Synthesis of 2,3-Dihydro-1H-azepine and 1H-Azepin-2(3H)-one Derivatives From Intramolecular Condensation between Stable Tertiary Enamides and Aldehydes.
Zhu, Wenju; Zhao, Liang; Wang, Mei-Xiang; The Journal of organic chemistry 80 (2015) 12047–12057; doi:10.1021/acs.joc.5b02021

data_4036446
_publ_section_title
;
 Synthesis of 2,3-Dihydro-1H-azepine and 1H-Azepin-2(3H)-one Derivatives
 From Intramolecular Condensation between Stable Tertiary Enamides and
 Aldehydes.
;
_journal_issue                   24
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12047
_journal_page_last               12057
_journal_paper_doi               10.1021/acs.joc.5b02021
_journal_volume                  80
_journal_year                    2015
_chemical_formula_moiety         'C19 H16 Br N O'
_chemical_formula_sum            'C19 H16 Br N O'
_chemical_formula_weight         354.24
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-08-28
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 111.247(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.013(6)
_cell_length_b                   6.262(2)
_cell_length_c                   18.876(7)
_cell_measurement_reflns_used    4752
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4852
_cell_measurement_theta_min      1.5592
_cell_volume                     1543.8(10)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution
;
'SHELXT (Sheldrick, 2014)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 5.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 180.0000
	             XTD: 45.0238
	          2theta: -19.9189
scan:
	Number of images: 270
	           Slice: -76.2500 - 58.7500
	     Image width: 0.5000
	        Exp time: 5.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 0.0000
	             XTD: 45.0238
	          2theta: -19.9189
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0749
_diffrn_orient_matrix_UB_12      -0.0090
_diffrn_orient_matrix_UB_13      0.0134
_diffrn_orient_matrix_UB_21      -0.0126
_diffrn_orient_matrix_UB_22      -0.0902
_diffrn_orient_matrix_UB_23      -0.1312
_diffrn_orient_matrix_UB_31      -0.0098
_diffrn_orient_matrix_UB_32      -0.0457
_diffrn_orient_matrix_UB_33      0.0324
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10024
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.541
_diffrn_reflns_theta_min         3.119
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.664
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7279
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.343
_refine_diff_density_min         -0.483
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         3524
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0329
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0212P)^2^+1.1069P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0674
_refine_ls_wR_factor_ref         0.0691
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3295
_reflns_number_total             3524
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b02021_si_002.cif
_cod_data_source_block           sa4319
_cod_original_cell_volume        1543.7(10)
_cod_database_code               4036446
_shelxl_version_number           2013-4
_diffrn_number_total             3856
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C15(H15),
 C16(H16), C18(H18), C19(H19)
;
_shelx_res_checksum              41941
_shelx_hkl_checksum              33001
_olex2_submission_special_instructions 'No special instructions were received'