Cascade Oxidation/Halogenoaminocyclization Reaction of Trifluoromethylated Homoallylic N-Acylhydrazines: Metal-free Synthesis of CF<sub>3</sub>-Substituted Pyrazolines.
Wang, Yuxiang; Wang, Ke-Hu; Su, Yingpeng; Yang, Zheng; Wen, Lan; Liu, Lili; Wang, Juanjuan; Huang, Danfeng; Hu, Yulai; The Journal of organic chemistry 83 (2018) 939–950; doi:10.1021/acs.joc.7b02934

data_4033321
_publ_section_title
;
 Cascade Oxidation/Halogenoaminocyclization Reaction of
 Trifluoromethylated Homoallylic N-Acylhydrazines: Metal-free Synthesis of
 CF<sub>3</sub>-Substituted Pyrazolines.
;
_journal_issue                   2
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              939
_journal_page_last               950
_journal_paper_doi               10.1021/acs.joc.7b02934
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C12 H11 F3 N2 O'
_chemical_formula_sum            'C12 H11 F3 N2 O'
_chemical_formula_weight         256.23
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-03-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 116.194(13)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.8530(10)
_cell_length_b                   19.2845(11)
_cell_length_c                   8.0635(8)
_cell_measurement_reflns_used    988
_cell_measurement_temperature    290.83(10)
_cell_measurement_theta_max      22.2650
_cell_measurement_theta_min      4.2280
_cell_volume                     1235.3(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      air
_diffrn_ambient_temperature      290.83(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega    0.00   25.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.1479  -99.0000 -150.0000 25

  2 omega  -20.00   32.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -57.0000 -180.0000 52

  3 omega   19.00   87.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854   57.0000  -60.0000 68

  4 omega   -4.00   24.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -17.1479  -99.0000  -30.0000 28

  5 omega   31.00   62.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -99.0000 -150.0000 31

  6 omega  -20.00    6.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -99.0000 -150.0000 26

  7 omega   36.00   90.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  178.0000 -150.0000 54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0595444000
_diffrn_orient_matrix_UB_12      -0.0273215000
_diffrn_orient_matrix_UB_13      -0.0339060000
_diffrn_orient_matrix_UB_21      0.0656900000
_diffrn_orient_matrix_UB_22      -0.0246118000
_diffrn_orient_matrix_UB_23      0.0409821000
_diffrn_orient_matrix_UB_31      -0.0102718000
_diffrn_orient_matrix_UB_32      0.0010071000
_diffrn_orient_matrix_UB_33      0.0823864000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_av_unetI/netI     0.0692
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            6013
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.32
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.120
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65857
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.378
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.292
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     163
_refine_ls_number_reflns         2389
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1195
_refine_ls_R_factor_gt           0.0637
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0578P)^2^+0.5543P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1407
_refine_ls_wR_factor_ref         0.1843
_reflns_number_gt                1308
_reflns_number_total             2389
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo7b02934_si_002.cif
_cod_data_source_block           dhh_1
_cod_depositor_comments
'Adding full bibliography for 4033321--4033322.cif.'
_cod_database_code               4033321
_chemical_oxdiff_formula         'C H N O'
_reflns_odcompleteness_completeness 98.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11)
2.c X=CH2 refined with riding coordinates:
 C12(H12A,H12B)
;
_olex2_date_sample_data_collection 2016-03-30
_olex2_submission_special_instructions 'No special instructions were received'