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_4035045
_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         'C23 H28 Cl3 N O'
_chemical_formula_sum            'C23.01 H28 Cl3 N O'
_chemical_formula_weight         440.99
_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     iterative
_audit_creation_date             2017-11-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                68.473(6)
_cell_angle_beta                 81.496(5)
_cell_angle_gamma                73.833(6)
_cell_formula_units_Z            2
_cell_length_a                   9.1989(6)
_cell_length_b                   11.3605(7)
_cell_length_c                   12.1333(6)
_cell_measurement_reflns_used    3567
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.7640
_cell_measurement_theta_min      3.0000
_cell_volume                     1131.40(13)
_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
;
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 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -25.00   20.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.2678  -99.0000   60.0000 45

  2 omega    8.00   47.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.2678   77.0000  -60.0000 39

  3 omega  -97.00  -39.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.2678 -178.0000  -90.0000 58

  4 omega  -16.00   19.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.2678  -99.0000 -150.0000 35

  5 omega   -4.00   60.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -       23.3616  -99.0000  -60.0000 64

  6 omega    4.00   89.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -       23.3616   57.0000 -150.0000 85

  7 omega  -45.00   55.00   1.0000   70.0000
omega____ theta____ kappa____ phi______ frames
    -       23.3616  -19.0000   30.0000 100
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0335361000
_diffrn_orient_matrix_UB_12      -0.0400083000
_diffrn_orient_matrix_UB_13      -0.0347113000
_diffrn_orient_matrix_UB_21      0.0427734000
_diffrn_orient_matrix_UB_22      -0.0458869000
_diffrn_orient_matrix_UB_23      0.0486014000
_diffrn_orient_matrix_UB_31      -0.0592277000
_diffrn_orient_matrix_UB_32      -0.0329058000
_diffrn_orient_matrix_UB_33      0.0198136000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_unetI/netI     0.0422
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9744
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         2.654
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.419
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95367
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       prism
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.522
_refine_diff_density_min         -0.538
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     269
_refine_ls_number_reflns         5170
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0417P)^2^+0.9834P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1085
_refine_ls_wR_factor_ref         0.1181
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4102
_reflns_number_total             5170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01406_si_008.cif
_cod_data_source_block           103-7072-8029_117
_cod_database_code               4035045
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Cl3 N O C23'
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.899
_reflns_odcompleteness_completeness 99.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.51
_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. Uiso/Uaniso restraints and constraints
Uanis(C13') = Uanis(C11) = Uanis(C12') = Uanis(C14') = Uanis(C15') = Uanis(C14)
= Uanis(C13) = Uanis(C12) = Uanis(C15)
Uanis(C13') = Uanis(C12') = Uanis(C14') = Uanis(C15') = Uanis(C14) = Uanis(C13)
= Uanis(C12) = Uanis(C15)
Uanis(C13') = Uanis(C11) = Uanis(C12') = Uanis(C5) = Uanis(C14') = Uanis(C15')
= Uanis(C14) = Uanis(C13) = Uanis(C12) = Uanis(C15)
Uanis(C5) = Uanis(C15') = Uanis(C14') = Uanis(C11) = Uanis(C13') = Uanis(C12')
Uanis(C21') = Uanis(C21)
3. Others
 Sof(C14)=Sof(C13)=Sof(H13)=Sof(C12)=Sof(C15)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C22)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=1-FVAR(1)
 Sof(C13')=Sof(C12')=Sof(C14')=Sof(C15')=Sof(H15')=Sof(C22')=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=Sof(C20')=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21')=
 Sof(H21D)=Sof(H21E)=Sof(H21F)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C2(H2)
4.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C15'(H15'), C13(H13)
4.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C17(H17A,H17B,
 H17C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22'(H22A,H22B,H22C),
 C20'(H20D,H20E,H20F), C23(H23A,H23B,H23C), C22(H22D,H22E,H22F), C21'(H21D,H21E,
 H21F)
4.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              7451
_shelx_hkl_checksum              27265
_olex2_date_sample_data_collection 2017-11-23
_olex2_submission_special_instructions 'No special instructions were received'