Reactions of 3,3,3-Trihalogeno-1-nitropropenes with Arenes in the Superacid CF<sub>3</sub>SO<sub>3</sub>H: Synthesis of ( Z)-3,3,3-Trihalogeno-1,2-diarylpropan-1-one Oximes and Study on the Reaction Mechanism.
Golushko, Andrei A.; Sandzhieva, Maria A.; Ivanov, Alexander Yu; Boyarskaya, Irina A.; Khoroshilova, Olesya V.; Barkov, Alexey Yu; Vasilyev, Aleksander V.; The Journal of organic chemistry 83 (2018) 10142–10157; doi:10.1021/acs.joc.8b01406

data_4035034
_publ_section_title
;
 Reactions of 3,3,3-Trihalogeno-1-nitropropenes with Arenes in the
 Superacid CF<sub>3</sub>SO<sub>3</sub>H: Synthesis of (
 Z)-3,3,3-Trihalogeno-1,2-diarylpropan-1-one Oximes and Study on the
 Reaction Mechanism.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10142
_journal_page_last               10157
_journal_paper_doi               10.1021/acs.joc.8b01406
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C11 H11 Cl F3 N O'
_chemical_formula_sum            'C11 H11 Cl F3 N O'
_chemical_formula_weight         265.66
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.9164(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.35148(12)
_cell_length_b                   13.2226(3)
_cell_length_c                   16.0719(3)
_cell_measurement_reflns_used    8764
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.8940
_cell_measurement_theta_min      2.7470
_cell_volume                     1128.98(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -39.00 -12.00   0.50    1.00    --  -41.35 100.00 147.00   54
  2  \w    -75.00 -50.00   0.50    1.00    --  -41.35 100.00 147.00   50
  3  \w     68.00 102.00   0.50    1.00    --  101.00-100.00  42.00   68
  4  \w     86.00 151.00   0.50    1.00    --  101.00 100.00 147.00  130
  5  \w    -91.00 -27.00   0.50    1.00    --  -41.35 -65.00 120.00  128
  6  \w    -94.00 -42.00   0.50    1.00    --  -41.35 -65.00  60.00  104
  7  \w    -48.00   2.00   0.50    1.00    --  -41.35  32.00 -60.00  100
  8  \w     33.00 101.00   0.50    1.00    --   41.35  43.00   0.00  136
  9  \w    -10.00  52.00   0.50    1.00    --   41.35 -54.00  30.00  124
 10  \w      7.00  52.00   0.50    1.00    --   41.35-100.00  42.00   90
 11  \w     28.00  82.00   0.50    1.00    --   41.35  43.00-180.00  108
 12  \w     42.00  84.00   0.50    1.00    --   41.35  32.00 -60.00   84
 13  \w     97.00 147.00   0.50    1.00    --  101.00  42.00  90.00  100
 14  \w     37.00 106.00   0.50    1.00    --  101.00-111.00  30.00  138
 15  \w     54.00 105.00   0.50    1.00    --  101.00 -68.00  60.00  102
 16  \w     54.00 106.00   0.50    1.00    --  101.00 -42.00   0.00  104
 17  \w    104.00 157.00   0.50    1.00    --  101.00  33.00-150.00  106
 18  \w     39.00  81.00   0.50    1.00    --  101.00-133.00-180.00   84
 19  \w     84.00 109.00   0.50    1.00    --  101.00 -33.00  60.00   50
 20  \w     76.00 154.00   0.50    1.00    --  101.00  77.00 -90.00  156
 21  \w     71.00 115.00   0.50    1.00    --  101.00 -59.00 120.00   88
 22  \w     36.00  62.00   0.50    1.00    --  101.00 -33.00  60.00   52
 23  \w     96.00 122.00   0.50    1.00    --  101.00-133.00-180.00   52
 24  \w     38.00 104.00   0.50    1.00    --  101.00-133.00-150.00  132
 25  \w     91.00 138.00   0.50    1.00    --  101.00  93.00 120.00   94
 26  \w     38.00  64.00   0.50    1.00    --  101.00 -59.00 -60.00   52
 27  \w     80.00 118.00   0.50    1.00    --  101.00 -59.00 -60.00   76
 28  \w     91.00 156.00   0.50    1.00    --  101.00  50.00-120.00  130
 29  \w    -11.00  15.00   0.50    1.00    --   41.35-100.00  42.00   52
 30  \w    -15.00  19.00   0.50    1.00    --  -41.35  21.00-180.00   68
 31  \w    -42.00 -16.00   0.50    1.00    --  -41.35  21.00-180.00   52
 32  \w     50.00  75.00   0.50    1.00    --   41.35-100.00  42.00   50
 33  \w     79.00 104.00   0.50    1.00    --   41.35  43.00-180.00   50
