Photocatalytic 1,3-difluoroalkylcarboxylation of alkenes by triple kinetic-controlled radical self-ordering.
Fu, Hong; Wang, Zuo-Shuai; Li, Si-Jia; Zhu, Lin-Yuan; Wang, Xiao-Jian; Wang, Hong-Chen; Han, Bing; Chemical science 16 (2025) 5849–5856; doi:10.1039/d4sc08607d

data_1573928
_publ_section_title
;
 Photocatalytic 1,3-difluoroalkylcarboxylation of alkenes by triple
 kinetic-controlled radical self-ordering.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              5849
_journal_page_last               5856
_journal_paper_doi               10.1039/d4sc08607d
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C22 H23 F2 N O3'
_chemical_formula_sum            'C22 H23 F2 N O3'
_chemical_formula_weight         387.41
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-31
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-09-02 deposited with the CCDC.	2025-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                108.444(6)
_cell_angle_beta                 102.977(6)
_cell_angle_gamma                113.996(7)
_cell_formula_units_Z            2
_cell_length_a                   9.9380(7)
_cell_length_b                   10.9753(9)
_cell_length_c                   11.0840(7)
_cell_measurement_reflns_used    5202
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      75.3210
_cell_measurement_theta_min      4.6000
_cell_volume                     956.77(17)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.930
_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   -104.00 -39.00   0.50    0.26    -- -102.00  77.00 -60.00  130
  2  \w    -65.00 -29.00   0.50    0.26    -- -102.00  61.00   0.00   72
  3  \w    -65.00 -33.00   0.50    0.26    -- -102.00  61.00  90.00   64
  4  \w    -87.00 -36.00   0.50    0.26    -- -102.00  77.00 120.00  102
  5  \w    -61.00 -32.00   0.50    0.06    --  -46.05  57.00  30.00   58
  6  \w    -35.00  26.00   0.50    0.06    --  -46.05  37.00 -90.00  122
  7  \w    -20.00   8.00   0.50    0.06    --  -46.05  19.00 -60.00   56
  8  \w     -9.00  16.00   0.50    0.06    --  -46.05  57.00  30.00   50
  9  \w    -42.00  27.00   0.50    0.06    --  -46.05  39.00 152.00  138
 10  \w   -107.00 -82.00   0.50    0.26    -- -102.00 110.00 171.77   50
 11  \w   -109.00 -73.00   0.50    0.26    -- -102.00 125.00 120.00   72
 12  \w    -71.00 -34.00   0.50    0.26    -- -102.00 110.00 171.77   74
 13  \w    -66.00 -40.00   0.50    0.26    -- -102.00 125.00 120.00   52
 14  \w   -111.00 -68.00   0.50    0.26    -- -102.00 125.00 -90.00   86
 15  \w    -66.00 -40.00   0.50    0.26    -- -102.00 125.00 -90.00   52
 16  \w   -132.00-102.00   0.50    0.26    -- -102.00 -39.00  -1.00   60
 17  \w   -165.00-139.00   0.50    0.26    -- -102.00 -39.00  -1.00   52
 18  \w   -170.00 -96.00   0.50    0.26    -- -102.00 -45.00  30.00  148
 19  \w   -110.00 -37.00   0.50    0.06    --  -46.05 -39.00  -1.00  146
 20  \w      9.00  34.00   0.50    0.06    --   46.05 -39.00  -1.00   50
 21  \w     56.00 102.00   0.50    0.26    --  104.76 -77.00 -90.00   92
 22  \w    136.00 168.00   0.50    0.26    --  104.76 125.00   0.00   64
 23  \w     81.00 106.00   0.50    0.26    --  104.76 125.00   0.00   50
 24  \w     53.00 108.00   0.50    0.26    --  104.76 -77.00  90.00  110
 25  \w     77.00 106.00   0.50    0.26    --  104.76 -94.00  30.00   58
 26  \w     52.00 112.00   0.50    0.26    --  104.76-125.00  60.00  120
 27  \w     36.00 112.00   0.50    0.26    --  104.76-125.00  30.00  152
 28  \w     19.00  88.00   0.50    0.06    --   46.05-125.00-150.00  138
 29  \w     53.00 112.00   0.50    0.26    --  104.76-125.00-120.00  118
 30  \w     95.00 177.00   0.50    0.26    --  104.76  15.00 120.00  164
 31  \w    134.00 161.00   0.50    0.26    --  104.76  39.00 152.00   54
 32  \w     98.00 132.00   0.50    0.26    --  104.76  39.00 152.00   68
 33  \w     54.00 112.00   0.50    0.06    --   46.05  39.00 152.00  116
 34  \w    103.00 175.00   0.50    0.26    --  104.76  45.00 -90.00  144
 35  \w     93.00 162.00   0.50    0.26    --  104.76  45.00-120.00  138
 36  \w     92.00 178.00   0.50    0.26    --  104.76  30.00-150.00  172
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1774359000
_diffrn_orient_matrix_UB_12      -0.0796555000
_diffrn_orient_matrix_UB_13      -0.0197491000
_diffrn_orient_matrix_UB_21      -0.0179381000
_diffrn_orient_matrix_UB_22      -0.1532878000
_diffrn_orient_matrix_UB_23      -0.0775653000
_diffrn_orient_matrix_UB_31      0.0521784000
_diffrn_orient_matrix_UB_32      -0.0054884000
_diffrn_orient_matrix_UB_33      0.1390562000
_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  0.0428
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            9613
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.912
_diffrn_reflns_theta_min         4.605
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.852
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82366
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
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    1.345
_exptl_crystal_description       block
_exptl_crystal_F_000             408
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     258
_refine_ls_number_reflns         3720
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0695
_refine_ls_R_factor_gt           0.0556
_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^)+(0.1079P)^2^+0.1801P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1613
_refine_ls_wR_factor_ref         0.1792
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2858
_reflns_number_total             3720
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08607d2.cif
_cod_data_source_block           fuhong_0730_auto
_cod_depositor_comments
'Adding full bibliography for 1573927--1573928.cif.'
_cod_original_cell_volume        956.77(13)
_cod_database_code               1573928
_shelx_shelxl_version_number     2018/1
_reflns_odcompleteness_completeness 98.01
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C4(H4), C6(H6), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C16(H16A,H16B), C23(H23A,H23B)
2.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C26(H26), C27(H27), C29(H29), C31(H31), C37(H37),
 C39(H39), C41(H41), C45(H45)
2.d Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C)
;
_shelx_res_checksum              6973
_shelx_hkl_checksum              39977
_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 1.477
_oxdiff_exptl_absorpt_empirical_full_min 0.721