Blue-Light Assisted Transformation of C=S and P=S Bonds of Thioamides and Thiophosphonyl Diamides into C=N and P=N bonds of N-Sulfonyl Amidines via Interaction with Iminoiodinanes
Ilkin, Vladimir; Silaichev, Pavel; Filimonov, Valeriy; Nikulin, Alexey; Beliaev, Nikolai; Beryozkina, Tetyana; Slepukhin, Pavel A.; Dehaen, Wim; Bakulev, Vasiliy Alekseevich; New Journal of Chemistry  (2025) –; doi:10.1039/D5NJ03889H

data_7064145
_publ_section_title
;
 Blue-Light Assisted Transformation of C=S and P=S Bonds of Thioamides and
 Thiophosphonyl Diamides into C=N and P=N bonds of N-Sulfonyl Amidines via
 Interaction with Iminoiodinanes
;
_journal_name_full               'New Journal of Chemistry'
_journal_paper_doi               10.1039/D5NJ03889H
_journal_year                    2025
_chemical_formula_moiety         'C22 H29 N3 O3 S'
_chemical_formula_sum            'C22 H29 N3 O3 S'
_chemical_formula_weight         415.54
_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             2025-08-31
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-09-08 deposited with the CCDC.	2025-11-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.710(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.1024(3)
_cell_length_b                   19.3688(6)
_cell_length_c                   12.6664(4)
_cell_measurement_reflns_used    2666
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      28.4410
_cell_measurement_theta_min      2.5820
_cell_volume                     2127.29(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.98a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      295(2)
_diffrn_detector_area_resol_mean 15.9555
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.833
_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    -37.00   8.00   1.00   30.00    --  -19.06 -77.00-180.00   45
  2  \w    -35.00  41.00   1.00   30.00    --   21.56 -77.00 -60.00   76
  3  \w     13.00  70.00   1.00   30.00    --   21.56  38.00  60.00   57
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur 3'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0254
_diffrn_reflns_av_unetI/netI     0.0555
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.833
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9274
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.833
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.080
_diffrn_reflns_theta_min         2.440
_exptl_absorpt_coefficient_mu    0.180
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.98a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       prism
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.279
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     299
_refine_ls_number_reflns         5691
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1069
_refine_ls_R_factor_gt           0.0597
_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^)+(0.1000P)^2^+0.1000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1558
_refine_ls_wR_factor_ref         0.1954
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3513
_reflns_number_total             5691
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj03889h2.cif
_cod_data_source_block           exp_1499
_cod_database_code               7064145
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.933
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(O3A) \\sim Ueq, Uanis(O2A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
2. Others
 Fixed Sof: O2(0.75) O3(0.75) H17A(0.65) H17B(0.65) H17C(0.35) H17D(0.35)
 H20A(0.65) H20B(0.65) H20C(0.35) H20D(0.35) C18(0.65) H18A(0.65) H18B(0.65)
 C19(0.65) H19A(0.65) H19B(0.65) C19A(0.35) H19C(0.35) H19D(0.35) C18A(0.35)
 H18C(0.35) H18D(0.35) O3A(0.25) O2A(0.25)
3.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C8(H8A,H8B), C16(H16A,H16B), C9(H9A,H9B), C22(H22A,H22B),
 C11(H11A,H11B), C17(H17A,H17B), C17(H17C,H17D), C21(H21A,H21B), C20(H20A,H20B),
  C20(H20C,H20D), C18(H18A,H18B), C19(H19A,H19B), C19A(H19C,H19D), C18A(H18C,
 H18D)
3.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C2(H2), C3(H3)
3.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_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
;