An Experimental and Computational Approach to Understanding the Reactions of Acyl Nitroso Compounds in [4 + 2] Cycloadditions.
Chaiyaveij, Duangduan; Batsanov, Andrei S.; Fox, Mark A.; Marder, Todd B.; Whiting, Andrew; The Journal of organic chemistry 80 (2015) 9518–9534; doi:10.1021/acs.joc.5b01470

data_4036310
_publ_section_title
;
 An Experimental and Computational Approach to Understanding the Reactions
 of Acyl Nitroso Compounds in [4 + 2] Cycloadditions.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9518
_journal_page_last               9534
_journal_paper_doi               10.1021/acs.joc.5b01470
_journal_volume                  80
_journal_year                    2015
_chemical_formula_moiety         'C12 H14 N2 O2'
_chemical_formula_sum            'C12 H14 N2 O2'
_chemical_formula_weight         218.25
_chemical_melting_point          369
_chemical_name_systematic
;
 (4,5-Dimethyl-3,6-dihydro-2H-1,2-oxazin-2-yl)(pyridin-2-yl)methanone
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-04
_audit_creation_method
;
 Olex2 1.2-alpha (compiled Mar  1 2013 17:37:24, GUI svn.r4404)
;
_cell_angle_alpha                77.293(3)
_cell_angle_beta                 68.194(3)
_cell_angle_gamma                84.734(3)
_cell_formula_units_Z            2
_cell_length_a                   7.7458(6)
_cell_length_b                   8.3388(6)
_cell_length_c                   9.2703(7)
_cell_measurement_reflns_used    1473
_cell_measurement_temperature    156
_cell_measurement_theta_max      24.32
_cell_measurement_theta_min      2.42
_cell_volume                     542.28(7)
_computing_cell_refinement       'SAINT v7.46A (Bruker, 2008)'
_computing_data_collection       'SMART v5.625 (Bruker, 2001)'
_computing_data_reduction        'SAINT v7.46A (Bruker, 2008)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL-2012, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      156
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.6
_diffrn_detector_type            'Bruker SMART CCD 6000 area detector'
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 6000 area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            4329
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.416
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           35.0
_diffrn_source_power             1.75
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.093
_exptl_absorpt_correction_type   none
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             232
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.179
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.950
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     149
_refine_ls_number_reflns         1896
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.950
_refine_ls_R_factor_all          0.0607
_refine_ls_R_factor_gt           0.0399
_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^)+(0.0553P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0924
_refine_ls_wR_factor_ref         0.1010
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1332
_reflns_number_total             1896
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b01470_si_002.cif
_cod_data_source_block           32
_cod_database_code               4036310
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Others
 Uiso(H14A)=Uiso(H14B)=Uiso(H14C)
 Uiso(H15A)=Uiso(H15B)=Uiso(H15C)
3.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C7(H7A,H7B)
3.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C12(H12), C13(H13), C16(H16)
3.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_shelxl_version_number           2012-9