Collaborative Activation of Trifluoroacetyl Diazoester by a Lewis Acid and Base for the Synthesis of Polysubstituted 4-Trifluoromethylpyrazoles.
Fang, Zheng; Yin, Hongshan; Lin, Lu; Wen, Shunli; Xie, Lili; Huang, Yangjie; Weng, Zhiqiang; The Journal of organic chemistry 85 (2020) 8714–8722; doi:10.1021/acs.joc.0c00737

data_4038507
_publ_section_title
;
 Collaborative Activation of Trifluoroacetyl Diazoester by a Lewis Acid
 and Base for the Synthesis of Polysubstituted 4-Trifluoromethylpyrazoles.
;
_journal_issue                   13
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8714
_journal_page_last               8722
_journal_paper_doi               10.1021/acs.joc.0c00737
_journal_volume                  85
_journal_year                    2020
_chemical_formula_moiety         'C18 H17 F3 N2 O5'
_chemical_formula_sum            'C18 H17 F3 N2 O5'
_chemical_formula_weight         398.33
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.684(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6117(6)
_cell_length_b                   13.1472(7)
_cell_length_c                   16.2550(13)
_cell_measurement_reflns_used    1880
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      71.5350
_cell_measurement_theta_min      4.3230
_cell_volume                     1831.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35c (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      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1281
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.971
_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    -35.00 -10.00   1.00   10.00    --  -33.50  57.00  90.00   25
  2  \w    -62.00  29.00   1.00   10.00    --  -33.50  19.00-150.00   91
  3  \w     15.00  49.00   1.00   10.00    --   36.37  77.00-150.00   34
  4  \w     54.00 104.00   1.00   10.00    --   36.37  77.00-150.00   50
  5  \w     10.00  73.00   1.00   10.00    --   36.37 -99.00 -90.00   63
  6  \w     -4.00  45.00   1.00   10.00    --   36.37 -99.00  30.00   49
  7  \w     91.00 175.00   1.00   30.00    --  108.00  45.00  60.00   84
  8  \w     94.00 120.00   1.00   30.00    --  108.00  61.00 -90.00   26
  9  \w    104.00 165.00   1.00   30.00    --  108.00  77.00   0.00   61
 10  \w     41.00 120.00   1.00   30.00    --  108.00 -61.00  90.00   79
 11  \w     78.00 121.00   1.00   30.00    --  108.00 -45.00 -90.00   43
 12  \w    129.00 173.00   1.00   30.00    --  108.00  61.00 -90.00   44
 13  \w     40.00 103.00   1.00   30.00    --  108.00 -94.00 -60.00   63
 14  \w     88.00 178.00   1.00   30.00    --  108.00  30.00 -30.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1245735000
_diffrn_orient_matrix_UB_12      0.0836384000
_diffrn_orient_matrix_UB_13      -0.0153387000
_diffrn_orient_matrix_UB_21      -0.0406983000
_diffrn_orient_matrix_UB_22      -0.0396017000
_diffrn_orient_matrix_UB_23      -0.0887555000
_diffrn_orient_matrix_UB_31      -0.1230317000
_diffrn_orient_matrix_UB_32      -0.0718301000
_diffrn_orient_matrix_UB_33      0.0310760000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            6675
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.870
_diffrn_reflns_theta_min         4.334
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.090
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88094
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35c (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    1.445
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_refine_diff_density_max         0.176
_refine_diff_density_min         -0.166
_refine_diff_density_rms         0.037
_refine_ls_extinction_coef       0.0016(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     285
_refine_ls_number_reflns         3497
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0761
_refine_ls_R_factor_gt           0.0509
_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^)+(0.0543P)^2^+0.2409P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1277
_refine_ls_wR_factor_ref         0.1461
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2385
_reflns_number_total             3497
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00737_si_001.cif
_cod_data_source_block           exp_10349
_cod_depositor_comments          'Adding full bibliography for 4038507.cif.'
_cod_database_code               4038507
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F2) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(F3A) \\sim
Ueq, Uanis(F2A) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq: with
sigma of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 F1, F2, F3, C1, F3A, F2A, F1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F3A)=Sof(F2A)=Sof(F1A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B)
5.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C7(H7), C9(H9), C6(H6), C15(H15), C14(H14)
5.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              27289
_shelx_hkl_checksum              44165
_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 1.139
_oxdiff_exptl_absorpt_empirical_full_min 0.817