Polysubstituted 3-trifluoromethylpyrazoles: regioselective (3 + 2)-cycloaddition of trifluoroacetonitrile imines with enol ethers and functional group transformations.
Utecht, Greta; Fruziński, Andrzej; Jasiński, Marcin; Organic & biomolecular chemistry 16 (2018) 1252–1257; doi:10.1039/c7ob03126b

data_7156073
_publ_section_title
;
 Polysubstituted 3-trifluoromethylpyrazoles: regioselective (3 +
 2)-cycloaddition of trifluoroacetonitrile imines with enol ethers and
 functional group transformations.
;
_journal_issue                   8
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1252
_journal_page_last               1257
_journal_paper_doi               10.1039/c7ob03126b
_journal_volume                  16
_journal_year                    2018
_chemical_formula_moiety         'C21 H18 F3 N3 O4'
_chemical_formula_sum            'C21 H18 F3 N3 O4'
_chemical_formula_weight         433.38
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-02-04
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_audit_update_record
;
2017-02-06 deposited with the CCDC.
2018-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.9764(4)
_cell_length_b                   6.8786(2)
_cell_length_c                   19.4161(4)
_cell_measurement_reflns_used    5712
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      78.2150
_cell_measurement_theta_min      5.4190
_cell_volume                     2000.18(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_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(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_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    -15.00  30.00   0.50    0.10    --   -5.34  38.00 -30.00   90
  2  \w      6.00  60.00   0.50    0.10    --   -5.34  77.00-180.00  108
  3  \w     33.00  68.00   0.50    0.10    --   -5.34  38.00 -30.00   70
  4  \w    112.00 145.00   0.50    0.11    --  107.75 125.00  30.00   66
  5  \w     51.00 144.00   0.50    0.11    --  107.75   0.00  90.00  186
  6  \w     35.00  64.00   0.50    0.11    --  107.75 -38.00 -60.00   58
  7  \w     33.00  69.00   0.50    0.11    --  107.75 -38.00 -90.00   72
  8  \w   -106.00 -76.00   0.50    0.11    --  -86.25  77.00-120.00   60
  9  \w    -71.00 -34.00   0.50    0.11    --  -86.25  38.00 -30.00   74
 10  \w    -67.00 -13.00   0.50    0.11    --  -86.25  38.00 -90.00  108
 11  \w    -71.00 -38.00   0.50    0.11    --  -86.25  77.00-120.00   66
 12  \w    -94.00 -16.00   0.50    0.11    --  -86.25  57.00-180.00  156
 13  \w     38.00 113.00   0.50    0.11    --  107.75-125.00-120.00  150
 14  \w     78.00 108.00   0.50    0.11    --  107.75 -99.00 -60.00   60
 15  \w     62.00 107.00   0.50    0.11    --  107.75 -99.00  90.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0178327000
_diffrn_orient_matrix_UB_12      -0.0145840000
_diffrn_orient_matrix_UB_13      0.0779729000
_diffrn_orient_matrix_UB_21      0.1012658000
_diffrn_orient_matrix_UB_22      -0.0015028000
_diffrn_orient_matrix_UB_23      -0.0138146000
_diffrn_orient_matrix_UB_31      0.0017804000
_diffrn_orient_matrix_UB_32      0.2235424000
_diffrn_orient_matrix_UB_33      0.0050023000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0252
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            9487
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.245
_diffrn_reflns_theta_min         4.555
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.026
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.626
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.16b (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.439
_exptl_crystal_description       column
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.931
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.151
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.135
_refine_diff_density_rms         0.028
_refine_ls_extinction_coef       0.0028(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         1989
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0577P)^2^+0.2544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1106
_refine_ls_wR_factor_ref         0.1151
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1607
_reflns_number_total             1989
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob03126b2.cif
_cod_data_source_block           gu-476
_cod_depositor_comments
'Adding full bibliography for 7156073--7156074.cif.'
_cod_database_code               7156073
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C18 H18 N3 O4 F3'
_diffrn_oxdiff_ac3_digest_frames
;
01c272d392b5032cba47492e94c1a9226e01414e9ad
;
_diffrn_oxdiff_ac3_digest_hkl
;
015db320596519858f4fa0b5a734ac808a0939
;
_reflns_odcompleteness_completeness 99.62
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(F14A)=1-FVAR(1)
 Sof(F16A)=0.5*(1-FVAR(2))
 Sof(F15)=0.5*FVAR(2)
 Sof(F14)=FVAR(1)
 Fixed Sof: H18A(0.5) H18B(0.5) H19A(0.5) H19B(0.5) H17A(0.5) H17B(0.5)
 H12A(0.5) H12B(0.5) H12C(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C17(H17A,H17B)
3.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C11(H11), C5(H5), C28(H28), C24(H24), C10(H10), C27(H27), C7(H7),
 C8(H8)
3.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              94727
_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 1.364
_oxdiff_exptl_absorpt_empirical_full_min 0.831