Generation and NMR Study of Short-Lived and Reactive Trifluoroalkyl Carbocations of the α-Halogenothiophene Series in Brønsted Superacids: Reactions of the Cations with Arenes.
Khoroshilova, Olesya V.; Vasilyev, Aleksander V.; The Journal of organic chemistry 85 (2020) 5872–5883; doi:10.1021/acs.joc.0c00170

data_4038259
_publ_section_title
;
 Generation and NMR Study of Short-Lived and Reactive Trifluoroalkyl
 Carbocations of the \a-Halogenothiophene Series in Br\/onsted Superacids:
 Reactions of the Cations with Arenes.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5872
_journal_page_last               5883
_journal_paper_doi               10.1021/acs.joc.0c00170
_journal_volume                  85
_journal_year                    2020
_chemical_formula_moiety         'C16 H17 F3 S'
_chemical_formula_sum            'C16 H17 F3 S'
_chemical_formula_weight         298.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
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;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
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_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_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    -71.00  -2.00   0.50    1.70    --  -38.95 112.00 -55.00  138
  2  \w     23.00  81.00   0.50    1.70    --   38.95-112.00-148.00  116
  3  \w    104.00 130.00   0.50    5.50    --  104.29 112.00 -55.00   52
  4  \w     35.00 109.00   0.50    5.50    --  104.29-112.00-148.00  148
  5  \w   -104.00 -17.00   0.50    1.70    --  -38.95 -65.00-180.00  174
  6  \w     39.00  65.00   0.50    1.70    --   38.95  32.00-150.00   52
  7  \w     16.00  62.00   0.50    1.70    --   38.95-104.00-120.00   92
  8  \w     11.00  49.00   0.50    1.70    --   38.95-138.00  60.00   76
  9  \w     52.00  91.00   0.50    1.70    --   38.95  32.00 150.00   78
 10  \w     26.00 102.00   0.50    1.70    --   38.95  43.00 -30.00  152
 11  \w     13.00 103.00   0.50    1.70    --   38.95  77.00  90.00  180
 12  \w     67.00  98.00   0.50    1.70    --   38.95  65.00  60.00   62
 13  \w     56.00  87.00   0.50    1.70    --   38.95-138.00  60.00   62
 14  \w     25.00  51.00   0.50    1.70    --   38.95 -54.00   0.00   52
 15  \w     17.00  85.00   0.50    1.70    --   38.95  65.00 150.00  136
 16  \w     20.00  45.00   0.50    1.70    --   38.95  65.00  60.00   50
 17  \w     39.00 106.00   0.50    5.50    --  104.29-111.00 -90.00  134
 18  \w     87.00 157.00   0.50    5.50    --  104.29  45.00 -30.00  140
 19  \w    107.00 157.00   0.50    5.50    --  104.29  69.00  30.00  100
 20  \w     64.00 111.00   0.50    5.50    --  104.29-111.00  30.00   94
 21  \w     32.00  69.00   0.50    5.50    --  104.29 -93.00 -90.00   74
 22  \w    126.00 152.00   0.50    5.50    --  104.29  15.00-120.00   52
 23  \w     88.00 124.00   0.50    5.50    --  104.29 -53.00-180.00   72
 24  \w     91.00 149.00   0.50    5.50    --  104.29  93.00 120.00  116
 25  \w     35.00  82.00   0.50    5.50    --  104.29-111.00   0.00   94
 26  \w    131.00 157.00   0.50    5.50    --  104.29  45.00-120.00   52
 27  \w     95.00 121.00   0.50    5.50    --  104.29  45.00-120.00   52
 28  \w     79.00 104.00   0.50    5.50    --  104.29 -93.00 -90.00   50
 29  \w     35.00  81.00   0.50    5.50    --  104.29 -30.00-150.00   92
 30  \w     94.00 153.00   0.50    5.50    --  104.29  37.00 -60.00  118
 31  \w     41.00 109.00   0.50    5.50    --  104.29-133.00-150.00  136
 32  \w    113.00 155.00   0.50    5.50    --  104.29  69.00   0.00   84
 33  \w     85.00 110.00   0.50    5.50    --  104.29  53.00   0.00   50
 34  \w     43.00  69.00   0.50    5.50    --  104.29 -53.00-180.00   52
 35  \w    107.00 154.00   0.50    5.50    --  104.29  30.00 -90.00   94
 36  \w    -18.00   8.00   0.50    1.70    --  -38.95 112.00 -55.00   52
 37  \w    -12.00  14.00   0.50    1.70    --  -38.95  32.00   0.00   52
 38  \w    -44.00 -11.00   0.50    1.70    --  -38.95 138.00   0.00   66
 39  \w    -51.00 -26.00   0.50    1.70    --  -38.95  32.00   0.00   50
;
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'SuperNova, Single source at offset/far, HyPix3000'
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_diffrn_orient_matrix_UB_13      -0.0657702000
_diffrn_orient_matrix_UB_21      -0.0148653000
_diffrn_orient_matrix_UB_22      0.1514033000
_diffrn_orient_matrix_UB_23      -0.0121873000
_diffrn_orient_matrix_UB_31      0.0250065000
_diffrn_orient_matrix_UB_32      0.0301389000
_diffrn_orient_matrix_UB_33      0.1306452000
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_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0236
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
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_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            7568
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
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_diffrn_reflns_theta_max         72.480
_diffrn_reflns_theta_min         3.186
_diffrn_source                   'micro-focus sealed X-ray tube'
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_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77094
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_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
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    1.391
_exptl_crystal_description       plate
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.332
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_refine_ls_number_reflns         2799
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_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0702P)^2^+2.3215P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1183
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_reflns_number_gt                2512
_reflns_number_total             2799
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_cod_depositor_comments          'Adding full bibliography for 4038259.cif.'
_cod_original_cell_volume        2848.72(9)
_cod_database_code               4038259
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'S F3 C12'
_diffrn_oxdiff_ac3_digest_frames
;
01af6a38156d1656f46cac1f5f4b8348b200026402a
;
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;
01af706b4157318df091197e64cff83af7cc52
;
_reflns_odcompleteness_completeness 99.79
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_reflns_odcompleteness_theta     70.93
_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
2.a Ternary CH refined with riding coordinates:
 C6(H6)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C2(H2), C10(H10)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C)
;
_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 1.569
_oxdiff_exptl_absorpt_empirical_full_min 0.656