Benzoates as photosensitization catalysts and auxiliaries in efficient, practical, light-powered direct C(sp3)–H fluorinations
Yakubov, Shahboz; Stockerl, Willibald J.; Tian, Xianhai; Shahin, Ahmed; Mandigma, Mark John P.; Gschwind, Ruth M.; Barham, Joshua P.; Chemical Science  (2022) –; doi:10.1039/D2SC05735B

data_1567966
_publ_section_title
;
 Benzoates as photosensitization catalysts and auxiliaries in efficient,
 practical, light-powered direct C(sp3)--H fluorinations
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC05735B
_journal_year                    2022
_chemical_formula_moiety         'C17 H19 F2 N O'
_chemical_formula_sum            'C17 H19 F2 N O'
_chemical_formula_weight         291.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-09-26
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.06.10 svn.r3fa896fb for OlexSys, GUI svn.r6535)
;
_audit_update_record
;
2022-10-11 deposited with the CCDC.	2022-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.6270(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.67810(10)
_cell_length_b                   11.11540(10)
_cell_length_c                   14.2033(2)
_cell_measurement_reflns_used    9868
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      73.7330
_cell_measurement_theta_min      5.0880
_cell_volume                     1484.92(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (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      123.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.977
_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      7.00  34.00   0.50    0.50    --   14.00  93.00-132.02   54
  2  \w     13.00  43.00   0.50    0.50    --   18.00  90.00 -70.48   60
  3  \w     13.00  43.00   0.50    0.50    --   18.00  90.00  -9.18   60
  4  \w     17.00  43.00   0.50    0.50    --   18.00  84.00  81.51   52
  5  \w     12.00  43.00   0.50    0.50    --   14.00  86.00 158.98   62
  6  \w    -48.00 -22.00   0.50    0.50    --  -10.00 142.00  48.59   52
  7  \w   -123.00 -40.00   0.50    1.00    --  -78.25 151.00 -13.83  166
  8  \w   -110.00 -36.00   0.50    1.00    --  -78.25 132.00  55.12  148
  9  \w   -100.00 -32.00   0.50    0.50    --  -73.72 125.00  30.00  136
 10  \w   -118.00 -38.00   0.50    1.00    --  -78.25 144.00 115.14  160
 11  \w    -90.00 -22.00   0.50    0.50    --  -63.82 125.00 150.00  136
 12  \w   -100.00 -32.00   0.50    0.50    --  -73.72 125.00  90.00  136
 13  \w   -100.00 -32.00   0.50    0.50    --  -73.72 125.00 -90.00  136
 14  \w   -100.00 -32.00   0.50    0.50    --  -73.72 125.00-120.00  136
 15  \w   -103.00 -35.00   0.50    1.00    --  -76.77 125.00-150.00  136
 16  \w    -70.00 -38.00   0.50    1.00    --  -78.25  65.00  53.71   64
 17  \w   -101.00 -26.00   0.50    0.50    --  -63.82   0.00 150.00  150
 18  \w     56.00  88.00   0.50    0.50    --   46.00  60.00 119.89   64
 19  \w     44.00  75.00   0.50    0.50    --   38.00  72.00  88.67   62
 20  \w     43.00  75.00   0.50    0.50    --   38.00  74.00 170.25   64
 21  \w     45.00  77.00   0.50    0.50    --   42.00  77.00  22.54   64
 22  \w     43.00  75.00   0.50    0.50    --   38.00  74.00  -3.22   64
 23  \w     53.00  84.00   0.50    0.50    --   46.00  70.00 -79.69   62
 24  \w     43.00  75.00   0.50    0.50    --   38.00  74.00-132.00   64
 25  \w     39.00 113.00   0.50    1.00    --   75.87   0.00 -30.00  148
 26  \w     61.00  92.00   0.50    0.50    --   54.00  70.00  74.44   62
 27  \w     60.00  91.00   0.50    0.50    --   54.00  73.00 123.10   62
 28  \w     76.00 127.00   0.50    1.00    --   79.75  26.00  23.36  102
 29  \w     39.00 113.00   0.50    1.00    --   75.87   0.00 150.00  148
 30  \w     64.00  95.00   0.50    0.50    --   58.00  72.00-128.15   62
 31  \w     38.00  84.00   0.50    1.00    --   75.87 -95.00-120.00   92
 32  \w     40.00  99.00   0.50    1.00    --   79.75-113.00  39.04  118
 33  \w     21.00  90.00   0.50    0.50    --   63.22-125.00  60.00  138
