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_4035046
_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_absolute_configuration unk
_chemical_formula_moiety         'C15 H12 Br3 N O'
_chemical_formula_sum            'C15 H12 Br3 N O'
_chemical_formula_weight         461.99
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.8087(3)
_cell_length_b                   15.6067(8)
_cell_length_c                   16.7214(8)
_cell_measurement_reflns_used    5800
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.7250
_cell_measurement_theta_min      3.7670
_cell_volume                     1515.87(13)
_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 0.991
_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    -53.00 -28.00   0.50    0.66    --  -41.49  37.00  55.00   50
  2  \w    -40.00 -14.00   0.50    0.66    --  -41.49 111.00 136.00   52
  3  \w    -85.00 -30.00   0.50    0.66    --  -41.49 -37.00-100.00  110
  4  \w     -9.00  21.00   0.50    0.66    --  -41.49  37.00  55.00   60
  5  \w    -38.00  -7.00   0.50    0.66    --  -41.49  88.00-116.00   62
  6  \w    -25.00  29.00   0.50    0.66    --   41.49 -88.00 127.00  108
  7  \w     -4.00  73.00   0.50    0.66    --   41.49-111.00  42.00  154
  8  \w     74.00 100.00   0.50    0.66    --   41.49  37.00  55.00   52
  9  \w     75.00 108.00   0.50    2.63    --  101.00 -37.00-100.00   66
 10  \w     92.00 129.00   0.50    2.63    --  101.00  37.00  55.00   74
 11  \w     58.00  83.00   0.50    2.63    --  101.00 -88.00 127.00   50
 12  \w     69.00 103.00   0.50    2.63    --  101.00-111.00  42.00   68
 13  \w     91.00 122.00   0.50    2.63    --  101.00  88.00-116.00   62
 14  \w    -81.00 -47.00   0.50    0.66    --  -41.49 -43.00-180.00   68
 15  \w     46.00  71.00   0.50    0.66    --   41.49  32.00-180.00   50
 16  \w      2.00  27.00   0.50    0.66    --   41.49 -37.00-100.00   50
 17  \w     30.00  92.00   0.50    0.66    --   41.49  43.00 -90.00  124
 18  \w     13.00  87.00   0.50    0.66    --   41.49-138.00 -90.00  148
 19  \w     96.00 124.00   0.50    2.63    --  101.00-133.00  30.00   56
 20  \w     37.00 105.00   0.50    2.63    --  101.00 -25.00   0.00  136
 21  \w     95.00 132.00   0.50    2.63    --  101.00 -93.00 -60.00   74
 22  \w     72.00 156.00   0.50    2.63    --  101.00   8.00 -90.00  168
 23  \w     45.00 104.00   0.50    2.63    --  101.00 -50.00  90.00  118
 24  \w     44.00  71.00   0.50    2.63    --  101.00 -77.00  60.00   54
 25  \w     80.00 125.00   0.50    2.63    --  101.00 -77.00  60.00   90
 26  \w     31.00  85.00   0.50    2.63    --  101.00  -8.00  60.00  108
 27  \w     89.00 121.00   0.50    2.63    --  101.00  -8.00  60.00   64
 28  \w     34.00 111.00   0.50    2.63    --  101.00 -17.00 -90.00  154
 29  \w     64.00  90.00   0.50    2.63    --  101.00 -33.00  60.00   52
 30  \w     37.00 112.00   0.50    2.63    --  101.00 -87.00-150.00  150
 31  \w    105.00 156.00   0.50    2.63    --  101.00 133.00   0.00  102
 32  \w    118.00 151.00   0.50    2.63    --  101.00  25.00 150.00   66
 33  \w     33.00  62.00   0.50    2.63    --  101.00 -93.00 -60.00   58
;
_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      -0.0006470000
_diffrn_orient_matrix_UB_12      -0.0884125000
_diffrn_orient_matrix_UB_13      0.0410338000
_diffrn_orient_matrix_UB_21      -0.2597656000
_diffrn_orient_matrix_UB_22      -0.0086143000
_diffrn_orient_matrix_UB_23      -0.0167574000
_diffrn_orient_matrix_UB_31      0.0536661000
_diffrn_orient_matrix_UB_32      -0.0431592000
_diffrn_orient_matrix_UB_33      -0.0807087000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0301
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            8334
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.336
_diffrn_reflns_theta_min         3.874
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.825
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37834
_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    2.024
_exptl_crystal_description       needle
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.665
_refine_diff_density_min         -0.911
_refine_diff_density_rms         0.145
_refine_ls_abs_structure_details
;
 Flack x determined using 1182 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     181
_refine_ls_number_reflns         2960
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0373
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0715P)^2^+3.2654P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1052
_refine_ls_wR_factor_ref         0.1058
_reflns_Friedel_coverage         0.699
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                2909
_reflns_number_total             2960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01406_si_014.cif
_cod_data_source_block           7072-9169_vasilev186
_cod_database_code               4035046
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C80 Br12 '
_shelx_estimated_absorpt_t_max   0.639
_shelx_estimated_absorpt_t_min   0.440
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C16(H16), C18(H18), C5(H5), C6(H6), C3(H3), C17(H17), C20(H20),
 C19(H19), C2(H2), C4(H4)
;
_shelx_res_checksum              67686
_shelx_hkl_checksum              90016
_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 1.929
_oxdiff_exptl_absorpt_empirical_full_min 0.619