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_4035038
_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         'C17 H16 Cl2.99 N O3'
_chemical_formula_sum            'C17 H16 Cl2.985 N O3'
_chemical_formula_weight         388.15
_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_Int_Tables_number      14
_audit_creation_date             2018-04-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.833(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5272(9)
_cell_length_b                   6.0424(6)
_cell_length_c                   24.9593(15)
_cell_measurement_reflns_used    3367
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.6220
_cell_measurement_theta_min      3.7410
_cell_volume                     1734.6(2)
_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  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.9583
_diffrn_measured_fraction_theta_max 0.9583
_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   -102.00 -76.00   0.50    0.71    --  -41.35 154.00 103.00   52
  2  \w    -93.00 -67.00   0.50    0.71    --  -41.35-154.00  63.00   52
  3  \w    -73.00  -7.00   0.50    0.71    --  -41.35 120.00 -54.00  132
  4  \w     13.00  87.00   0.50    0.71    --   41.35-120.00-138.00  148
  5  \w     56.00  82.00   0.50    0.71    --   41.35 154.00 103.00   52
  6  \w     77.00 136.00   0.50    2.84    --  101.00-154.00  63.00  118
  7  \w     37.00  99.00   0.50    2.84    --  101.00-120.00-138.00  124
  8  \w     82.00 107.00   0.50    2.84    --  101.00 154.00 103.00   50
  9  \w     78.00 122.00   0.50    2.84    --  101.00 120.00 -54.00   88
 10  \w    -42.00 -16.00   0.50    0.71    --  -41.35  65.00   0.00   52
 11  \w    -60.00 -19.00   0.50    0.71    --  -41.35  65.00 120.00   82
 12  \w    -64.00 -34.00   0.50    0.71    --  -41.35 -32.00-150.00   60
 13  \w    -93.00 -67.00   0.50    0.71    --  -41.35 -32.00-150.00   52
 14  \w    -14.00  18.00   0.50    0.71    --  -41.35  65.00 120.00   64
 15  \w     -8.00  17.00   0.50    0.71    --  -41.35  65.00   0.00   50
 16  \w     16.00  44.00   0.50    0.71    --   41.35  77.00 -60.00   56
 17  \w     -1.00  58.00   0.50    0.71    --   41.35 -54.00  90.00  118
 18  \w     33.00  58.00   0.50    0.71    --   41.35  32.00-120.00   50
 19  \w     48.00 103.00   0.50    0.71    --   41.35  77.00 -60.00  110
 20  \w     65.00 107.00   0.50    0.71    --   41.35  32.00-120.00   84
 21  \w     49.00  74.00   0.50    0.71    --   41.35  32.00   0.00   50
 22  \w     63.00  88.00   0.50    0.71    --   41.35  32.00 -90.00   50
 23  \w     81.00 106.00   0.50    0.71    --   41.35  32.00   0.00   50
 24  \w     84.00 115.00   0.50    2.84    --  101.00  59.00 120.00   62
 25  \w     96.00 121.00   0.50    2.84    --  101.00 -68.00  30.00   50
 26  \w     43.00  90.00   0.50    2.84    --  101.00 -68.00  30.00   94
 27  \w     39.00 103.00   0.50    2.84    --  101.00-133.00  60.00  128
 28  \w    111.00 155.00   0.50    2.84    --  101.00  42.00-150.00   88
 29  \w     92.00 145.00   0.50    2.84    --  101.00  93.00-120.00  106
 30  \w    119.00 144.00   0.50    2.84    --  101.00 111.00  60.00   50
 31  \w     91.00 117.00   0.50    2.84    --  101.00 111.00  60.00   52
 32  \w     76.00 157.00   0.50    2.84    --  101.00  77.00 -60.00  162
 33  \w     94.00 120.00   0.50    2.84    --  101.00 -87.00-150.00   52
 34  \w     40.00  65.00   0.50    2.84    --  101.00-133.00 -30.00   50
 35  \w    131.00 157.00   0.50    2.84    --  101.00  59.00 120.00   52
 36  \w     47.00 109.00   0.50    2.84    --  101.00 -42.00 150.00  124
 37  \w     40.00 130.00   0.50    2.84    --  101.00 -93.00  30.00  180
 38  \w    111.00 136.00   0.50    2.84    --  101.00  42.00-120.00   50
 39  \w    120.00 146.00   0.50    2.84    --  101.00 111.00-180.00   52
 40  \w     60.00 113.00   0.50    2.84    --  101.00-111.00-120.00  106
 41  \w     89.00 114.00   0.50    2.84    --  101.00 111.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0567
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9630
_diffrn_reflns_theta_full        74.1670
_diffrn_reflns_theta_max         74.17
_diffrn_reflns_theta_min         3.55
_exptl_absorpt_coefficient_mu    4.901
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66507
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.4862
_exptl_crystal_description       prism
_exptl_crystal_F_000             805.4262
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.3985
_refine_diff_density_min         -0.5805
_refine_diff_density_rms         0.0916
_refine_ls_d_res_high            0.8013
_refine_ls_d_res_low             12.4517
_refine_ls_goodness_of_fit_ref   1.0514
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    43
_refine_ls_number_parameters     340
_refine_ls_number_reflns         3398
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0514
_refine_ls_R_factor_all          0.0743
_refine_ls_R_factor_gt           0.0604
_refine_ls_shift/su_max          0.0245
_refine_ls_shift/su_mean         0.0018
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0774P)^2^+2.6472P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1565
_refine_ls_wR_factor_ref         0.1743
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              14
_reflns_limit_h_min              -14
_reflns_limit_k_max              7
_reflns_limit_k_min              0
_reflns_limit_l_max              30
_reflns_limit_l_min              0
_reflns_number_gt                2718
_reflns_number_total             3398
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            jo8b01406_si_009.cif
_cod_data_source_block           ov_ca_155
_cod_database_code               4035038
_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. Others
 Sof(Cl2A)=Sof(C9A)=Sof(H9A)=Sof(C11A)=Sof(O3A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(H16A)=Sof(C13A)=Sof(H13A)=Sof(C12A)=Sof(H12A)=Sof(C17A)=Sof(H17d)=
 Sof(H17e)=Sof(H17f)=Sof(C14A)=Sof(Cl1A)=Sof(C10A)=1-FVAR(1)
 Sof(O3)=Sof(C12)=Sof(H12)=Sof(C15)=Sof(H15)=Sof(C14)=Sof(C16)=Sof(H16)=
 Sof(C13)=Sof(H13)=Sof(C17)=Sof(H17a)=Sof(H17b)=Sof(H17c)=Sof(C11)=Sof(Cl1)=
 Sof(Cl3)=Sof(Cl2)=Sof(C10)=Sof(C9)=Sof(H9)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C9A(H9A), C9(H9)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C7(H7), C6(H6), C12(H12), C15(H15), C16(H16), C13(H13),
 C15A(H15A), C16A(H16A), C13A(H13A), C12A(H12A)
3.c Idealised Me refined as rotating group:
 C8(H8a,H8b,H8c), C17(H17a,H17b,H17c), C17A(H17d,H17e,H17f)
3.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
;