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_7159848
_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 H18 Cl2 F2 N4 O'
_chemical_formula_sum            'C25 H18 Cl2 F2 N4 O'
_chemical_formula_weight         499.33
_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             2023-03-28
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-04-03 deposited with the CCDC.	2024-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.020(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.8243(4)
_cell_length_b                   7.18030(10)
_cell_length_c                   16.7155(3)
_cell_measurement_reflns_used    11936
_cell_measurement_temperature    274.7(3)
_cell_measurement_theta_max      76.0480
_cell_measurement_theta_min      2.7180
_cell_volume                     2308.48(7)
_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 1.5 (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 (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      274.7(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.943
_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    134.00 173.00   0.50    0.05    --  109.62  45.00 150.00   78
  2  \w    135.00 162.00   0.50    0.05    --  109.62 125.00  90.00   54
  3  \w     81.00 122.00   0.50    0.05    --  109.62 125.00  90.00   82
  4  \w    100.00 125.00   0.50    0.05    --  109.62 123.00 -13.00   50
  5  \w     60.00 117.00   0.50    0.05    --   44.26 148.00 150.00  114
  6  \w     91.00 118.00   0.50    0.05    --  109.62  45.00 150.00   54
  7  \w   -174.00 -74.00   0.50    0.05    -- -100.00 -77.00 -90.00  200
  8  \w   -132.00 -89.00   0.50    0.05    -- -100.00-125.00-150.00   86
  9  \w   -153.00-128.00   0.50    0.05    -- -100.00-123.00 -93.00   50
 10  \w   -117.00 -69.00   0.50    0.05    --  -44.26-148.00 102.00   96
 11  \w   -128.00-102.00   0.50    0.05    -- -100.00 148.00 150.00   52
 12  \w    -94.00 -50.00   0.50    0.05    --  -44.26 123.00 -13.00   88
 13  \w   -109.00 -35.00   0.50    0.05    -- -100.00  77.00   0.00  148
 14  \w    -54.00 -29.00   0.50    0.05    -- -100.00  45.00 150.00   50
 15  \w    -54.00 -29.00   0.50    0.05    -- -100.00  45.00  30.00   50
 16  \w    -54.00 -27.00   0.50    0.05    -- -100.00  61.00-150.00   54
 17  \w    -53.00 -28.00   0.50    0.05    -- -100.00  45.00-150.00   50
 18  \w    -53.00 -25.00   0.50    0.05    -- -100.00  45.00-180.00   56
 19  \w    -32.00  39.00   0.50    0.05    --   44.26 -37.00 -60.00  142
 20  \w    -18.00  23.00   0.50    0.05    --   44.26 -19.00 -30.00   82
 21  \w    -30.00  -3.00   0.50    0.05    --   44.26 -19.00 -90.00   54
 22  \w    -28.00  -3.00   0.50    0.05    --   44.26 -19.00-120.00   50
 23  \w     54.00  80.00   0.50    0.05    --   44.26-123.00 -93.00   52
 24  \w     37.00 107.00   0.50    0.05    --  109.62-123.00 -93.00  140
 25  \w     57.00 107.00   0.50    0.05    --  109.62-125.00 -30.00  100
 26  \w     62.00 128.00   0.50    0.05    --  109.62-148.00 102.00  132
;
_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      0.0626219000
_diffrn_orient_matrix_UB_12      -0.1283177000
_diffrn_orient_matrix_UB_13      0.0342479000
_diffrn_orient_matrix_UB_21      0.0485778000
_diffrn_orient_matrix_UB_22      0.1706154000
_diffrn_orient_matrix_UB_23      0.0146697000
_diffrn_orient_matrix_UB_31      -0.0116085000
_diffrn_orient_matrix_UB_32      0.0216543000
_diffrn_orient_matrix_UB_33      0.0873664000
_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  0.0407
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            14610
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.382
_diffrn_reflns_theta_min         5.382
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.899
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44383
_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    1.437
_exptl_crystal_description       block
_exptl_crystal_F_000             1024
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.362
_refine_diff_density_min         -0.562
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         4553
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0551
_refine_ls_R_factor_gt           0.0533
_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^)+(0.0894P)^2^+0.6323P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1391
_refine_ls_wR_factor_ref         0.1410
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4214
_reflns_number_total             4553
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00044g2.cif
_cod_data_source_block           fy_0328_auto
_cod_depositor_comments
'Adding full bibliography for 7159847--7159850.cif.'
_cod_database_code               7159848
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.27
_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:
 C8(H8), C17(H17)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C13(H13), C14(H14), C16(H16), C18(H18), C19(H19), C20(H20),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              53100
_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 2.260
_oxdiff_exptl_absorpt_empirical_full_min 0.558