 34  \w     23.00  71.00   0.50    1.00    --   41.35  65.00-120.00   96
 35  \w     71.00  97.00   0.50    1.00    --   41.35  32.00 -60.00   52
 36  \w     43.00  69.00   0.50    1.00    --   41.35 -89.00 -60.00   52
 37  \w    -23.00  18.00   0.50    1.00    --   41.35 -89.00 -60.00   82
 38  \w     45.00 100.00   0.50    1.00    --  101.00 -33.00-150.00  110
 39  \w     83.00 111.00   0.50    1.00    --  101.00-111.00 -90.00   56
 40  \w     34.00 109.00   0.50    1.00    --  101.00 -25.00 -30.00  150
 41  \w     88.00 116.00   0.50    1.00    --  101.00-133.00  60.00   56
 42  \w     37.00  63.00   0.50    1.00    --  101.00-111.00-150.00   52
 43  \w     79.00 106.00   0.50    1.00    --  101.00-111.00-150.00   54
 44  \w     45.00  89.00   0.50    1.00    --  101.00 -93.00-150.00   88
 45  \w    102.00 148.00   0.50    1.00    --  101.00 111.00   0.00   92
 46  \w     38.00  72.00   0.50    1.00    --  101.00 -17.00 -30.00   68
 47  \w     82.00 126.00   0.50    1.00    --  101.00  93.00 -60.00   88
 48  \w    123.00 148.00   0.50    1.00    --  101.00  68.00  60.00   50
 49  \w     79.00 112.00   0.50    1.00    --  101.00 -17.00 -30.00   66
 50  \w     81.00 106.00   0.50    1.00    --  101.00  68.00  60.00   50
 51  \w     56.00  82.00   0.50    1.00    --  101.00-111.00 -90.00   52
 52  \w     83.00 109.00   0.50    1.00    --  101.00 -25.00  90.00   52
 53  \w     38.00  64.00   0.50    1.00    --  101.00 -25.00  90.00   52
 54  \w     36.00 120.00   0.50    1.00    --  101.00 -87.00  60.00  168
 55  \w     73.00  99.00   0.50    1.00    --  101.00 -33.00  60.00   52
 56  \w    132.00 157.00   0.50    1.00    --  101.00  33.00 -90.00   50
 57  \w     85.00 114.00   0.50    1.00    --  101.00  50.00  30.00   58
 58  \w    102.00 112.50   0.50    1.00    --  101.00 -93.00-150.00   21
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2290570000
_diffrn_orient_matrix_UB_12      -0.0089334000
_diffrn_orient_matrix_UB_13      -0.0491566000
_diffrn_orient_matrix_UB_21      0.0725802000
_diffrn_orient_matrix_UB_22      0.1102565000
_diffrn_orient_matrix_UB_23      0.0226122000
_diffrn_orient_matrix_UB_31      0.1623433000
_diffrn_orient_matrix_UB_32      -0.0366968000
_diffrn_orient_matrix_UB_33      0.0799310000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0168
_diffrn_reflns_av_unetI/netI     0.0109
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            10472
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.956
_diffrn_reflns_theta_min         4.343
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.262
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81933
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.563
_exptl_crystal_description       prism
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.312
_refine_diff_density_min         -0.331
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     157
_refine_ls_number_reflns         2214
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0293
_refine_ls_R_factor_gt           0.0290
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0398P)^2^+0.7584P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0776
_refine_ls_wR_factor_ref         0.0778
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2185
_reflns_number_total             2214
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01406_si_011.cif
_cod_data_source_block           7072-8253_rqo137
_cod_database_code               4035034
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'F3 C20 O N'
_shelx_estimated_absorpt_t_max   0.562
_shelx_estimated_absorpt_t_min   0.562
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C8(H8), C7(H7)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              9880
_shelx_hkl_checksum              76131
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.250
_oxdiff_exptl_absorpt_empirical_full_min 0.868