Photoredox catalysed reductive cleavage of dibenzothiophene dioxides enabled by a temperature-controlled photoreactor
Wang, Siyuan; Le, Quang Truong; Shishido, Yoshiteru; Kokculer, Ismail Y.; Yamazaki, Ken; Perry, Gregory J. P.; Nightingale, Adrian Matthew; Yorimitsu, Hideki; Chemical Science  (2025) –; doi:10.1039/D5SC05889A

data_1576071
_publ_section_title
;
 Photoredox catalysed reductive cleavage of dibenzothiophene dioxides
 enabled by a temperature-controlled photoreactor
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC05889A
_journal_year                    2025
_chemical_formula_moiety         'C12 H9 F O2 S'
_chemical_formula_sum            'C12 H9 F O2 S'
_chemical_formula_weight         236.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-27
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.02.13 svn.rdd3e1f77 for OlexSys, GUI svn.r7147)
;
_audit_update_record
;
2025-08-04 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.9900(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.5997(2)
_cell_length_b                   7.95050(10)
_cell_length_c                   18.3482(2)
_cell_measurement_reflns_used    25462
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.8860
_cell_measurement_theta_min      3.6510
_cell_volume                     2118.14(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 44.90a 64-bit (release 21-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_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 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.955
_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    -38.00 -12.00   0.50    1.50    --   -2.00 115.00 -42.32   52
  2  \w    -46.00 -21.00   0.50    1.50    --  -26.00 -67.00 108.97   50
  3  \w    -51.00 -26.00   0.50    1.50    --  -30.00 -65.00  65.43   50
  4  \w    -51.00 -26.00   0.50    1.50    --  -30.00 -64.00  -3.74   50
  5  \w    -51.00 -26.00   0.50    1.50    --  -30.00 -64.00  26.75   50
  6  \w    -54.00 -29.00   0.50    1.50    --  -34.00 -63.00 145.36   50
  7  \w    -62.00 -37.00   0.50    1.50    --  -38.00 -57.00  99.87   50
  8  \w    -69.00 -43.00   0.50    1.50    --  -46.00 -53.00  24.47   52
  9  \w    -68.00 -42.00   0.50    1.50    --  -46.00 -54.00  36.40   52
 10  \w    -69.00 -43.00   0.50    1.50    --  -46.00 -53.00  -5.10   52
 11  \w    -71.00 -45.00   0.50    1.50    --  -46.00 -43.00  62.07   52
 12  \w    -69.00 -43.00   0.50    1.50    --  -46.00 -52.00  12.35   52
 13  \w    -68.00 -42.00   0.50    1.50    --  -46.00 -54.00 113.94   52
 14  \w    -75.00 -49.00   0.50    1.50    --  -50.00 -50.00 -18.08   52
 15  \w    -75.00 -49.00   0.50    1.50    --  -52.65 -53.00  14.89   52
 16  \w    -77.00 -52.00   0.50    1.50    --  -52.65 -52.00  43.16   50
 17  \w    -75.00 -17.00   0.50    1.50    --  -52.65 125.00-150.00  116
 18  \w    -77.00 -51.00   0.50    1.50    --  -52.65 -53.00  -1.26   52
 19  \w    -77.00 -52.00   0.50    1.50    --  -54.00 -48.00 -11.79   50
 20  \w    -85.00 -59.00   0.50    1.50    --  -62.00 -54.00  45.08   52
 21  \w    -85.00 -59.00   0.50    1.50    --  -62.00 -54.00  73.50   52
 22  \w    -83.00 -58.00   0.50    1.50    --  -62.00 -54.00  61.05   50
 23  \w    -84.00 -58.00   0.50    1.50    --  -62.00 -54.00  37.51   52
 24  \w    -88.00 -62.00   0.50    1.50    --  -66.00 -54.00  92.87   52
 25  \w    -87.00 -62.00   0.50    1.50    --  -66.00 -54.00  17.53   50
 26  \w    -89.00 -63.00   0.50    1.50    --  -66.00 -54.00  24.37   52
 27  \w    -91.00 -66.00   0.50    1.50    --  -70.00 -53.00  68.60   50
 28  \w    -93.00 -67.00   0.50    1.50    --  -70.00 -53.00   5.69   52
