Capture-Collapse Heterocyclization: 1,3-Diazepanes by C-N Reductive Elimination from Rhodacyclopentanones.
McCreanor, Niall G.; Stanton, Steven; Bower, John F.; Journal of the American Chemical Society 138 (2016) 11465–11468; doi:10.1021/jacs.6b07046

data_4130804
_publ_section_title
;
 Capture-Collapse Heterocyclization: 1,3-Diazepanes by C-N Reductive
 Elimination from Rhodacyclopentanones.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11465
_journal_page_last               11468
_journal_paper_doi               10.1021/jacs.6b07046
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C19 H22 N2 O'
_chemical_formula_sum            'C19 H22 N2 O'
_chemical_formula_weight         294.38
_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_Hall           'F 2 -2d'
_space_group_name_H-M_alt        'F d d 2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-10-01
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   17.6684(6)
_cell_length_b                   50.2977(16)
_cell_length_c                   7.4226(3)
_cell_measurement_reflns_used    7014
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.72
_cell_measurement_theta_min      2.44
_cell_volume                     6596.3(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_device_type  'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0319
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       66
_diffrn_reflns_limit_k_min       -66
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            21740
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.865
_diffrn_reflns_theta_min         1.619
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6338
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1127 before and 0.0455 after correction.
The Ratio of minimum to maximum transmission is 0.8501.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.186
_exptl_crystal_description       plate
_exptl_crystal_F_000             2528
_exptl_crystal_size_max          0.82
_exptl_crystal_size_mid          0.76
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.155
_refine_diff_density_rms         0.033
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     242
_refine_ls_number_reflns         3919
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0473
_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^)+(0.0436P)^2^+5.4670P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0920
_refine_ls_wR_factor_ref         0.0962
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                3495
_reflns_number_total             3919
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b07046_si_002.cif
_cod_data_source_block           nmc_10_122
_cod_database_code               4130804
_shelxl_version_number           2013-4
_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. Others
 Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17C)=Sof(H17D)=Sof(C18A)=Sof(H18A)=
 Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(1)
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18)=Sof(C19)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C16(H16), C16A(H16A), C18(H18), C18A(H18A)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C9(H9A,H9B), C17(H17A,H17B), C17A(H17C,H17D)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15)
3.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C19A(H19D,H19E,H19F)
;
_shelx_res_checksum              82509
_shelx_hkl_checksum              26914
_olex2_submission_special_instructions 'No special instructions were received'