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_7156074
_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         'C13 H13 F3 N2 O'
_chemical_formula_sum            'C13 H13 F3 N2 O'
_chemical_formula_weight         270.25
_chemical_name_systematic
trans-1-(p-Totyl)-3-trifluoromethyl-3a,4,5,6a-tetrahydro-1H-furo[2,3-c]pyrazole
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-02-02
_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            8
_cell_length_a                   15.5438(3)
_cell_length_b                   7.15478(11)
_cell_length_c                   23.2224(4)
_cell_measurement_reflns_used    7688
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      78.4810
_cell_measurement_theta_min      4.7420
_cell_volume                     2582.62(8)
_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 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -70.00 -33.00   0.50    0.27    --  -86.25 125.00-120.00   74
  2  \w     12.00  67.00   0.50    0.10    --   -5.34  38.00 -60.00  110
  3  \w      3.00  74.00   0.50    0.10    --    5.34  57.00 -30.00  142
  4  \w    -69.00 -15.00   0.50    0.27    --  -86.25  38.00  30.00  108
  5  \w    -69.00 -11.00   0.50    0.27    --  -86.25  38.00 -90.00  116
  6  \w    -70.00 -34.00   0.50    0.27    --  -86.25  38.00-180.00   72
  7  \w     99.00 152.00   0.50    0.27    --  107.75  19.00  60.00  106
  8  \w     99.00 176.00   0.50    0.27    --  107.75  19.00 150.00  154
  9  \w     80.00 109.00   0.50    0.27    --  107.75 -99.00 -30.00   58
 10  \w     40.00  65.00   0.50    0.27    --  107.75 -99.00 -30.00   50
 11  \w     78.00 111.00   0.50    0.27    --  107.75 -99.00-150.00   66
 12  \w   -143.00 -71.00   0.50    0.27    --  -86.25-125.00 -60.00  144
 13  \w     34.00  59.00   0.50    0.27    --  107.75 -38.00 150.00   50
 14  \w     39.00  79.00   0.50    0.27    --  107.75 -57.00 -30.00   80
 15  \w     44.00 119.00   0.50    0.27    --  107.75 -77.00-120.00  150
;
_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      -0.0961343000
_diffrn_orient_matrix_UB_12      0.0358778000
_diffrn_orient_matrix_UB_13      0.0117258000
_diffrn_orient_matrix_UB_21      0.0166549000
_diffrn_orient_matrix_UB_22      -0.0139202000
_diffrn_orient_matrix_UB_23      0.0652602000
_diffrn_orient_matrix_UB_31      0.0173756000
_diffrn_orient_matrix_UB_32      0.2118564000
_diffrn_orient_matrix_UB_33      0.0022892000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_av_unetI/netI     0.0294
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            11966
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.243
_diffrn_reflns_theta_min         4.754
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.029
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.397
_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    1.390
_exptl_crystal_description       plate
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.853
_exptl_crystal_size_mid          0.422
_exptl_crystal_size_min          0.129
_refine_diff_density_max         0.180
_refine_diff_density_min         -0.154
_refine_diff_density_rms         0.049
_refine_ls_extinction_coef       0.0066(4)
_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   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         2371
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0482P)^2^+0.4044P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1010
_refine_ls_wR_factor_ref         0.1049
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1972
_reflns_number_total             2371
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob03126b2.cif
_cod_data_source_block           gu-480
_cod_depositor_comments
'Adding full bibliography for 7156073--7156074.cif.'
_cod_database_code               7156074
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C13 H13 N2 O1 F3'
_diffrn_oxdiff_ac3_digest_frames
;
013fae8a261492761cf581ccbc042f7fe0014804727
;
_diffrn_oxdiff_ac3_digest_hkl
;
01c7b575154c18937e56a9f9a3b6c89529f28b
;
_reflns_odcompleteness_completeness 99.74
_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,H,H,H) groups
2. Restrained distances
 C16-F17A \\sim C16-F18A \\sim C16-F19A \\sim C16-F17 \\sim C16-F18 \\sim
C16-F19
 with sigma of 0.02
 F17A-F18A \\sim F17A-F19A \\sim F18A-F19A \\sim F17-F18 \\sim F17-F19 \\sim
F18-F19
 with sigma of 0.02
3. Others
 Sof(F19A)=Sof(F18A)=Sof(F17A)=1-FVAR(1)
 Sof(F17)=Sof(F18)=Sof(F19)=FVAR(1)
 Fixed Sof: H15A(0.5) H15B(0.5) H15C(0.5) H15D(0.5) H15E(0.5) H15F(0.5)
4.a Ternary CH refined with riding coordinates:
 C8(H8), C4(H4)
4.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C5(H5A,H5B)
4.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C14(H14), C11(H11), C13(H13)
4.d Disordered Me refined with riding coordinates:
 C15(H15A,H15B,H15C,H15D,H15E,H15F)
;
_shelx_res_checksum              59284
_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 1.196
_oxdiff_exptl_absorpt_empirical_full_min 0.678