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_7159849
_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           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-01
_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                 96.9104(11)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   18.9993(2)
_cell_length_b                   11.37225(15)
_cell_length_c                   43.5762(5)
_cell_measurement_reflns_used    15359
_cell_measurement_temperature    301.71(10)
_cell_measurement_theta_max      76.3870
_cell_measurement_theta_min      2.0360
_cell_volume                     9346.89(19)
_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      301.71(10)
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.939
_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    -25.00  17.00   0.50    0.05    --   47.45 -19.00   0.00   84
  2  \w    -22.00  23.00   0.50    0.05    --   47.45 -19.00  30.00   90
  3  \w     95.00 156.00   0.50    0.05    --  107.75 105.00-130.00  122
  4  \w     76.00 102.00   0.50    0.05    --  107.75 -77.00 120.00   52
  5  \w     39.00  68.00   0.50    0.05    --  107.75 -77.00 120.00   58
  6  \w     37.00  62.00   0.50    0.05    --  107.75 -57.00 150.00   50
  7  \w     35.00  62.00   0.50    0.05    --  107.75 -57.00 120.00   54
  8  \w     37.00  62.00   0.50    0.05    --  107.75 -57.00   0.00   50
  9  \w     53.00  79.00   0.50    0.05    --  107.75 -77.00-180.00   52
 10  \w     35.00  63.00   0.50    0.05    --  107.75 -57.00 -90.00   56
 11  \w     38.00  63.00   0.50    0.05    --  107.75 -57.00 -60.00   50
 12  \w     28.00  56.00   0.50    0.05    --   47.45-105.00 128.00   56
 13  \w     55.00 106.00   0.50    0.05    --  107.75-105.00 128.00  102
 14  \w    -15.00  26.00   0.50    0.05    --  -47.45  37.00  90.00   82
 15  \w    -59.00 -27.00   0.50    0.05    -- -100.00 125.00 -90.00   64
 16  \w   -103.00 -61.00   0.50    0.05    -- -100.00 105.00-130.00   84
 17  \w    -80.00 -14.00   0.50    0.05    --  -47.45 105.00-130.00  132
 18  \w    -66.00 -27.00   0.50    0.05    -- -100.00  57.00-150.00   78
 19  \w    -63.00 -36.00   0.50    0.05    -- -100.00  57.00-180.00   54
 20  \w    -68.00 -28.00   0.50    0.05    -- -100.00  57.00  30.00   80
 21  \w    -66.00 -34.00   0.50    0.05    -- -100.00  57.00  60.00   64
 22  \w    -61.00 -32.00   0.50    0.05    -- -100.00  57.00  90.00   58
 23  \w   -120.00 -43.00   0.50    0.05    --  -47.45 -57.00 150.00  154
 24  \w   -162.00-107.00   0.50    0.05    -- -100.00-105.00 128.00  110
 25  \w   -172.00 -99.00   0.50    0.05    -- -100.00-125.00-180.00  146
;
_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      0.0055404000
_diffrn_orient_matrix_UB_12      0.1306408000
_diffrn_orient_matrix_UB_13      0.0093368000
_diffrn_orient_matrix_UB_21      0.0803901000
_diffrn_orient_matrix_UB_22      -0.0030142000
_diffrn_orient_matrix_UB_23      -0.0019544000
_diffrn_orient_matrix_UB_31      -0.0133194000
_diffrn_orient_matrix_UB_32      0.0357434000
_diffrn_orient_matrix_UB_33      -0.0343130000
_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  0.0332
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -54
_diffrn_reflns_number            30745
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.401
_diffrn_reflns_theta_min         2.043
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.864
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31568
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_description       block
_exptl_crystal_F_000             4096
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.799
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     615
_refine_ls_number_reflns         9322
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.159
_refine_ls_R_factor_all          0.0760
_refine_ls_R_factor_gt           0.0644
_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^)+(0.1236P)^2^+3.5605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1957
_refine_ls_wR_factor_ref         0.2087
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7295
_reflns_number_total             9322
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00044g2.cif
_cod_data_source_block           a-21-1_auto
_cod_depositor_comments
;
Adding full bibliography for 7159847--7159850.cif.

2024-10-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C50 H36 Cl4 F4 N8 O2'
_cod_original_formula_weight         998.67
_cod_original_formula_moiety         '2(C25 H18 Cl2 F2 N4 O)'
_cod_original_formula_units_Z            8
_cod_original_cell_volume        9346.9(2)
_cod_database_code               7159849
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.870
_shelx_estimated_absorpt_t_min   0.783
_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. Uiso/Uaniso restraints and constraints
Uanis(F2) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq: with
sigma of 0.01 and sigma for terminal atoms of 0.005
3.a Ternary CH refined with riding coordinates:
 C4(H4), C48(H48), C2(H2), C44(H44)
3.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C17(H17), C18(H18), C21(H21), C35(H35), C36(H36),
 C37(H37), C41(H41), C42(H42), C43(H43), C45(H45), C46(H46), C15(H15), C20(H20),
  C23(H23), C25(H25), C29(H29), C30(H30), C33(H33), C38(H38), C39(H39),
 C40(H40), C47(H47), C49(H49), C50(H50)
3.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              62931
_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 2.354
_oxdiff_exptl_absorpt_empirical_full_min 0.579