Iodine-mediated regioselective C-3 sulfenylation using elemental sulfur and arylhydrazine hydrochloride to access 3-sulfenylated imidazo[1,2-<i>a</i>]pyridines.
Kishor, Kaushal; Prabhakar, Neha Sharma; Singh, Krishna Nand; Organic & biomolecular chemistry 23 (2025) 2418–2423; doi:10.1039/d4ob02095b

data_7160355
_publ_section_title
;
 Iodine-mediated regioselective C-3 sulfenylation using elemental sulfur
 and arylhydrazine hydrochloride to access 3-sulfenylated
 imidazo[1,2-<i>a</i>]pyridines.
;
_journal_issue                   10
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2418
_journal_page_last               2423
_journal_paper_doi               10.1039/d4ob02095b
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C20 H13 F3 N2 S'
_chemical_formula_sum            'C20 H13 F3 N2 S'
_chemical_formula_weight         370.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-23
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-23 deposited with the CCDC.	2025-01-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.1380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.71930(10)
_cell_length_b                   10.18290(10)
_cell_length_c                   18.9834(2)
_cell_measurement_reflns_used    14168
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.9590
_cell_measurement_theta_min      2.3340
_cell_volume                     1685.49(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.90a 64-bit (release 14-04-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.991
_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    -75.00  24.00   0.50    0.20    --  -40.83  99.00 -55.00  198
  2  \w    -32.00  29.00   0.50    0.20    --  -40.83  26.00 132.00  122
  3  \w   -109.00 -53.00   0.50    0.20    --  -40.83-154.00 -40.00  112
  4  \w   -111.00 -26.00   0.50    0.20    --  -40.83 -26.00 -31.00  170
  5  \w     27.00 111.00   0.50    0.20    --   40.83  26.00 132.00  168
  6  \w     49.00 110.00   0.50    0.20    --   40.83-154.00 -40.00  122
  7  \w     31.00  87.00   0.50    0.20    --   40.83-121.00 117.00  112
  8  \w   -152.00 -68.00   0.50    0.76    --  -82.50 -26.00 -31.00  168
  9  \w    -81.00 -10.00   0.50    0.76    --  -82.50  99.00 -55.00  142
 10  \w   -155.00 -85.00   0.50    0.76    --  -82.50 -99.00-161.00  140
 11  \w   -146.00 -75.00   0.50    0.76    --  -82.50-121.00 117.00  142
 12  \w    107.00 168.00   0.50    0.76    --   96.04  99.00 -55.00  122
 13  \w     24.00 107.00   0.50    0.76    --   96.04 -99.00-161.00  166
 14  \w     49.00 133.00   0.50    0.76    --   96.04-154.00 -40.00  168
 15  \w     97.00 160.00   0.50    0.76    --   96.04 121.00-159.00  126
 16  \w     82.00 166.00   0.50    0.76    --   96.04  26.00 132.00  168
 17  \w    -27.00  37.00   0.50    0.20    --   40.83 -32.00-120.00  128
 18  \w    -35.00  24.00   0.50    0.20    --   40.83 -11.00  30.00  118
 19  \w     -2.00  75.00   0.50    0.20    --   40.83 -99.00-161.00  154
 20  \w    -35.00  24.00   0.50    0.20    --   40.83 -11.00  90.00  118
 21  \w    -47.00 -15.00   0.50    0.76    --  -82.50  42.00   0.00   64
 22  \w    -47.00 -15.00   0.50    0.76    --  -82.50  42.00  90.00   64
 23  \w     28.00  68.00   0.50    0.76    --   96.04 -59.00-150.00   80
 24  \w     29.00  57.00   0.50    0.76    --   96.04 -50.00-120.00   56
 25  \w     29.00  57.00   0.50    0.76    --   96.04 -50.00 -30.00   56
 26  \w     28.00  68.00   0.50    0.76    --   96.04 -59.00 -30.00   80
 27  \w     28.00  83.00   0.50    0.76    --   96.04 -68.00-180.00  110
 28  \w     29.00  57.00   0.50    0.76    --   96.04 -50.00 -90.00   56
 29  \w     29.00  57.00   0.50    0.76    --   96.04 -50.00  90.00   56
 30  \w     28.00  68.00   0.50    0.76    --   96.04 -59.00  60.00   80
 31  \w     29.00  57.00   0.50    0.76    --   96.04 -50.00   0.00   56
 32  \w     28.00  68.00   0.50    0.76    --   96.04 -59.00  90.00   80
