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_4035040
_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         'C19 H20 Cl3 N O'
_chemical_formula_sum            'C19 H20 Cl3 N O'
_chemical_formula_weight         384.71
_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     dual
_audit_creation_date             2017-12-22
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_cell_angle_alpha                66.390(3)
_cell_angle_beta                 76.807(2)
_cell_angle_gamma                80.568(2)
_cell_formula_units_Z            2
_cell_length_a                   8.3415(2)
_cell_length_b                   11.0216(3)
_cell_length_c                   11.7741(3)
_cell_measurement_reflns_used    6480
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.9080
_cell_measurement_theta_min      4.1850
_cell_volume                     962.49(5)
_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 0.999
_diffrn_measured_fraction_theta_max 0.994
_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    -48.00  21.00   0.50    0.20    --  -41.35  94.00  25.00  138
  2  \w    -12.00  15.00   0.50    0.20    --   41.35 -94.00 -86.00   54
  3  \w    119.00 144.00   0.50    0.20    --  101.00  94.00  25.00   50
  4  \w     63.00 104.00   0.50    0.20    --  101.00 -94.00 -86.00   82
  5  \w     -3.00  22.00   0.50    0.20    --  -41.35  32.00 -60.00   50
  6  \w    -46.00 -21.00   0.50    0.20    --  -41.35 -65.00 -90.00   50
  7  \w    -16.00  21.00   0.50    0.20    --  -41.35  77.00-180.00   74
  8  \w    -94.00 -53.00   0.50    0.20    --  -41.35 -65.00 -60.00   82
  9  \w    -50.00 -14.00   0.50    0.20    --  -41.35  32.00 -60.00   72
 10  \w    -65.00 -26.00   0.50    0.20    --  -41.35  11.00 -90.00   78
 11  \w    -47.00 -22.00   0.50    0.20    --  -41.35 -65.00 -60.00   50
 12  \w    -65.00 -26.00   0.50    0.20    --  -41.35  77.00-180.00   78
 13  \w      7.00  32.00   0.50    0.20    --  -41.35  11.00 -90.00   50
 14  \w   -103.00 -71.00   0.50    0.20    --  -41.35 -65.00 -90.00   64
 15  \w    -57.00 -32.00   0.50    0.20    --  -41.35 -21.00   0.00   50
 16  \w     17.00  46.00   0.50    0.20    --   41.35 -54.00  90.00   58
 17  \w    -17.00   9.00   0.50    0.20    --   41.35 -54.00  90.00   52
 18  \w     13.00  64.00   0.50    0.20    --   41.35 -89.00-180.00  102
 19  \w     74.00 102.00   0.50    0.20    --   41.35  54.00 120.00   56
 20  \w     79.00 105.00   0.50    0.20    --   41.35  21.00-150.00   52
 21  \w     24.00  67.00   0.50    0.20    --   41.35  54.00 120.00   86
 22  \w     36.00  74.00   0.50    0.20    --   41.35  21.00-150.00   76
 23  \w     24.00  76.00   0.50    0.20    --   41.35-104.00  30.00  104
 24  \w     21.00  64.00   0.50    0.20    --   41.35 -94.00 -86.00   86
 25  \w     -5.00  20.00   0.50    0.20    --   41.35-104.00  30.00   50
 26  \w    -22.00  36.00   0.50    0.20    --   41.35 -32.00 -30.00  116
 27  \w    132.00 157.00   0.50    0.20    --  101.00  77.00-180.00   50
 28  \w     77.00 112.00   0.50    0.20    --  101.00  77.00-180.00   70
 29  \w     38.00  93.00   0.50    0.20    --  101.00-133.00 -90.00  110
 30  \w     81.00 124.00   0.50    0.20    --  101.00-133.00 150.00   86
 31  \w     83.00 113.00   0.50    0.20    --  101.00-111.00-120.00   60
 32  \w     35.00  72.00   0.50    0.20    --  101.00-111.00 150.00   74
 33  \w     38.00 113.00   0.50    0.20    --  101.00 -50.00-150.00  150
 34  \w     87.00 112.00   0.50    0.20    --  101.00  17.00  30.00   50
 35  \w     40.00  65.00   0.50    0.20    --  101.00 -33.00-150.00   50
 36  \w     89.00 135.00   0.50    0.20    --  101.00  50.00-120.00   92
 37  \w     88.00 141.00   0.50    0.20    --  101.00 133.00 -60.00  106
 38  \w    103.00 156.00   0.50    0.20    --  101.00 111.00 -90.00  106
 39  \w     50.00 105.00   0.50    0.20    --  101.00 -77.00 120.00  110
 40  \w     94.00 153.00   0.50    0.20    --  101.00  93.00  60.00  118
 41  \w     43.00  71.00   0.50    0.20    --  101.00 -77.00  60.00   56
 42  \w     80.00 107.00   0.50    0.20    --  101.00 -68.00 -30.00   54
 43  \w     54.00  80.00   0.50    0.20    --  101.00-133.00-150.00   52
 44  \w     77.00 156.00   0.50    0.20    --  101.00  77.00  90.00  158