 34  \w   -109.00 -78.00   0.50    0.50    --  -74.00 -76.00 138.31   62
 35  \w   -113.00 -80.00   0.50    1.00    --  -78.25 -79.00 119.57   66
 36  \w   -106.00 -75.00   0.50    0.50    --  -70.00 -74.00  90.54   62
 37  \w   -114.00 -82.00   0.50    1.00    --  -78.25 -76.00  69.72   64
 38  \w   -114.00 -83.00   0.50    0.50    --  -74.00 -64.00  74.65   62
 39  \w   -115.00 -84.00   0.50    1.00    --  -78.25 -72.00  -9.49   62
 40  \w   -106.00 -74.00   0.50    0.50    --  -70.00 -75.00 -32.22   64
 41  \w   -113.00 -81.00   0.50    1.00    --  -78.25 -77.00-116.34   64
 42  \w   -114.00 -82.00   0.50    1.00    --  -78.25 -76.00 -83.37   64
 43  \w   -115.00 -83.00   0.50    0.50    --  -74.00 -62.00   2.49   64
 44  \w   -121.00 -89.00   0.50    1.00    --  -78.25 -55.00  11.46   64
 45  \w   -119.00 -87.00   0.50    1.00    --  -78.25 -62.00 175.03   64
 46  \w   -125.00 -91.00   0.50    1.00    --  -78.25 -39.00 123.67   68
 47  \w   -121.00 -89.00   0.50    1.00    --  -78.25 -55.00  44.87   64
 48  \w   -114.00 -81.00   0.50    0.50    --  -70.00 -51.00  18.45   66
 49  \w   -124.00 -90.00   0.50    1.00    --  -78.25 -43.00-177.10   68
 50  \w   -113.00 -79.00   0.50    1.00    --  -78.25 -86.00 -52.80   68
 51  \w   -118.00 -73.00   0.50    1.00    --  -76.77-125.00-180.00   90
 52  \w   -118.00 -73.00   0.50    1.00    --  -76.77-125.00-150.00   90
 53  \w   -118.00 -73.00   0.50    1.00    --  -76.77-125.00   0.00   90
 54  \w   -118.00 -73.00   0.50    1.00    --  -76.77-125.00 150.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1592237000
_diffrn_orient_matrix_UB_12      0.0030486000
_diffrn_orient_matrix_UB_13      0.0002415000
_diffrn_orient_matrix_UB_21      -0.0338456000
_diffrn_orient_matrix_UB_22      0.0763842000
_diffrn_orient_matrix_UB_23      -0.0931191000
_diffrn_orient_matrix_UB_31      0.0181745000
_diffrn_orient_matrix_UB_32      0.1155183000
_diffrn_orient_matrix_UB_33      0.0616311000
_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  0.0215
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14494
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.076
_diffrn_reflns_theta_min         5.109
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.812
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.646
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.108a (Rigaku Oxford Diffraction, 2021)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_description       plate
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.217
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.022
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.313
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1298 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     194
_refine_ls_number_reflns         2928
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0537P)^2^+0.7882P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0949
_refine_ls_wR_factor_ref         0.0962
_reflns_Friedel_coverage         0.953
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.935
_reflns_number_gt                2818
_reflns_number_total             2928
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05735b2.cif
_cod_data_source_block           v100
_cod_database_code               1567966
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C17 H19 F2 N O'
_chemical_oxdiff_usercomment     Yabukov_Barham_SY220a
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.844
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C13(H13), C16(H16), C14(H14)
;
_shelx_res_checksum              93919
_shelx_hkl_checksum              65707
_olex2_date_sample_data_collection 2022-09-20
_olex2_date_sample_submission    2022-09-14
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder inert oil'
_olex2_submission_original_sample_id SY220a
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.330
_oxdiff_exptl_absorpt_empirical_full_min 0.595