Access to 4-(pyridin-2-yloxy)-1,2,4-thiadiazol-5(4<i>H</i>)-ones <i>via</i> an amidoxime O-heteroarylation/cyclization reaction sequence.
Solodyankina, Olga V.; Baykova, Svetlana O.; Baykov, Sergey V.; Togyzbayeva, Nurila; Zhussupova, Leilya; Novikov, Mikhail S.; Turmanov, Rakhymzhan; Boyarskiy, Vadim P.; Organic & biomolecular chemistry 23 (2025) 10398–10407; doi:10.1039/d5ob01387a

data_7160821
_publ_section_title
;
 Access to 4-(pyridin-2-yloxy)-1,2,4-thiadiazol-5(4<i>H</i>)-ones
 <i>via</i> an amidoxime O-heteroarylation/cyclization reaction sequence.
;
_journal_issue                   45
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10398
_journal_page_last               10407
_journal_paper_doi               10.1039/d5ob01387a
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C14 H15 N3 O'
_chemical_formula_sum            'C14 H15 N3 O'
_chemical_formula_weight         241.29
_chemical_name_systematic        N'-((3,5-dimethylpyridin-2-yl)oxy)benzimidamide
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-17
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-07-21 deposited with the CCDC.	2025-10-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   10.23780(10)
_cell_length_b                   10.23780(10)
_cell_length_c                   10.7057(2)
_cell_measurement_reflns_used    4957
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.6820
_cell_measurement_theta_min      4.1280
_cell_volume                     971.76(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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 -33.00   0.50    0.25    --  -41.10 111.00 -49.00   84
  2  \w    -29.00  -1.00   0.50    0.25    --  -41.10 111.00 -49.00   56
  3  \w     39.00  95.00   0.50    1.00    --  100.00 -36.00 -61.00  112
  4  \w     73.00 118.00   0.50    1.00    --  100.00 -74.00 101.00   90
  5  \w     37.00  79.00   0.50    1.00    --  100.00 -64.00 -63.00   84
  6  \w    113.00 146.00   0.50    1.00    --  100.00  17.00 141.00   66
  7  \w    -75.00 -31.00   0.50    0.25    --  -41.10 -21.00 -30.00   88
  8  \w     33.00  59.00   0.50    0.25    --   41.10  43.00-120.00   52
  9  \w      5.00  51.00   0.50    0.25    --   41.10 -43.00   0.00   92
 10  \w     39.00  65.00   0.50    0.25    --   41.10 -11.00 150.00   52
 11  \w     63.00  97.00   0.50    0.25    --   41.10  43.00-120.00   68
 12  \w    -22.00   3.00   0.50    0.25    --   41.10 -11.00 150.00   50
 13  \w     94.00 142.00   0.50    1.00    --  100.00  42.00-180.00   96
 14  \w    118.00 151.00   0.50    1.00    --  100.00  33.00  30.00   66
 15  \w    131.00 156.00   0.50    1.00    --  100.00 111.00-180.00   50
 16  \w    109.00 157.00   0.50    1.00    --  100.00  17.00 -30.00   96
 17  \w     60.00 109.00   0.50    1.00    --  100.00 -25.00 -60.00   98
 18  \w     91.00 127.00   0.50    1.00    --  100.00  25.00-180.00   72
 19  \w     32.00  96.00   0.50    1.00    --  100.00 -25.00-120.00  128
 20  \w     97.00 153.00   0.50    1.00    --  100.00  36.00  95.00  112
 21  \w     82.00 118.00   0.50    1.00    --  100.00 122.00-146.00   72
 22  \w   -100.00 -70.00   0.50    0.25    --  -41.10 -43.00-180.00   60
 23  \w    -58.00 -32.00   0.50    0.25    --  -41.10 -43.00-180.00   52
 24  \w     37.00  67.00   0.50    0.25    --   41.10 -77.00-150.00   60
 25  \w     82.00 107.00   0.50    0.25    --   41.10  32.00-120.00   50
 26  \w    -15.00  23.00   0.50    0.25    --   41.10 -77.00-150.00   76
 27  \w     41.00  69.00   0.50    1.00    --  100.00 -68.00 -30.00   56
 28  \w    112.00 157.00   0.50    1.00    --  100.00  93.00 -30.00   90
 29  \w     67.00 114.00   0.50    1.00    --  100.00 -50.00 -30.00   94
 30  \w    123.00 157.00   0.50    1.00    --  100.00  42.00  60.00   68
 31  \w     36.00  77.00   0.50    1.00    --  100.00 -68.00  90.00   82
 32  \w     87.00 113.00   0.50    1.00    --  100.00  42.00  60.00   52
 33  \w     78.00 117.00   0.50    1.00    --  100.00-133.00   0.00   78
 34  \w     82.00 107.00   0.50    1.00    --  100.00-111.00 150.00   50
 35  \w     92.00 118.00   0.50    1.00    --  100.00 -68.00 -30.00   52
 36  \w     38.00  92.00   0.50    1.00    --  100.00 -68.00 150.00  108
 37  \w     52.00  97.00   0.50    1.00    --  100.00 -93.00-150.00   90
 38  \w     37.00  99.00   0.50    1.00    --  100.00 -50.00-180.00  124
 39  \w     56.00  98.00   0.50    1.00    --  100.00 -93.00-120.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0216788000
_diffrn_orient_matrix_UB_12      0.1592499000
_diffrn_orient_matrix_UB_13      -0.0159031000
_diffrn_orient_matrix_UB_21      0.0323229000
_diffrn_orient_matrix_UB_22      -0.0038016000
_diffrn_orient_matrix_UB_23      -0.1400729000
_diffrn_orient_matrix_UB_31      -0.1693367000
_diffrn_orient_matrix_UB_32      -0.0695254000
_diffrn_orient_matrix_UB_33      -0.0287406000
_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  0.0243
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            5945
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.528
_diffrn_reflns_theta_min         4.988
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.646
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65572
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
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    1.237
_exptl_crystal_description       prism
_exptl_crystal_F_000             384
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: chloroform'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.165
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1071 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     170
_refine_ls_number_reflns         2387
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0488P)^2^+0.1567P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0838
_refine_ls_wR_factor_ref         0.0845
_reflns_Friedel_coverage         0.881
_reflns_Friedel_fraction_full    0.905
_reflns_Friedel_fraction_max     0.880
_reflns_number_gt                2347
_reflns_number_total             2387
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01387a3.cif
_cod_data_source_block           syn-557
_cod_depositor_comments
'Adding full bibliography for 7160818--7160821.cif.'
_cod_original_cell_volume        971.76(3)
_cod_database_code               7160821
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C14 H15 N3 O'
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.893
_reflns_odcompleteness_completeness 97.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Rotating group:
 N2(H2A)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C10(H10), C12(H12), C5(H5), C6(H6), C3(H3), C4(H4)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              35482
_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 2.300
_oxdiff_exptl_absorpt_empirical_full_min 0.580