Synthesis of 3,5-bis(fluoroalkyl)pyrazoles/pyrazolines <i>via</i> [3 + 2] cycloaddition of di/trifluoroacetohydrazonoyl bromides and trifluoromethyl-substituted alkenes.
Wang, Ruikang; Jin, Peng; Yang, Gaowang; Fan, Ying; Bai, Zuyu; Huang, Danfeng; Wang, Ke-Hu; Wang, Junjiao; Hu, Yulai; Organic & biomolecular chemistry 23 (2025) 638–648; doi:10.1039/d4ob01160k

data_7160246
_publ_section_title
;
 Synthesis of 3,5-bis(fluoroalkyl)pyrazoles/pyrazolines <i>via</i> [3 + 2]
 cycloaddition of di/trifluoroacetohydrazonoyl bromides and
 trifluoromethyl-substituted alkenes.
;
_journal_issue                   3
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              638
_journal_page_last               648
_journal_paper_doi               10.1039/d4ob01160k
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C17 H12 Br F5 N2'
_chemical_formula_sum            'C17 H12 Br F5 N2'
_chemical_formula_weight         419.20
_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     dual
_audit_creation_date             2024-08-30
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-08-31 deposited with the CCDC.	2024-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                86.890(3)
_cell_angle_beta                 73.961(4)
_cell_angle_gamma                70.172(4)
_cell_formula_units_Z            2
_cell_length_a                   7.4520(4)
_cell_length_b                   10.0443(4)
_cell_length_c                   11.7716(5)
_cell_measurement_reflns_used    8208
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.2640
_cell_measurement_theta_min      3.8830
_cell_volume                     795.85(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.942
_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     32.00  59.00   0.50    0.05    --  104.75 -61.00 -90.00   54
  2  \w    -19.00  28.00   0.50    0.05    --   46.68 -19.00-120.00   94
  3  \w    -21.00  27.00   0.50    0.05    --   46.68 -19.00 -30.00   96
  4  \w    -27.00  27.00   0.50    0.05    --   46.68 -19.00  30.00  108
  5  \w    -25.00  37.00   0.50    0.05    --   46.68 -37.00 120.00  124
  6  \w     75.00 103.00   0.50    0.05    --  104.75 -94.00 150.00   56
  7  \w     39.00  83.00   0.50    0.05    --  104.75-125.00  60.00   88
  8  \w     37.00 112.00   0.50    0.05    --  104.75-125.00 120.00  150
  9  \w     83.00 110.00   0.50    0.05    --  104.75-125.00  30.00   54
 10  \w     79.00 111.00   0.50    0.05    --  104.75-125.00   0.00   64
 11  \w     46.00  71.00   0.50    0.05    --  104.75-125.00  30.00   50
 12  \w     72.00 110.00   0.50    0.05    --  104.75-125.00 -90.00   76
 13  \w     35.00  68.00   0.50    0.05    --  104.75-125.00 -90.00   66
 14  \w     46.00 112.00   0.50    0.05    --  104.75-125.00-180.00  132
 15  \w     36.00  69.00   0.50    0.05    --   46.68-125.00-180.00   66
 16  \w    -25.00  77.00   0.50    0.05    --   46.68 -94.00  36.00  204
 17  \w     65.00  99.00   0.50    0.05    --  104.75 -94.00  90.00   68
 18  \w     69.00  95.00   0.50    0.05    --  104.75 -94.00  36.00   52
 19  \w     93.00 172.00   0.50    0.05    --  104.75  45.00 120.00  158
 20  \w    112.00 137.00   0.50    0.05    --  104.75  94.00 146.00   50
 21  \w    144.00 169.00   0.50    0.05    --  104.75  77.00-180.00   50
 22  \w     82.00 136.00   0.50    0.05    --  104.75  77.00-180.00  108
 23  \w    -83.00 -40.00   0.50    0.05    -- -102.00  77.00 -30.00   86
 24  \w    -67.00 -30.00   0.50    0.05    -- -102.00  61.00  90.00   74
 25  \w    -67.00 -41.00   0.50    0.05    -- -102.00  61.00-120.00   52
 26  \w    -67.00 -35.00   0.50    0.05    -- -102.00  61.00-150.00   64
 27  \w   -100.00 -32.00   0.50    0.05    -- -102.00 125.00-120.00  136
 28  \w    -29.00   8.00   0.50    0.05    --  -46.68  94.00 146.00   74
 29  \w    -77.00 -51.00   0.50    0.05    -- -102.00  94.00 146.00   52
 30  \w   -175.00 -90.00   0.50    0.05    -- -102.00 -61.00 -90.00  170
 31  \w   -127.00 -89.00   0.50    0.05    -- -102.00 -45.00 -30.00   76
 32  \w   -159.00-131.00   0.50    0.05    -- -102.00 -45.00 -30.00   56
 33  \w   -133.00 -84.00   0.50    0.05    -- -102.00 -77.00 120.00   98
 34  \w   -174.00-116.00   0.50    0.05    -- -102.00 -94.00 120.00  116
 35  \w   -157.00 -84.00   0.50    0.05    -- -102.00 -94.00  36.00  146
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1416059000
_diffrn_orient_matrix_UB_12      -0.1524145000
_diffrn_orient_matrix_UB_13      0.0023075000
_diffrn_orient_matrix_UB_21      0.1220293000
_diffrn_orient_matrix_UB_22      0.0121227000
_diffrn_orient_matrix_UB_23      -0.1267390000
_diffrn_orient_matrix_UB_31      0.1314843000
_diffrn_orient_matrix_UB_32      0.0570649000
_diffrn_orient_matrix_UB_33      0.0500981000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0251
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8425
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.919
_diffrn_reflns_theta_min         3.911
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.064
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78271
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.749
_exptl_crystal_description       block
_exptl_crystal_F_000             416
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.389
_refine_diff_density_min         -0.558
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3125
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0300
_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^)+(0.0370P)^2^+0.8019P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0748
_refine_ls_wR_factor_ref         0.0750
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3093
_reflns_number_total             3125
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01160k2.cif
_cod_data_source_block           rkw_0830-1_auto
_cod_depositor_comments
'Adding full bibliography for 7160245--7160246.cif.'
_cod_database_code               7160246
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C8(H8), C11(H11), C14(H14), C15(H15), C16(H16),
 C17(H17)
;
_shelx_res_checksum              26180
_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 1.378
_oxdiff_exptl_absorpt_empirical_full_min 0.689