Synthesis of difluoromethylated spiropyrazolones <i>via</i> [3 + 2] cycloaddition of difluoroacetohydrazonoyl bromides with alkylidene pyrazolones.
Feng, Yang; Ren, Yuanyuan; Tang, Duoduo; Wang, Ke-Hu; Wang, Junjiao; Huang, Danfeng; Lv, Xiaobo; Hu, Yulai; Organic & biomolecular chemistry 22 (2024) 2797–2812; doi:10.1039/d4ob00044g

data_7159850
_publ_section_title
;
 Synthesis of difluoromethylated spiropyrazolones <i>via</i> [3 + 2]
 cycloaddition of difluoroacetohydrazonoyl bromides with alkylidene
 pyrazolones.
;
_journal_issue                   14
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2797
_journal_page_last               2812
_journal_paper_doi               10.1039/d4ob00044g
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C25 H19 F3 N4 O'
_chemical_formula_sum            'C25 H19 F3 N4 O'
_chemical_formula_weight         448.44
_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             2021-12-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-04-03 deposited with the CCDC.	2024-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.0820(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.01840(10)
_cell_length_b                   19.8009(3)
_cell_length_c                   12.6774(2)
_cell_measurement_reflns_used    12915
_cell_measurement_temperature    287.3(2)
_cell_measurement_theta_max      77.1580
_cell_measurement_theta_min      4.1900
_cell_volume                     2221.62(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      287.3(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.947
_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     69.00 115.00   0.50    0.05    --   47.57 138.00-106.00   92
  2  \w     68.00  98.00   0.50    0.05    --  107.75 138.00-106.00   60
  3  \w    145.00 171.00   0.50    0.05    --  107.75  19.00  90.00   52
  4  \w     97.00 125.00   0.50    0.05    --  107.75  19.00  90.00   56
  5  \w     99.00 124.00   0.50    0.05    --  107.75 131.00  77.00   50
  6  \w     78.00 117.00   0.50    0.05    --   47.57 131.00  77.00   78
  7  \w    -68.00 -32.00   0.50    0.05    -- -100.00  57.00 -90.00   72
  8  \w    -98.00 -57.00   0.50    0.05    --  -47.57 138.00-106.00   82
  9  \w    -77.00 -51.00   0.50    0.05    --  -47.57 131.00  77.00   52
 10  \w    -27.00  23.00   0.50    0.05    --   47.57 -19.00  60.00  100
 11  \w    -24.00  22.00   0.50    0.05    --   47.57 -19.00   0.00   92
 12  \w    -20.00  10.00   0.50    0.05    --   47.57 -19.00 -30.00   60
 13  \w    -23.00   2.00   0.50    0.05    --   47.57 -19.00-120.00   50
 14  \w    -12.00  13.00   0.50    0.05    --   47.57 -19.00-150.00   50
 15  \w     79.00 104.00   0.50    0.05    --  107.75 -99.00   0.00   50
 16  \w     51.00  76.00   0.50    0.05    --  107.75-131.00   6.00   50
 17  \w     35.00 120.00   0.50    0.05    --  107.75-138.00-168.00  170
 18  \w     36.00  61.00   0.50    0.05    --   47.57-131.00   6.00   50
 19  \w     52.00 102.00   0.50    0.05    --  107.75 -77.00   0.00  100
 20  \w     37.00  63.00   0.50    0.05    --  107.75 -57.00  60.00   52
 21  \w     35.00  62.00   0.50    0.05    --  107.75 -57.00 150.00   54
 22  \w   -108.00 -36.00   0.50    0.05    -- -100.00 109.00 -32.35  144
 23  \w   -121.00 -64.00   0.50    0.05    -- -100.00 138.00  19.27  114
 24  \w   -100.00 -75.00   0.50    0.05    -- -100.00 138.00-106.00   50
 25  \w   -120.00 -86.00   0.50    0.05    -- -100.00 136.00-140.65   68
 26  \w    -78.00 -37.00   0.50    0.05    -- -100.00 136.00-140.65   82
 27  \w   -113.00 -85.00   0.50    0.05    -- -100.00 -57.00  90.00   56
 28  \w   -172.00-121.00   0.50    0.05    -- -100.00 -57.00  90.00  102
 29  \w   -169.00-103.00   0.50    0.05    -- -100.00 -57.00-150.00  132
 30  \w   -139.00-101.00   0.50    0.05    -- -100.00-138.00-168.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1161616000
_diffrn_orient_matrix_UB_12      -0.0579821000
_diffrn_orient_matrix_UB_13      -0.0160568000
_diffrn_orient_matrix_UB_21      0.1294601000
_diffrn_orient_matrix_UB_22      -0.0518653000
_diffrn_orient_matrix_UB_23      0.0223669000
_diffrn_orient_matrix_UB_31      -0.0052254000
_diffrn_orient_matrix_UB_32      0.0019075000
_diffrn_orient_matrix_UB_33      0.1207328000
_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  0.0283
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            17080
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.289
_diffrn_reflns_theta_min         4.197
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.855
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74533
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.520
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.034
_refine_ls_extinction_coef       0.0078(10)
_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   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         4459
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0581
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0769P)^2^+0.5430P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1510
_refine_ls_wR_factor_ref         0.1555
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3872
_reflns_number_total             4459
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00044g2.cif
_cod_data_source_block           xray_1207_auto
_cod_depositor_comments
'Adding full bibliography for 7159847--7159850.cif.'
_cod_original_cell_volume        2221.62(5)
_cod_database_code               7159850
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.854
_reflns_odcompleteness_completeness 99.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C5(H5)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C)
;
_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 2.203
_oxdiff_exptl_absorpt_empirical_full_min 0.392