
_cell_measurement_theta_max      71.2460
_cell_measurement_theta_min      4.4270
_cell_volume                     2590.69(16)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      289(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_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   -105.00  34.00   1.00    1.49    --  -35.37   0.00 -30.00  139
  2  \w   -105.00 -16.00   1.00    1.49    --  -35.37 -38.00 120.00   89
  3  \w    -52.00  32.00   1.00    1.49    --  -35.37  57.00  -1.00   84
  4  \w     23.00  89.00   1.00    1.49    --   35.37-125.00-120.00   66
  5  \w     23.00  89.00   1.00    1.49    --   35.37-125.00 150.00   66
  6  \w     23.00  89.00   1.00    1.49    --   35.37-125.00  90.00   66
  7  \w     23.00  89.00   1.00    1.49    --   35.37-125.00 -60.00   66
  8  \w     40.00 125.00   1.00    6.00    --  106.50 -61.00 120.00   85
  9  \w     88.00 173.00   1.00    6.00    --  106.50  61.00  30.00   85
 10  \w     37.00 176.00   1.00    6.00    --  106.50   0.00-150.00  139
 11  \w     37.00 109.00   1.00    6.00    --  106.50 -95.00  60.00   72
 12  \w     37.00 128.00   1.00    6.00    --  106.50 -30.00   0.00   91
 13  \w     37.00 112.00   1.00    6.00    --  106.50-111.00 150.00   75
 14  \w     37.00 112.00   1.00    6.00    --  106.50-111.00   0.00   75
 15  \w     88.00 173.00   1.00    6.00    --  106.50  61.00-150.00   85
 16  \w     80.00 174.00   1.00    6.00    --  106.50  77.00  60.00   94
 17  \w     37.00 112.00   1.00    6.00    --  106.50-111.00 -90.00   75
 18  \w     38.00 124.00   1.00    6.00    --  106.50 -45.00 -90.00   86
 19  \w     38.00 124.00   1.00    6.00    --  106.50 -45.00  90.00   86
 20  \w     40.00 125.00   1.00    6.00    --  106.50 -61.00-120.00   85
 21  \w     39.00 133.00   1.00    6.00    --  106.50 -77.00   0.00   94
 22  \w     37.00 109.00   1.00    6.00    --  106.50 -95.00-150.00   72
 23  \w   -103.00  -9.00   1.00    1.49    --  -35.37 -77.00 -90.00   94
;
_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      0.1090452000
_diffrn_orient_matrix_UB_12      0.0143184000
_diffrn_orient_matrix_UB_13      -0.0201699000
_diffrn_orient_matrix_UB_21      0.0584763000
_diffrn_orient_matrix_UB_22      0.1029516000
_diffrn_orient_matrix_UB_23      0.0634786000
_diffrn_orient_matrix_UB_31      0.0504329000
_diffrn_orient_matrix_UB_32      -0.0633988000
_diffrn_orient_matrix_UB_33      0.0719146000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0210
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24264
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.254
_diffrn_reflns_theta_min         3.493
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.497
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84964
_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    0.991
_exptl_crystal_description       needle
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_platon_squeeze_details
;
TITL 3bb_a.res in P-1
CELL   12.8963   13.1501   17.1010     92.31    111.82    103.59
SPGR P-1
C101 0.799 0.908 0.073 !      10.61 eA-3
C102 0.482 0.900 0.126 !       5.38 eA-3
C103 0.901 0.922 0.058 !       4.17 eA-3
C104 0.841 0.854 0.190 !       2.77 eA-3
C105 0.702 0.784 0.014 !       2.71 eA-3
C106 0.438 0.887 0.223 !       2.01 eA-3
C107 0.602 0.977 0.138 !       1.94 eA-3
C108 0.411 1.005 0.094 !       1.51 eA-3
C109 0.620 0.892 0.220 !       1.08 eA-3
Q110 0.606 0.535 0.177 !       0.57 eA-3
;
_refine_diff_density_max         0.410
_refine_diff_density_min         -0.338
_refine_diff_density_rms         0.035
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     531
_refine_ls_number_reflns         9887
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0637
_refine_ls_R_factor_gt           0.0537
_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^)+(0.0824P)^2^+0.3952P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1524
_refine_ls_wR_factor_ref         0.1603
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8040
_reflns_number_total             9887
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01830a2.cif
_cod_data_source_block           3bb_sq
_cod_depositor_comments
'Adding full bibliography for 7157080--7157083.cif.'
_cod_original_cell_volume        2590.69(15)
_cod_database_code               7157080
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.907
_reflns_odcompleteness_completeness 99.90
_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. Rigid bond restraints
 C42, C43
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
3.a Ternary CH refined with riding coordinates:
 C12(H12), C13(H13), C21(H21), C37(H37), C38(H38), C46(H46)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C39(H39A,H39B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C16(H16), C17(H17),
 C19(H19), C20(H20), C26(H26), C27(H27), C30(H30), C31(H31), C32(H32), C33(H33),
  C35(H35), C41(H41), C42(H42), C44(H44), C45(H45)
3.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C47(H47A,H47B,
 H47C), C48(H48A,H48C,H48B), C50(H50A,H50B,H50C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1A), O3(H3)
;
_platon_squeeze_void_probe_radius 1.20
_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 1.317
_oxdiff_exptl_absorpt_empirical_full_min 0.649