Difluoroenol phosphinates as difluoroenolate surrogates: synthesis and applications in defluorination and deoxygenative coupling.
Kurosawa, Miki B.; Shimoyama, Shuhei; Tanaka, Hiroki; Yamaguchi, Junichiro; Chemical science 16 (2025) 13390–13400; doi:10.1039/d5sc03915k

data_1574897
_publ_section_title
;
 Difluoroenol phosphinates as difluoroenolate surrogates: synthesis and
 applications in defluorination and deoxygenative coupling.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              13390
_journal_page_last               13400
_journal_paper_doi               10.1039/d5sc03915k
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C24 H23 F2 O2 P'
_chemical_formula_sum            'C24 H23 F2 O2 P'
_chemical_formula_weight         412.39
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2lq5n5
_audit_creation_date             2024-11-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-11-22 deposited with the CCDC.	2025-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.24160(10)
_cell_length_b                   14.70540(10)
_cell_length_c                   22.9539(2)
_cell_measurement_reflns_used    16689
_cell_measurement_temperature    100.02(10)
_cell_measurement_theta_max      75.0690
_cell_measurement_theta_min      3.0270
_cell_volume                     4132.11(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_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      100.02(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.961
_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     55.00  98.00   0.50    0.15    --  108.78 -77.00-150.00   86
  2  \w     67.00 111.00   0.50    0.15    --  108.78-125.00  30.00   88
  3  \w     37.00  96.00   0.50    0.15    --  108.78-128.00  54.00  118
  4  \w     64.00 105.00   0.50    0.15    --  108.78 -95.00  60.00   82
  5  \w     39.00  97.00   0.50    0.15    --  108.78 -77.00  60.00  116
  6  \w     87.00 154.00   0.50    0.15    --  108.78  45.00  60.00  134
  7  \w    -28.00  38.00   0.50    0.05    --  -42.85  19.00 -30.00  132
  8  \w    -26.00  38.00   0.50    0.05    --  -42.85  19.00 -90.00  128
  9  \w    -28.00  38.00   0.50    0.05    --  -42.85  19.00  30.00  132
 10  \w    -51.00 -21.00   0.50    0.15    --  -96.00  45.00 -90.00   60
 11  \w    -46.00 -21.00   0.50    0.15    --  -96.00  45.00   0.00   50
 12  \w    -49.00 -20.00   0.50    0.15    --  -96.00  45.00  60.00   58
 13  \w    -69.00 -27.00   0.50    0.15    --  -96.00  61.00 150.00   84
 14  \w    -72.00 -29.00   0.50    0.15    --  -96.00 119.00  44.00   86
 15  \w    -80.00 -46.00   0.50    0.15    --  -96.00 128.00 129.00   68
 16  \w    -99.00 -56.00   0.50    0.05    --  -42.85 143.00 -60.00   86
 17  \w   -107.00 -41.00   0.50    0.15    --  -96.00 -11.00 117.00  132
 18  \w   -176.00-129.00   0.50    0.15    --  -96.00 -11.00 117.00   94
 19  \w   -143.00 -71.00   0.50    0.15    --  -96.00 -77.00 150.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1247004000
_diffrn_orient_matrix_UB_12      -0.0138349000
_diffrn_orient_matrix_UB_13      -0.0025602000
_diffrn_orient_matrix_UB_21      0.0038592000
_diffrn_orient_matrix_UB_22      -0.0061366000
_diffrn_orient_matrix_UB_23      0.0669741000
_diffrn_orient_matrix_UB_31      -0.0167673000
_diffrn_orient_matrix_UB_32      -0.1036289000
_diffrn_orient_matrix_UB_33      -0.0035632000
_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  0.0285
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            23326
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.381
_diffrn_reflns_theta_min         3.852
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.482
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.213
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_description       block
_exptl_crystal_F_000             1728
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.32
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.406
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         4115
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0319
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0383P)^2^+1.9888P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0811
_refine_ls_wR_factor_ref         0.0822
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3890
_reflns_number_total             4115
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03915k2.cif
_cod_data_source_block           SS601
_cod_depositor_comments          'Adding full bibliography for 1574897.cif.'
_cod_database_code               1574897
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.648
_shelx_estimated_absorpt_t_min   0.519
_olex2_refinement_description
;
1.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C14(H14), C5(H5), C7(H7), C18(H18), C20(H20), C16(H16),
 C17(H17), C24(H24), C15(H15), C21(H21), C23(H23), C22(H22)
1.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              66377
_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 1.595
_oxdiff_exptl_absorpt_empirical_full_min 0.792