 29  \w    -96.00 -70.00   0.50    1.50    --  -70.00 -53.00  85.70   52
 30  \w    -92.00 -66.00   0.50    1.50    --  -70.00 -54.00 -53.61   52
 31  \w   -142.00-116.00   0.50    1.50    --  -74.00 -54.00  -3.68   52
 32  \w    -96.00 -71.00   0.50    1.50    --  -74.00 -51.00  33.79   50
 33  \w    -98.00 -72.00   0.50    1.50    --  -74.00 -54.00 -11.45   52
 34  \w    -95.00 -70.00   0.50    1.50    --  -74.00 -54.00  -3.68   50
 35  \w   -100.00 -74.00   0.50    1.50    --  -74.92 -45.00 120.00   52
 36  \w    -99.00 -74.00   0.50    1.50    --  -78.00 -54.00 -18.00   50
 37  \w   -101.00 -75.00   0.50    1.50    --  -78.00 -54.00 101.57   52
 38  \w   -102.00 -76.00   0.50    1.50    --  -78.00 -54.00   9.69   52
 39  \w   -104.00 -78.00   0.50    1.50    --  -82.00 -53.00  27.14   52
 40  \w   -106.00 -80.00   0.50    1.50    --  -82.00 -54.00  -2.73   52
 41  \w    -92.00 -66.00   0.50    1.50    --  -82.00  90.00 104.76   52
 42  \w    -93.00 -48.00   0.50    1.50    --  -82.00 101.00  38.41   90
 43  \w   -104.00 -78.00   0.50    1.50    --  -82.00 -54.00  62.96   52
 44  \w   -105.00 -79.00   0.50    1.50    --  -82.00 -49.00 -26.88   52
 45  \w    -92.00 -66.00   0.50    1.50    --  -82.00  91.00  81.04   52
 46  \w   -111.00 -85.00   0.50    1.50    --  -82.00 -56.00  13.39   52
 47  \w   -104.00 -78.00   0.50    1.50    --  -82.00 -53.00  49.35   52
 48  \w    -92.00 -65.00   0.50    1.50    --  -82.00 100.00   3.53   54
 49  \w   -104.00 -78.00   0.50    1.50    --  -82.00 -54.00 -23.41   52
 50  \w   -110.00 -78.00   0.50    1.50    --  -82.00 -54.00  89.13   64
 51  \w   -147.00 -78.00   0.50    1.50    --  -82.00 -53.00 -43.49  138
 52  \w    -55.00 -20.00   0.50    1.50    --  -82.00  96.00 130.82   70
 53  \w    -92.00 -65.00   0.50    1.50    --  -82.00  96.00 130.82   54
 54  \w   -113.00 -79.00   0.50    1.50    --  -82.00 -54.00 112.49   68
 55  \w     92.00 145.00   0.50    1.50    --   90.71  45.00 150.00  106
 56  \w     89.00 139.00   0.50    1.50    --   90.71  45.00 120.00  100
 57  \w     72.00 101.00   0.50    1.50    --   90.71-125.00 150.00   58
 58  \w     24.00  60.00   0.50    1.50    --   90.71-125.00 150.00   72
 59  \w     85.00 111.00   0.50    1.50    --   90.71  61.00   0.00   52
 60  \w     73.00 100.00   0.50    1.50    --   90.71-125.00  60.00   54
 61  \w     43.00  69.00   0.50    1.50    --   90.71-125.00  60.00   52
 62  \w     26.00  62.00   0.50    1.50    --   90.71-125.00-180.00   72
 63  \w    130.00 156.00   0.50    1.50    --   90.71  45.00  30.00   52
 64  \w     94.00 120.00   0.50    1.50    --   90.71  45.00  30.00   52
 65  \w     75.00 101.00   0.50    1.50    --   90.71-125.00  30.00   52
 66  \w     87.00 161.00   0.50    1.50    --   90.71  61.00 150.00  148
 67  \w     92.00 118.00   0.50    1.50    --   90.71  45.00-180.00   52
 68  \w     48.00  74.00   0.50    1.50    --   90.71 -95.00 120.00   52
 69  \w     30.00  57.00   0.50    1.50    --   90.71 -77.00   0.00   54
 70  \w    121.00 153.00   0.50    1.50    --   90.71 125.00-120.00   64
 71  \w     85.00 117.00   0.50    1.50    --   90.71  61.00  30.00   64
 72  \w     44.00  70.00   0.50    1.50    --   90.71 -95.00-180.00   52
 73  \w    104.00 129.00   0.50    1.50    --   90.71  15.00 -30.00   50
 74  \w    125.00 156.00   0.50    1.50    --   90.71  61.00 120.00   62
 75  \w     86.00 112.00   0.50    1.50    --   90.71  61.00 120.00   52
 76  \w     46.00  85.00   0.50    1.50    --   90.71 -95.00 -90.00   78
 77  \w     71.00  98.00   0.50    1.50    --   90.71-125.00  90.00   54
 78  \w     36.00  80.00   0.50    1.50    --   90.71-125.00-150.00   88
