Synthesis of 2,2-difunctionalized 2<i>H</i>-azirines <i>via</i> I<sub>2</sub>-mediated annulation of enamines.
Lu, Qing; He, Yanmin; Chang, Junbiao; Yu, Wenquan; Organic & biomolecular chemistry 22 (2024) 2292–2299; doi:10.1039/d4ob00156g

data_7159813
_publ_section_title
;
 Synthesis of 2,2-difunctionalized 2<i>H</i>-azirines <i>via</i>
 I<sub>2</sub>-mediated annulation of enamines.
;
_journal_issue                   11
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2292
_journal_page_last               2299
_journal_paper_doi               10.1039/d4ob00156g
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C17 H14 N4 O2'
_chemical_formula_sum            'C17 H14 N4 O2'
_chemical_formula_weight         306.32
_chemical_melting_point          381.5(5)
_chemical_name_systematic
'Ethyl 2-(1H-benzo[d][1,2,3]triazol-1-yl)-3-phenyl-2H-azirine-2-carboxylate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2022-10-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-01-08 deposited with the CCDC.	2024-02-20 downloaded from the CCDC.
;
_cell_angle_alpha                113.649(8)
_cell_angle_beta                 108.152(6)
_cell_angle_gamma                94.284(6)
_cell_formula_units_Z            2
_cell_length_a                   9.5735(6)
_cell_length_b                   9.5741(7)
_cell_length_c                   10.0303(8)
_cell_measurement_reflns_used    1354
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.0950
_cell_measurement_theta_min      4.9890
_cell_volume                     778.90(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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   -108.00 -32.00   1.00    1.00    --  -33.50 178.00-150.00   76
  2  \w    -52.00  35.00   1.00    1.00    --  -33.50  57.00-150.00   87
  3  \w   -102.00 -15.00   1.00    1.00    --  -33.50 -57.00  60.00   87
  4  \w     14.00 107.00   1.00    1.00    --   36.62  37.00  90.00   93
  5  \w     57.00 111.00   1.00    1.00    --   36.62 178.00 -30.00   54
  6  \w     57.00 111.00   1.00    1.00    --   36.62 178.00  30.00   54
  7  \w     -4.00  77.00   1.00    1.00    --   36.62 -99.00-150.00   81
  8  \w     -1.00 109.00   1.00    1.00    --   36.62  19.00  90.00  110
  9  \w     -4.00  45.00   1.00    1.00    --   36.62 -99.00   0.00   49
 10  \w     81.00 110.00   1.00    1.00    --   36.62 178.00  60.00   29
 11  \w     49.00  74.00   1.00    1.00    --   36.62 -99.00   0.00   25
 12  \w     17.00 104.00   1.00    1.00    --   36.62  37.00-180.00   87
 13  \w     42.00  71.00   1.00    1.00    --   36.62 -99.00 120.00   29
 14  \w     46.00 108.00   1.00    3.00    --  108.00-111.00 -60.00   62
 15  \w     93.00 120.00   1.00    3.00    --  108.00 -30.00   0.00   27
 16  \w     69.00 108.00   1.00    3.00    --  108.00 -94.00 120.00   39
 17  \w     67.00 137.00   1.00    3.00    --  108.00 178.00  90.00   70
 18  \w    101.00 163.00   1.00    3.00    --  108.00 111.00  90.00   62
 19  \w     41.00 119.00   1.00    3.00    --  108.00 -45.00 150.00   78
 20  \w     85.00 137.00   1.00    3.00    --  108.00  77.00 -90.00   52
 21  \w     37.00 106.00   1.00    3.00    --  108.00-111.00  60.00   69
 22  \w    107.00 135.00   1.00    3.00    --  108.00 178.00-150.00   28
 23  \w     42.00 128.00   1.00    3.00    --  108.00 -61.00  60.00   86
 24  \w     96.00 126.00   1.00    3.00    --  108.00 -61.00 -60.00   30
 25  \w     38.00  74.00   1.00    3.00    --  108.00 -30.00   0.00   36
 26  \w     77.00 177.00   1.00    3.00    --  108.00  15.00-120.00  100
 27  \w     72.00 109.00   1.00    3.00    --  108.00 -94.00-180.00   37
 28  \w     75.00 103.00   1.00    3.00    --  108.00 178.00-150.00   28
 29  \w     89.00 176.00   1.00    3.00    --  108.00  61.00 150.00   87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0334895000
_diffrn_orient_matrix_UB_12      -0.1045975000
_diffrn_orient_matrix_UB_13      0.0748046000
_diffrn_orient_matrix_UB_21      0.0304300000
_diffrn_orient_matrix_UB_22      0.1469984000
_diffrn_orient_matrix_UB_23      0.1544148000
_diffrn_orient_matrix_UB_31      -0.1679994000
_diffrn_orient_matrix_UB_32      0.0046050000
_diffrn_orient_matrix_UB_33      -0.0569354000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            5569
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.023
_diffrn_reflns_theta_max         67.023
_diffrn_reflns_theta_min         4.995
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.729
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96988
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             320
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane/hexane'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.191
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2761
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0739
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0769P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1285
_refine_ls_wR_factor_ref         0.1504
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1912
_reflns_number_total             2761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00156g2.cif
_cod_data_source_block           202209181
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '381-382' was changed to
'381.5(5)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7159813.cif.
;
_cod_original_cell_volume        778.90(11)
_cod_database_code               7159813
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O3N2
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.886
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;
_shelx_res_checksum              85517
_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 1.174
_oxdiff_exptl_absorpt_empirical_full_min 0.914