Elucidating the mechanism, origin of regioselectivity and substrate scope of structurally diverse 1,2,4-triazoles synthesis via rare type of diazo compounds reactivity
Kuznetsov, Roman; Kantin, Grigory; Sapegin, Alexander; Novikov, Mikhail Sergeevich; Dar'in, Dmitry; Organic & Biomolecular Chemistry  (2025) –; doi:10.1039/D5OB01650A

data_7160876
_publ_section_title
;
 Elucidating the mechanism, origin of regioselectivity and substrate scope
 of structurally diverse 1,2,4-triazoles synthesis via rare type of diazo
 compounds reactivity
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D5OB01650A
_journal_year                    2025
_chemical_formula_moiety         '0.571(C18 H14 Cl N3 O2)'
_chemical_formula_sum            'C10.29 H8 Cl0.57 N1.71 O1.14'
_chemical_formula_weight         194.15
_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             2025-09-03
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-14 deposited with the CCDC.	2025-11-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.0140(10)
_cell_angle_gamma                90
_cell_formula_units_Z            7
_cell_length_a                   18.05750(10)
_cell_length_b                   9.68530(10)
_cell_length_c                   9.10770(10)
_cell_measurement_reflns_used    20622
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.2920
_cell_measurement_theta_min      2.5600
_cell_volume                     1545.46(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (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 2014/7 (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            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.970
_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    -26.00  28.00   0.50    0.05    --  -47.34  19.00  30.00  108
  2  \w    -42.00  26.00   0.50    0.05    --  -47.34  37.00  90.00  136
  3  \w    -70.00  25.00   0.50    0.05    --  -47.34  77.00 -30.00  190
  4  \w    -70.00  25.00   0.50    0.05    --  -47.34  77.00 -30.00  190
  5  \w    -26.00  28.00   0.50    0.05    --  -47.34  19.00-120.00  108
  6  \w   -106.00 -33.00   0.50    0.20    -- -106.00  77.00 -60.00  146
  7  \w    -71.00 -33.00   0.50    0.20    -- -106.00  61.00-120.00   76
  8  \w   -106.00 -33.00   0.50    0.20    -- -106.00  77.00 -90.00  146
  9  \w   -125.00 -33.00   0.50    0.20    -- -106.00 143.00 -52.05  184
 10  \w   -125.00 -33.00   0.50    0.20    -- -106.00 143.00 -52.05  184
 11  \w   -112.00 -36.00   0.50    0.20    -- -106.00 125.00  60.00  152
 12  \w   -122.00 -33.00   0.50    0.20    -- -106.00 139.00  56.22  178
 13  \w   -127.00 -33.00   0.50    0.20    -- -106.00 146.00 113.24  188
 14  \w   -127.00 -33.00   0.50    0.20    -- -106.00 146.00 113.24  188
 15  \w   -118.00 -35.00   0.50    0.20    -- -106.00 134.00  89.33  166
 16  \w   -112.00 -36.00   0.50    0.20    -- -106.00 125.00  60.00  152
 17  \w   -112.00 -36.00   0.50    0.20    -- -106.00 125.00 -90.00  152
 18  \w   -108.00 -36.00   0.50    0.20    -- -106.00 110.00 -82.47  144
 19  \w   -108.00 -36.00   0.50    0.20    -- -106.00 110.00 -82.47  144
 20  \w   -108.00 -37.00   0.50    0.20    -- -106.00 111.00 -42.29  142
 21  \w   -177.00 -92.00   0.50    0.20    -- -106.00 -15.00 150.00  170
 22  \w   -177.00 -92.00   0.50    0.20    -- -106.00 -51.00  73.37  170
 23  \w   -177.00 -86.00   0.50    0.20    -- -106.00 -69.00-134.59  182
 24  \w   -177.00 -87.00   0.50    0.20    -- -106.00 -68.00-169.58  180
 25  \w   -177.00 -87.00   0.50    0.20    -- -106.00 -68.00-169.58  180
 26  \w   -177.00 -92.00   0.50    0.20    -- -106.00 -51.00-107.28  170
 27  \w   -177.00 -92.00   0.50    0.20    -- -106.00 -48.00 -36.58  170
 28  \w   -177.00 -93.00   0.50    0.20    -- -106.00 -47.00 146.20  168
 29  \w   -122.00 -35.00   0.50    0.05    --  -47.34 -19.00  60.00  174
 30  \w     54.00  96.00   0.50    0.20    --  113.25 -77.00  30.00   84
 31  \w     44.00  70.00   0.50    0.20    --  113.25 -61.00  60.00   52
 32  \w     43.00  69.00   0.50    0.20    --  113.25 -61.00   0.00   52
 33  \w     42.00  67.00   0.50    0.20    --  113.25 -61.00-150.00   50
 34  \w     44.00  71.00   0.50    0.20    --  113.25 -61.00-180.00   54
 35  \w     13.00  93.00   0.50    0.05    --   47.34-125.00 -60.00  160
 36  \w     13.00  93.00   0.50    0.05    --   47.34-125.00-120.00  160
 37  \w     71.00 102.00   0.50    0.20    --  113.25-125.00 -90.00   62
 38  \w     52.00 103.00   0.50    0.20    --  113.25 -94.00-180.00  102
 39  \w     80.00 109.00   0.50    0.20    --  113.25-125.00  30.00   58
 40  \w     48.00  95.00   0.50    0.20    --  113.25-108.00  36.68   94
 41  \w     43.00  69.00   0.50    0.20    --  113.25 -94.00  60.00   52
 42  \w     43.00 102.00   0.50    0.20    --  113.25 -94.00 150.00  118
 43  \w    112.00 158.00   0.50    0.20    --  113.25  15.00  60.00   92
 44  \w     97.00 164.00   0.50    0.20    --  113.25  61.00  60.00  134
 45  \w    -27.00  26.00   0.50    0.05    --   47.34 -19.00-120.00  106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0855528000
_diffrn_orient_matrix_UB_12      -0.0086621000
_diffrn_orient_matrix_UB_13      -0.0030099000
_diffrn_orient_matrix_UB_21      0.0015562000
_diffrn_orient_matrix_UB_22      -0.1568745000
_diffrn_orient_matrix_UB_23      -0.0268692000
_diffrn_orient_matrix_UB_31      0.0203114000
_diffrn_orient_matrix_UB_32      -0.0246596000
_diffrn_orient_matrix_UB_33      0.1722314000
_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  0.0428
_diffrn_reflns_av_unetI/netI     0.0213
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            30604
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.923
_diffrn_reflns_theta_min         2.522
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.328
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69779
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light white'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.460
_exptl_crystal_description       prism
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.229
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     217
_refine_ls_number_reflns         3270
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0372
_refine_ls_R_factor_gt           0.0359
_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^)+(0.0572P)^2^+0.6855P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.0995
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3097
_reflns_number_total             3270
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01650a2.cif
_cod_data_source_block           047-648_auto
_cod_database_code               7160876
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C18H14ClN3O3
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.736
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16a,H16b), C17(H17a,H17b)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C4(H4), C8(H8), C13(H13), C14(H14), C11(H11), C5(H5), C6(H6), C7(H7)
;
_shelx_res_checksum              69616
_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 1.751
_oxdiff_exptl_absorpt_empirical_full_min 0.783