 79  \w     24.00  52.00   0.50    1.50    --   90.71-125.00  90.00   56
 80  \w     85.00 136.00   0.50    1.50    --   90.71  61.00  60.00  102
 81  \w     28.00  67.00   0.50    1.50    --   90.71 -77.00 -90.00   78
 82  \w    133.00 158.00   0.50    1.50    --   90.71 125.00 150.00   50
 83  \w     65.00  91.00   0.50    1.50    --   90.71 -95.00 150.00   52
 84  \w    107.00 133.00   0.50    1.50    --   90.71  77.00-150.00   52
 85  \w     91.00 117.00   0.50    1.50    --   90.71 125.00 150.00   52
 86  \w     54.00  83.00   0.50    1.50    --   90.71 -95.00-120.00   58
 87  \w     26.00  54.00   0.50    1.50    --   90.71 -77.00-120.00   56
 88  \w    127.00 161.00   0.50    1.50    --   90.71  61.00  90.00   68
 89  \w     85.00 111.00   0.50    1.50    --   90.71  61.00  90.00   52
 90  \w     89.00 138.00   0.50    1.50    --   90.71  45.00  90.00   98
 91  \w     76.00 101.00   0.50    1.50    --   90.71-125.00 120.00   50
 92  \w     21.00  46.00   0.50    1.50    --   90.71 -61.00  30.00   50
 93  \w     89.00 147.00   0.50    1.50    --   90.71  45.00  60.00  116
 94  \w     23.00  48.00   0.50    1.50    --   90.71-125.00 120.00   50
 95  \w     73.00 100.00   0.50    1.50    --   90.71-125.00-180.00   54
 96  \w     26.00  56.00   0.50    1.50    --   94.00 -69.00 -23.41   60
 97  \w     95.00 164.00   0.50    1.50    --   98.00  33.00-172.01  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0783535000
_diffrn_orient_matrix_UB_12      0.0076625000
_diffrn_orient_matrix_UB_13      -0.0499823000
_diffrn_orient_matrix_UB_21      -0.0713898000
_diffrn_orient_matrix_UB_22      0.0186223000
_diffrn_orient_matrix_UB_23      -0.0675538000
_diffrn_orient_matrix_UB_31      0.0037876000
_diffrn_orient_matrix_UB_32      0.1926937000
_diffrn_orient_matrix_UB_33      0.0085104000
_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  0.0381
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            44180
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.131
_diffrn_reflns_theta_min         3.687
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.705
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.700
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.482
_exptl_crystal_description       plate
_exptl_crystal_F_000             976
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of hexane and DCM  by ---'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.463
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     289
_refine_ls_number_reflns         4052
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0682P)^2^+0.9855P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1127
_refine_ls_wR_factor_ref         0.1145
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3749
_reflns_number_total             4052
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05889a4.cif
_cod_data_source_block           2025sot0001_d1_100k
_cod_database_code               1576071
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C12H9FO2S
_chemical_oxdiff_usercomment     'SW-01-004F, CSD: CAZMEV'
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.551
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C202(H202), C203(H203), C204(H204), C205(H205), C208(H208), C209(H209),
 C210(H210), C211(H211), C212(H212), C102(H102), C103(H103), C104(H104),
 C105(H105), C108(H108), C109(H109), C110(H110), C111(H111), C112(H112)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with silicon oil'
_olex2_submission_original_sample_id SW-01-004F
_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 1.359
_oxdiff_exptl_absorpt_empirical_full_min 0.811