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_7159847
_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 H20 F2 N4 O'
_chemical_formula_sum            'C25 H20 F2 N4 O'
_chemical_formula_weight         430.45
_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             2022-06-13
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-04-03 deposited with the CCDC.	2024-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.475(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9855(2)
_cell_length_b                   19.7009(3)
_cell_length_c                   12.8893(2)
_cell_measurement_reflns_used    8057
_cell_measurement_temperature    301.78(10)
_cell_measurement_theta_max      75.9680
_cell_measurement_theta_min      4.1750
_cell_volume                     2227.83(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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      301.78(10)
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.935
_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    102.00 128.00   0.50    0.25    --  107.75  24.00-152.00   52
  2  \w    150.00 175.00   0.50    0.25    --  107.75  19.00 -30.00   50
  3  \w    116.00 142.00   0.50    0.25    --  107.75  19.00 -30.00   52
  4  \w     45.00 100.00   0.50    0.08    --   47.57  24.00-152.00  110
  5  \w   -109.00 -81.00   0.50    0.25    -- -100.00  77.00  30.00   56
  6  \w    -75.00 -31.00   0.50    0.25    -- -100.00  77.00  30.00   88
  7  \w    -69.00 -39.00   0.50    0.25    -- -100.00  57.00   0.00   60
  8  \w    -69.00 -27.00   0.50    0.25    -- -100.00  57.00  30.00   84
  9  \w    -66.00 -36.00   0.50    0.25    -- -100.00  57.00 -30.00   60
 10  \w    -69.00 -33.00   0.50    0.25    -- -100.00  57.00  90.00   72
 11  \w    -54.00 -27.00   0.50    0.25    -- -100.00  57.00 -60.00   54
 12  \w    -68.00 -28.00   0.50    0.25    -- -100.00  77.00-180.00   80
 13  \w    -69.00 -34.00   0.50    0.25    -- -100.00  57.00-180.00   70
 14  \w   -108.00 -79.00   0.50    0.25    -- -100.00  77.00-180.00   58
 15  \w    -69.00 -27.00   0.50    0.25    -- -100.00  57.00 120.00   84
 16  \w    -69.00 -33.00   0.50    0.25    -- -100.00  57.00 150.00   72
 17  \w   -174.00 -87.00   0.50    0.25    -- -100.00 -24.00  42.00  174
 18  \w   -122.00 -40.00   0.50    0.08    --  -47.57 -24.00  42.00  164
 19  \w    -93.00 -64.00   0.50    0.08    --  -47.57 125.00 -30.00   58
 20  \w    -50.00 -23.00   0.50    0.08    --  -47.57 125.00 -30.00   54
 21  \w     43.00 109.00   0.50    0.25    --  107.75-125.00 -60.00  132
 22  \w     35.00  60.00   0.50    0.25    --  107.75 -57.00-150.00   50
 23  \w     59.00  85.00   0.50    0.25    --  107.75 -99.00 -60.00   52
 24  \w     36.00  61.00   0.50    0.25    --  107.75 -57.00 120.00   50
 25  \w     -3.00  27.00   0.50    0.08    --   47.57 -24.00  42.00   60
 26  \w    -27.00  23.00   0.50    0.08    --   47.57 -19.00 -90.00  100
 27  \w    -25.00   0.00   0.50    0.08    --  -47.57  24.00-152.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1691356000
_diffrn_orient_matrix_UB_12      -0.0145805000
_diffrn_orient_matrix_UB_13      -0.0484650000
_diffrn_orient_matrix_UB_21      0.0232221000
_diffrn_orient_matrix_UB_22      0.0231219000
_diffrn_orient_matrix_UB_23      -0.1096073000
_diffrn_orient_matrix_UB_31      0.0408834000
_diffrn_orient_matrix_UB_32      -0.0732695000
_diffrn_orient_matrix_UB_33      -0.0249864000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0273
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.935
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            15574
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.512
_diffrn_reflns_theta_min         4.168
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.764
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87963
_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    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.501
_refine_diff_density_min         -0.410
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         4439
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.249
_refine_ls_R_factor_all          0.0711
_refine_ls_R_factor_gt           0.0621
_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^)+(0.1077P)^2^+0.4269P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1853
_refine_ls_wR_factor_ref         0.1944
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3589
_reflns_number_total             4439
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00044g2.cif
_cod_data_source_block           a-2_auto
_cod_depositor_comments
'Adding full bibliography for 7159847--7159850.cif.'
_cod_original_cell_volume        2227.82(7)
_cod_database_code               7159847
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C22-F1B \\sim C22-F1
 with sigma of 0.02
 C22-F2 \\sim C22-F2B
 with sigma of 0.02
 F1B-F2 \\sim F1B-F2B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F1) \\sim Ueq, Uanis(F1B) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2B)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.005
4. Others
 Fixed Sof: F1(0.5) F1B(0.5) F2(0.5) F2B(0.5) H22A(0.5) H22(0.5)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C22(H22A), C22(H22)
5.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24), C25(H25)
5.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_shelx_res_checksum              17204
_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 3.624
_oxdiff_exptl_absorpt_empirical_full_min 0.571