Stereo- and Regioselective Synthesis of Polysubstituted Chiral 1,4-Oxazepanes
Michelle Bezanson; Joshua Pottel; Rana Bilbeisi; Sylvestre Toumieux; Mickaël Cueto; Nicolas Moitessier; Journal of Organic Chemistry 78 (2013) 872–885; doi:10.1021/jo3021715

data_4027884
_publ_section_title
;
 Stereo- and Regioselective Synthesis of Polysubstituted Chiral
 1,4-Oxazepanes
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              872
_journal_page_last               885
_journal_paper_doi               10.1021/jo3021715
_journal_volume                  78
_journal_year                    2013
_chemical_absolute_configuration rmad
_chemical_compound_source        'Synthesized by the authors. See text'
_chemical_formula_moiety         'C21 H23 Br N2 O7 S'
_chemical_formula_sum            'C21 H23 Br N2 O7 S'
_chemical_formula_weight         527.38
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90
_cell_angle_beta                 94.7460(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.44210(10)
_cell_length_b                   13.8099(3)
_cell_length_c                   25.0821(5)
_cell_measurement_reflns_used    9913
_cell_measurement_temperature    100
_cell_measurement_theta_max      71.67
_cell_measurement_theta_min      3.66
_cell_volume                     2223.77(7)
_computing_cell_refinement       'SAINT V8.27B(Bruker AXS, 2012)'
_computing_data_collection       'APEX2  (Bruker AXS, 2012)'
_computing_data_reduction        'SAINT V8.27B(Bruker AXS, 2012)'
_computing_molecular_graphics    'SHELXTL  (Bruker AXS, 2003)'
_computing_publication_material  'UdMX (Maris, 2004)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.3
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX II'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  'Quazar MX'
_diffrn_radiation_source         'Incoatec I\muS Microsource '
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.027
_diffrn_reflns_av_sigmaI/netI    0.0202
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            60602
_diffrn_reflns_theta_full        71.85
_diffrn_reflns_theta_max         71.85
_diffrn_reflns_theta_min         1.77
_exptl_absorpt_coefficient_mu    3.804
_exptl_absorpt_correction_T_max  0.6836
_exptl_absorpt_correction_T_min  0.6016
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Sadabs (Sheldrick, 2012)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.575
_exptl_crystal_description       block
_exptl_crystal_F_000             1080
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.949
_refine_diff_density_min         -0.271
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
Flack x refined as a 2-component inversion twin   
(Flack, H.D., Schwarzenbach, D.(1999),  3989 Friedel Pairs):
0.000(8)

By comparison:

1) Flack x determined using 3929 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Shelx 2012 method, Parsons and Flack (2004), Acta Cryst. A60, s61):
0.018(4)

2) Bayesian Hooft Analysis

Space Group P21
Wavelength    1.54178
Flack x ....    0.000
Flack (su) .    0.008
 
 
Bijvoet Pairs    4013
Coverage ...       97
DiffCalcMax.  1359.51
Outlier Crit  2719.01
Scatter Plot
sigma Crit..     0.25
Select Pairs     3521
Number Plus      3142
Number Minus      379
Aver. Ratio     0.974
Slope ......    0.975
 
 
Normal Prob. Plot
Sample Size.     4013
Corr. Coeff.    0.994
Intercept ..    0.063
Slope ......    0.961
 
 
Bayesian Statistics
Type ....... gaussian
Select Pairs     4013
P2(true)....    1.000
P3(true)....    1.000
P3(rac-twin)  0.0E+00
P3(false) ..  0.0E+00
G ..........   0.9750
G (su) .....   0.0016
Hooft y ....    0.013
Hooft (su) .  0.1E-02

;
_refine_ls_abs_structure_Flack   0.000(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         8525
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0238
_refine_ls_R_factor_gt           0.0235
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0441P)^2^+0.3958P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0629
_refine_ls_wR_factor_ref         0.0632
_reflns_number_gt                8453
_reflns_number_total             8525
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            jo3021715_si_002.cif
_cod_data_source_block           moite1
_cod_database_code               4027884