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_1567967
_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_absolute_configuration ad
_chemical_formula_moiety         'C25 H35.086 F0.914 O5'
_chemical_formula_sum            'C25 H35.086 F0.914 O5'
_chemical_formula_weight         433.023
_chemical_name_systematic        'SY 635'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_Int_Tables_number      4
_atom_sites_solution_primary     dual
_audit_creation_date             2022-09-28
_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                 108.458(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.4636(4)
_cell_length_b                   6.90652(18)
_cell_length_c                   16.1323(6)
_cell_measurement_reflns_used    3924
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      73.2540
_cell_measurement_theta_min      2.8700
_cell_volume                     1105.86(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.39a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 42.68a 64-bit (release 08-09-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.39a (Rigaku OD, 2022)'
_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  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(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 0.9895
_diffrn_measured_fraction_theta_max 0.9686
_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     43.00  68.00   0.50    1.20    --   78.43-111.00-136.00   50
  2  \w     19.00  81.00   0.50    1.20    --   60.79-111.00-136.00  124
  3  \w     33.00  94.00   0.50    1.20    --   74.37-111.00-136.00  122
  4  \w     38.00  84.00   0.50    1.20    --   82.00-121.00  23.12   92
  5  \w     40.00 109.00   0.50    1.20    --   82.00  -3.00  79.79  138
  6  \w     43.00  81.00   0.50    1.20    --   82.00  -4.00  35.96   76
  7  \w     11.00  36.00   0.50    1.20    --   60.79 -30.00-180.00   50
  8  \w     48.00  75.00   0.50    1.20    --   82.00  -4.00  -8.27   54
  9  \w     89.00 122.00   0.50    1.20    --   82.00  93.00 -49.80   66
 10  \w     47.00  94.00   0.50    1.20    --   82.00   1.00 -52.18   94
 11  \w     64.00  99.00   0.50    1.20    --   56.00  61.00  44.78   70
 12  \w     55.00  81.00   0.50    1.20    --   44.00  68.00 114.88   52
 13  \w     87.00 130.00   0.50    1.20    --   82.00  18.00 178.23   86
 14  \w     96.00 128.00   0.50    1.20    --   82.00  50.00  90.46   64
 15  \w     90.00 127.00   0.50    1.20    --   82.00  57.00  58.98   74
 16  \w     55.00 100.00   0.50    1.20    --   82.00  20.00  35.66   90
 17  \w     98.00 124.00   0.50    1.20    --   82.00  61.00-177.94   52
 18  \w    -74.00 -49.00   0.50    1.20    --  -80.00  70.00  83.56   50
 19  \w    -87.00 -42.00   0.50    1.20    --  -80.00  97.00 124.13   90
 20  \w   -105.00 -61.00   0.50    1.20    --  -80.00 121.00  21.68   88
 21  \w    -81.00 -19.00   0.50    1.20    --  -61.39 111.00 -43.00  124
 22  \w    -86.00 -38.00   0.50    1.20    --  -75.76 111.00 -43.00   96
 23  \w    -90.00 -44.00   0.50    1.20    --  -80.00  95.00 -52.24   92
 24  \w   -123.00 -98.00   0.50    1.20    --  -80.00 -44.00-147.75   50
 25  \w   -122.00 -91.00   0.50    1.20    --  -80.00 -57.00-157.24   62
 26  \w   -106.00 -81.00   0.50    1.20    --  -80.00 -79.00 -94.18   50
 27  \w   -109.00 -84.00   0.50    1.20    --  -72.00 -74.00-107.08   50
 28  \w   -115.00 -89.00   0.50    1.20    --  -80.00 -76.00 -43.69   52
 29  \w   -124.00 -97.00   0.50    1.20    --  -80.00 -57.00   8.47   54
 30  \w   -113.00 -86.00   0.50    1.20    --  -68.00 -51.00  70.95   54
 31  \w   -111.00 -77.00   0.50    1.20    --  -68.00 -50.00 -60.77   68
 32  \w   -111.00 -85.00   0.50    1.20    --  -80.00 -81.00 -62.75   52
 33  \w   -113.00 -74.00   0.50    1.20    --  -75.28-125.00 -90.00   78
;
_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      0.1314916000
_diffrn_orient_matrix_UB_12      0.0990931000
_diffrn_orient_matrix_UB_13      -0.0006567000
_diffrn_orient_matrix_UB_21      -0.0361829000
_diffrn_orient_matrix_UB_22      -0.0398116000
_diffrn_orient_matrix_UB_23      -0.0987179000
_diffrn_orient_matrix_UB_31      -0.0740229000
_diffrn_orient_matrix_UB_32      0.1958175000
_diffrn_orient_matrix_UB_33      -0.0197038000
_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  0.0407
_diffrn_reflns_av_unetI/netI     0.0565
_diffrn_reflns_Laue_measured_fraction_full 0.9895
_diffrn_reflns_Laue_measured_fraction_max 0.9686
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            11859
_diffrn_reflns_point_group_measured_fraction_full 0.8780
_diffrn_reflns_point_group_measured_fraction_max 0.8444
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         75.16
_diffrn_reflns_theta_min         2.89
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.768
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63507
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.39a (Rigaku Oxford Diffraction, 2022)
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    1.300
_exptl_crystal_description       needle
_exptl_crystal_F_000             468.262
_exptl_crystal_size_max          0.256
_exptl_crystal_size_mid          0.031
_exptl_crystal_size_min          0.028
_refine_diff_density_max         0.2077
_refine_diff_density_min         -0.2155
_refine_diff_density_rms         0.0549
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   0.12(12)
_refine_ls_d_res_high            0.7975
_refine_ls_d_res_low             15.3024
_refine_ls_goodness_of_fit_ref   1.0399
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    17
_refine_ls_number_parameters     413
_refine_ls_number_reflns         3857
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.0381
_refine_ls_R_factor_all          0.0666
_refine_ls_R_factor_gt           0.0443
_refine_ls_shift/su_max          -0.0010
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0485P)^2^+0.1782P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0947
_refine_ls_wR_factor_ref         0.1052
_reflns_Friedel_coverage         0.697
_reflns_limit_h_max              12
_reflns_limit_h_min              -13
_reflns_limit_k_max              8
_reflns_limit_k_min              -8
_reflns_limit_l_max              20
_reflns_limit_l_min              -19
_reflns_number_gt                2981
_reflns_number_total             3857
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d2sc05735b2.cif
_cod_data_source_block           V108
_cod_original_cell_volume        1105.87(7)
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               1567967
_chemical_oxdiff_formula         'C25 H35 F O5'
_chemical_oxdiff_usercomment     Yabukov_Barham_SY635
_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. Uiso/Uaniso restraints and constraints
F1 \\sim C00E: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 2A
Uanis(F4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
3. Others
 Sof(H00w)=1-FVAR(1)
 Sof(F002)=FVAR(1)
 Sof(H00y)=1-FVAR(2)
 Sof(F4)=FVAR(2)
 Sof(H00E)=1-FVAR(3)
 Sof(F1)=FVAR(3)
4.a Ternary CH refined with riding coordinates:
 C00E(H00E)
4.b Secondary CH2 refined with riding coordinates:
 C00Q(H00v,H00w), C00R(H00y,H00x)
4.c Idealised Me refined as rotating group with stretchable bonds:
 C00V(H2,Hd,He)
;
_olex2_date_sample_data_collection 2022-09-27
_olex2_date_sample_submission    2022-08-26
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with mineral oil'
_olex2_submission_original_sample_id 'SY 635'
_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 1.738
_oxdiff_exptl_absorpt_empirical_full_min 0.517