Nitrene-mediated aminative N–N–N coupling: facile access to triazene 1-oxides
Zhu, Shiyang; Zhang, Hairuo; Sun, Boyang; Bai, Ziqian; He, Gang; Chen, Gong; Wang, Hao; Chemical Science 16 (2025) 6458–6467; doi:10.1039/D5SC00064E

data_1574119
_publ_section_title
;
 Nitrene-mediated aminative N--N--N coupling: facile access to triazene
 1-oxides
;
_journal_issue                   15
_journal_name_full               'Chemical Science'
_journal_page_first              6458
_journal_page_last               6467
_journal_paper_doi               10.1039/D5SC00064E
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C16 H17 Cl N4 O'
_chemical_formula_sum            'C16 H17 Cl N4 O'
_chemical_formula_weight         316.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-27
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2024-11-04 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.678(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.5060(2)
_cell_length_b                   11.5648(2)
_cell_length_c                   34.8112(5)
_cell_measurement_reflns_used    12647
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      39.0750
_cell_measurement_theta_min      3.4070
_cell_volume                     3021.59(11)
_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-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_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     18.00  45.00   0.50    1.00    --   -0.38  58.00-179.33   54
  2  \w     12.00  37.00   0.50    1.00    --   -0.38  67.00-105.04   50
  3  \w     13.00  41.00   0.50    1.00    --   -0.38  66.00 -90.27   56
  4  \w     16.00  42.00   0.50    1.00    --    8.02  19.00  30.00   52
  5  \w     15.00  41.00   0.50    1.00    --   -0.38  53.00  99.18   52
  6  \w    -58.00 -33.00   0.50    1.00    --   -8.77 -19.00  90.00   50
  7  \w    -41.00 -16.00   0.50    1.00    --   -0.38 -68.00  53.60   50
  8  \w    -41.00  -9.00   0.50    1.00    --    6.00 -38.00-102.27   64
  9  \w     12.00  38.00   0.50    0.05    --   -0.38  66.00 138.75   52
 10  \w     12.00  37.00   0.50    0.05    --   -0.38  67.00-164.19   50
 11  \w     15.00  40.00   0.50    0.05    --   -0.38  52.00  -7.27   50
 12  \w     15.00  40.00   0.50    0.05    --   -0.38  55.00  -8.27   50
 13  \w     13.00  38.00   0.50    0.05    --   -0.38  61.00-133.12   50
 14  \w     25.00  52.00   0.50    0.05    --    8.02  19.00  30.00   54
 15  \w     21.00  48.00   0.50    0.05    --    8.02  19.00-180.00   54
 16  \w    -57.00 -27.00   0.50    0.05    --   -8.77 -19.00-180.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0122474000
_diffrn_orient_matrix_UB_12      -0.0479861000
_diffrn_orient_matrix_UB_13      0.0123837000
_diffrn_orient_matrix_UB_21      -0.0034551000
_diffrn_orient_matrix_UB_22      -0.0374085000
_diffrn_orient_matrix_UB_23      -0.0161371000
_diffrn_orient_matrix_UB_31      0.0936349000
_diffrn_orient_matrix_UB_32      -0.0076778000
_diffrn_orient_matrix_UB_33      0.0012689000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0738
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            27068
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.572
_diffrn_reflns_theta_min         3.236
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.260
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83133
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_description       prism
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.364
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         4240
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0366
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0475P)^2^+1.4174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0993
_refine_ls_wR_factor_ref         0.1036
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3589
_reflns_number_total             4240
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00064e2.cif
_cod_data_source_block           38-mr-20240926a_auto
_cod_depositor_comments          'Adding full bibliography for 1574119.cif.'
_cod_database_code               1574119
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C16H17N4OCl
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.899
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16)
;
_shelx_res_checksum              2441
_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 2.183
_oxdiff_exptl_absorpt_empirical_full_min 0.281