Direct conversion of carboxylic acids to free thiols <i>via</i> radical relay acridine photocatalysis enabled by N-O bond cleavage.
Lipilin, Dmitry L.; Zubkov, Mikhail O.; Kosobokov, Mikhail D.; Dilman, Alexander D.; Chemical science 15 (2024) 644–650; doi:10.1039/d3sc05513b

data_1570496
_publ_section_title
;
 Direct conversion of carboxylic acids to free thiols <i>via</i> radical
 relay acridine photocatalysis enabled by N-O bond cleavage.
;
_journal_issue                   2
_journal_name_full               'Chemical science'
_journal_page_first              644
_journal_page_last               650
_journal_paper_doi               10.1039/d3sc05513b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C19 H21 N O4 S2'
_chemical_formula_sum            'C19 H21 N O4 S2'
_chemical_formula_weight         391.49
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-05-03
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_audit_update_record
;
2023-06-20 deposited with the CCDC.	2023-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.29180(10)
_cell_length_b                   7.95790(10)
_cell_length_c                   37.0360(5)
_cell_measurement_reflns_used    8211
_cell_measurement_temperature    99.9(3)
_cell_measurement_theta_max      77.3020
_cell_measurement_theta_min      2.3760
_cell_volume                     1854.37(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.990
_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    -77.00  24.00   0.50    1.00    --  -48.70  91.00 -23.00  202
  2  \w    -40.00  24.00   0.50    1.00    --  -48.70  35.00-153.00  128
  3  \w   -154.00 -81.00   0.50    4.30    --  -86.25-112.00 -31.00  146
  4  \w    103.00 176.00   0.50    4.30    --  107.75 112.00  60.00  146
  5  \w     36.00 106.00   0.50    4.30    --  107.75 -91.00-136.00  140
  6  \w     97.00 178.00   0.50    4.30    --  107.75  35.00-153.00  162
  7  \w   -118.00 -73.00   0.50    1.00    --  -48.70-125.00 -90.00   90
  8  \w    -26.00  26.00   0.50    1.00    --  -48.70  19.00 -90.00  104
  9  \w   -159.00-114.00   0.50    4.30    --  -86.25 -35.00  49.00   90
 10  \w     37.00  62.00   0.50    4.30    --  107.75 -61.00  30.00   50
 11  \w     36.00  71.00   0.50    4.30    --  107.75 -61.00  90.00   70
 12  \w    105.00 133.00   0.50    4.30    --  107.75  45.00 -30.00   56
 13  \w     39.00  64.00   0.50    4.30    --  107.75 -61.00 120.00   50
 14  \w    137.00 171.00   0.50    4.30    --  107.75 125.00  30.00   68
 15  \w     41.00  66.00   0.50    4.30    --  107.75 -68.00 155.69   50
 16  \w     44.00  76.00   0.50    4.30    --  107.75-106.00  33.30   64
 17  \w     36.00  62.00   0.50    4.30    --  107.75 -61.00-120.00   52
 18  \w     39.00  81.00   0.50    4.30    --  107.75 -90.00 169.35   84
 19  \w     95.00 124.00   0.50    4.30    --  107.75 125.00  30.00   58
 20  \w    137.00 163.00   0.50    4.30    --  107.75  45.00 -30.00   52
 21  \w     39.00  71.00   0.50    4.30    --  107.75 -61.00 -60.00   64
 22  \w     80.00 105.00   0.50    4.30    --  107.75-106.00  33.30   50
 23  \w     72.00 102.00   0.50    4.30    --  107.75 -77.00  90.00   60
 24  \w    126.00 156.00   0.50    4.30    --  107.75  30.00   0.00   60
 25  \w     69.00  95.00   0.50    4.30    --  107.75 -95.00 120.00   52
 26  \w     42.00  70.00   0.50    4.30    --  107.75 -61.00-150.00   56
;
_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      0.0668701000
_diffrn_orient_matrix_UB_12      -0.0302884000
_diffrn_orient_matrix_UB_13      -0.0394909000
_diffrn_orient_matrix_UB_21      -0.0860493000
_diffrn_orient_matrix_UB_22      0.1746412000
_diffrn_orient_matrix_UB_23      -0.0103807000
_diffrn_orient_matrix_UB_31      0.2192675000
_diffrn_orient_matrix_UB_32      0.0777826000
_diffrn_orient_matrix_UB_33      0.0079583000
_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  0.0488
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            13457
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.798
_diffrn_reflns_theta_min         2.386
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.815
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53768
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.517
_refine_diff_density_min         -0.437
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.18(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3782
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0552P)^2^+2.2477P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1219
_reflns_Friedel_coverage         0.650
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.917
_reflns_number_gt                3618
_reflns_number_total             3782
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05513b2.cif
_cod_data_source_block           km1765-1
_cod_depositor_comments          'Adding full bibliography for 1570496.cif.'
_cod_database_code               1570496
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C19H21NO4S2
_chemical_oxdiff_usercomment     KM1765-1
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.82(3)
 0.18(3)
2. 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
3.a Ternary CH refined with riding coordinates:
 C10(H10)
3.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19)
3.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              6235
_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 1.662
_oxdiff_exptl_absorpt_empirical_full_min 0.545