 45  \w    123.00 149.00   0.50    0.20    --  101.00  50.00  30.00   52
 46  \w    121.00 147.00   0.50    0.20    --  101.00  59.00   0.00   52
 47  \w     85.00 111.00   0.50    0.20    --  101.00  50.00  30.00   52
 48  \w     38.00  82.00   0.50    0.20    --  101.00-111.00 -30.00   88
 49  \w    114.00 154.00   0.50    0.20    --  101.00  59.00  60.00   80
 50  \w     70.00 118.00   0.50    0.20    --  101.00 -68.00 150.00   96
 51  \w     74.00 105.00   0.50    0.20    --  101.00 -33.00 -30.00   62
 52  \w     93.00 148.00   0.50    0.20    --  101.00  25.00-180.00  110
 53  \w     88.00 124.00   0.50    0.20    --  101.00 -93.00 -30.00   72
 54  \w     90.00 130.00   0.50    0.20    --  101.00  42.00  60.00   80
 55  \w     76.00 102.00   0.50    0.20    --  101.00 -87.00-150.00   52
 56  \w    132.00 157.00   0.50    0.20    --  101.00  17.00  30.00   50
 57  \w     37.00  62.00   0.50    0.20    --  101.00 -93.00 -30.00   50
 58  \w     50.00  76.00   0.50    0.20    --  101.00-111.00-120.00   52
 59  \w     38.00 115.00   0.50    0.20    --  101.00 -59.00 -60.00  154
 60  \w     44.00 110.00   0.50    0.20    --  101.00-111.00   0.00  132
 61  \w     83.00 108.00   0.50    0.20    --  101.00  59.00   0.00   50
 62  \w     75.00 114.00   0.50    0.20    --  101.00-111.00 150.00   78
 63  \w    109.00 157.00   0.50    0.20    --  101.00  59.00 120.00   96
 64  \w     98.00 124.00   0.50    0.20    --  101.00  94.00  25.00   52
 65  \w    -40.00 -15.00   0.50    0.20    --    4.00 118.00 -32.49   50
 66  \w    -19.00   6.00   0.50    0.20    --   20.00 110.00 -11.49   50
 67  \w    -42.00 -17.00   0.50    0.20    --   24.00 151.00 177.97   50
 68  \w     -2.00  23.00   0.50    0.20    --   28.00  93.00  17.13   50
 69  \w     -3.00  22.00   0.50    0.20    --   28.00  94.00-111.46   50
 70  \w      3.00  28.00   0.50    0.20    --   32.00  90.00 117.30   50
 71  \w      3.00  28.00   0.50    0.20    --   32.00  89.00-137.52   50
 72  \w      4.00  20.00   0.50    0.20    --   32.00  88.00 -26.90   32
;
_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      -0.0416595000
_diffrn_orient_matrix_UB_12      -0.1275465000
_diffrn_orient_matrix_UB_13      0.1163190000
_diffrn_orient_matrix_UB_21      -0.1146803000
_diffrn_orient_matrix_UB_22      -0.0325074000
_diffrn_orient_matrix_UB_23      -0.0678953000
_diffrn_orient_matrix_UB_31      0.1460671000
_diffrn_orient_matrix_UB_32      -0.0781008000
_diffrn_orient_matrix_UB_33      -0.0541548000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0366
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            9619
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.964
_diffrn_reflns_theta_min         4.166
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.347
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31181
_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    1.327
_exptl_crystal_description       prism
_exptl_crystal_F_000             400
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.438
_refine_diff_density_min         -0.324
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         3767
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0692P)^2^+0.4715P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1187
_refine_ls_wR_factor_ref         0.1209
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3485
_reflns_number_total             3767
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01406_si_007.cif
_cod_data_source_block           159
_cod_database_code               4035040
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'c19 h20 n1'
_diffrn_oxdiff_ac3_digest_frames
;
01a9cdc7e0572a547b11785a64563f63bf000355caa
;
_diffrn_oxdiff_ac3_digest_hkl
;
015d5aebf91c360fff65b2a15421a3b122773f
;
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     70.53
_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:
 C15(H15), C5(H5), C13(H13), C12(H12), C8(H8), C7(H7)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C17(H17A,H17B,H17C), C16(H16A,H16B,
 H16C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_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 2.151
_oxdiff_exptl_absorpt_empirical_full_min 0.565