Acetylene-based two-step diastereoselective synthesis of bridgehead dihydro-oxadiazines using ketones and hydrazine as the only reactants
Schmidt, Elena; Semenova, Nadezhda; Ivanova, Elena; Tatarinova, Inna; Ushakov, Igor; Vashchenko, A. V.; Trofimov, Boris; Chemical Communications  (2019) –; doi:10.1039/C9CC00315K

data_7122940
_publ_section_title
;
 Acetylene-based two-step diastereoselective synthesis of bridgehead
 dihydro-oxadiazines using ketones and hydrazine as the only reactants
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC00315K
_journal_year                    2019
_chemical_formula_moiety         'C22 H20 F6 N2 O'
_chemical_formula_sum            'C22 H20 F6 N2 O'
_chemical_formula_weight         442.40
_chemical_name_systematic
4,7-dimethyl-1,5-bis(3-(trifluoromethyl)phenyl)-9-oxa-2,3-diazabicyclo[3.3.1]non-3-ene
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-10-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-11-16 deposited with the CCDC.
2019-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                77.15(3)
_cell_angle_beta                 85.43(3)
_cell_angle_gamma                72.57(6)
_cell_formula_units_Z            2
_cell_length_a                   9.291(8)
_cell_length_b                   10.358(10)
_cell_length_c                   11.840(10)
_cell_measurement_reflns_used    793
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.3
_cell_measurement_theta_min      2.5
_cell_volume                     1059.8(17)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker  D8 Venture'
_diffrn_measurement_method       '\w and \f'
_diffrn_radiation_monochromator  No
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            28212
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.773
_diffrn_reflns_theta_min         2.298
_diffrn_source                   IuS
_exptl_absorpt_coefficient_mu    0.122
_exptl_absorpt_correction_T_max  0.981
_exptl_absorpt_correction_T_min  0.975
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0919 before and 0.0506 after correction.
The Ratio of minimum to maximum transmission is 0.9065.
The \l/2 correction factor is Not present.
;
_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    1.386
_exptl_crystal_description       block
_exptl_crystal_F_000             456
_exptl_crystal_size_max          0.259
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.151
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.196
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     342
_refine_ls_number_reflns         4499
_refine_ls_number_restraints     186
_refine_ls_restrained_S_all      1.149
_refine_ls_R_factor_all          0.1057
_refine_ls_R_factor_gt           0.0511
_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^)+(0.0612P)^2^+0.2063P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1171
_refine_ls_wR_factor_ref         0.1411
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2630
_reflns_number_total             4517
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc00315k2.cif
_cod_data_source_block           b_a
_cod_database_code               7122940
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.967
_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. Restrained distances
 F5-F6 \\sim F5-F7 \\sim F6-F7 \\sim F5A-F6A \\sim F5A-F7A \\sim F6A-F7A
 with sigma of 0.04
 C18-F5 \\sim C18-F6 \\sim C18-F7 \\sim C18-C14 \\sim C18-F5A \\sim C18-F6A
\\sim C18-F7A
 with sigma of 0.02
 F2-F3 \\sim F2-F4 \\sim F3-F4 \\sim F2A-F4A \\sim F2A-F3A \\sim F4A-F3A
 with sigma of 0.04
 C24-F2 \\sim C24-F3 \\sim C24-F4 \\sim C24-C21 \\sim C24-F2A \\sim C24-F4A
\\sim C24-F3A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F2, F3, F4, F5, F6, F7, C18, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5A, F6A, F7A, C18, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F2, F3, F4, F5, F6, F7, C24, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5A, F6A, F7A, F2A, F4A, F3A, C24, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F5A)=Sof(F6A)=Sof(F7A)=1-FVAR(1)
 Sof(F5)=Sof(F6)=Sof(F7)=FVAR(1)
 Sof(F2A)=Sof(F4A)=Sof(F3A)=1-FVAR(2)
 Sof(F2)=Sof(F3)=Sof(F4)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C7(H7)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C6(H6A,H6B)
5.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C13(H13), C20(H20), C22(H22), C1AA(H1AA), C23(H23), C16(H16),
 C17(H17)
5.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              26810
_olex2_submission_special_instructions 'No special instructions were received'