 33  \w   -109.00 -14.00   0.50    0.20    --  -40.83 -77.00 -90.00  190
 34  \w   -109.00 -14.00   0.50    0.20    --  -40.83 -77.00-150.00  190
 35  \w   -108.00 -17.00   0.50    0.20    --  -40.83 -65.00   0.00  182
 36  \w   -109.00 -14.00   0.50    0.20    --  -40.83 -77.00 120.00  190
 37  \w   -109.00 -14.00   0.50    0.20    --  -40.83 -77.00  60.00  190
 38  \w   -108.00 -17.00   0.50    0.20    --  -40.83 -65.00 -60.00  182
 39  \w   -108.00 -17.00   0.50    0.20    --  -40.83 -65.00-120.00  182
 40  \w    -27.00  37.00   0.50    0.20    --   40.83 -32.00-180.00  128
 41  \w     18.00 109.00   0.50    0.20    --   40.83  65.00-180.00  182
 42  \w   -150.00 -58.00   0.50    0.76    --  -82.50 -68.00  60.00  184
 43  \w     23.00 106.00   0.50    0.76    --   96.04 -96.00   0.00  166
 44  \w     74.00 163.00   0.50    0.76    --   96.04  59.00 150.00  178
 45  \w     79.00 162.00   0.50    0.76    --   96.04  42.00 -90.00  166
 46  \w     74.00 163.00   0.50    0.76    --   96.04  59.00 -60.00  178
 47  \w     74.00 163.00   0.50    0.76    --   96.04  59.00 -30.00  178
 48  \w     82.00 164.00   0.50    0.76    --   96.04  33.00-150.00  164
 49  \w     44.00 127.00   0.50    0.76    --   96.04-145.00-150.00  166
 50  \w     77.00 163.00   0.50    0.76    --   96.04  50.00-120.00  172
 51  \w     74.00 163.00   0.50    0.76    --   96.04  59.00   0.00  178
 52  \w     69.00 136.00   0.50    0.76    --   96.04  77.00  90.00  134
 53  \w     74.00 163.00   0.50    0.76    --   96.04  59.00  60.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1642635000
_diffrn_orient_matrix_UB_12      -0.0319677000
_diffrn_orient_matrix_UB_13      -0.0243111000
_diffrn_orient_matrix_UB_21      -0.0620628000
_diffrn_orient_matrix_UB_22      -0.0393403000
_diffrn_orient_matrix_UB_23      -0.0730868000
_diffrn_orient_matrix_UB_31      0.0196844000
_diffrn_orient_matrix_UB_32      0.1425261000
_diffrn_orient_matrix_UB_33      -0.0255692000
_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  0.0485
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            21745
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.059
_diffrn_reflns_theta_min         4.659
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.045
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20186
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.124a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.460
_exptl_crystal_description       block
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         3052
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0391
_refine_ls_R_factor_gt           0.0355
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0528P)^2^+0.3321P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0941
_refine_ls_wR_factor_ref         0.0970
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2740
_reflns_number_total             3052
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob02095b2.cif
_cod_data_source_block           cf3ph
_cod_depositor_comments          'Adding full bibliography for 7160355.cif.'
_cod_database_code               7160355
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N F S'
_shelx_estimated_absorpt_t_max   0.837
_shelx_estimated_absorpt_t_min   0.736
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F5-C7 \\sim F1-C7
 with sigma of 0.02
 F2-C7 \\sim F3-C7
 with sigma of 0.02
 F6-C7 \\sim F4-C7
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F5, F2, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F3, F4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F1)=Sof(F4)=Sof(F3)=1-FVAR(1)
 Sof(F5)=Sof(F2)=Sof(F6)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C16(H16), C18(H18), C20(H20), C5(H5), C11(H11), C3(H3), C13(H13),
 C15(H15), C2(H2), C17(H17), C9(H9), C19(H19)
;
_shelx_res_checksum              156
_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 2.393
_oxdiff_exptl_absorpt_empirical_full_min 0.777