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_4035044
_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         'C15 H12 Br3 N O, C H2 Cl2'
_chemical_formula_sum            'C16 H14 Br3 Cl2 N O'
_chemical_formula_weight         546.91
_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     iterative
_audit_creation_date             2017-10-18
_audit_creation_method
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Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.632(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.2867(5)
_cell_length_b                   6.1746(2)
_cell_length_c                   21.3414(7)
_cell_measurement_reflns_used    2317
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.6210
_cell_measurement_theta_min      3.1440
_cell_volume                     1880.64(11)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 16.2096
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega   47.00   86.00   1.0000   50.0500
omega____ theta____ kappa____ phi______ frames
    -       23.3406  178.0000 -150.0000 39

  2 omega  -14.00   62.00   1.0000   50.0500
omega____ theta____ kappa____ phi______ frames
    -       23.3406  -99.0000 -150.0000 76

  3 omega  -21.00   91.00   1.0000   50.0500
omega____ theta____ kappa____ phi______ frames
    -       23.3406   19.0000   30.0000 112
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0408878000
_diffrn_orient_matrix_UB_12      0.0053117000
_diffrn_orient_matrix_UB_13      -0.0175972000
_diffrn_orient_matrix_UB_21      0.0223711000
_diffrn_orient_matrix_UB_22      -0.0762884000
_diffrn_orient_matrix_UB_23      0.0205233000
_diffrn_orient_matrix_UB_31      -0.0173629000
_diffrn_orient_matrix_UB_32      -0.0856689000
_diffrn_orient_matrix_UB_33      -0.0193695000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_unetI/netI     0.0676
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            8063
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.498
_diffrn_reflns_theta_min         2.855
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.721
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27370
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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    1.932
_exptl_crystal_description       plate
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.853
_refine_diff_density_min         -0.856
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         4303
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.999
_refine_ls_R_factor_all          0.0581
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0294P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0766
_refine_ls_wR_factor_ref         0.0859
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3288
_reflns_number_total             4303
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01406_si_010.cif
_cod_data_source_block           103-7072-7719_ca87
_cod_original_cell_volume        1880.64(12)
_cod_database_code               4035044
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Br3 O N C15'
_shelx_estimated_absorpt_t_max   0.553
_shelx_estimated_absorpt_t_min   0.202
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.51
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C0AA(H0AA)
2.b Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C7(H7), C5(H5), C11(H11), C6(H6), C8(H8), C14(H14), C15(H15),
 C13(H13), C12(H12)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              19280
_shelx_hkl_checksum              36202
_olex2_submission_special_instructions 'No special instructions were received'