2H-Azirine-2-carbonyl Azides: Preparation and Use as N-Heterocyclic Building Blocks.
Funt, Liya D.; Krivolapova, Yulia V.; Khoroshilova, Olesya V.; Novikov, Mikhail Sergeevich; Khlebnikov, Alexander F.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.9b03367

data_4038042
_publ_section_title
;
 2H-Azirine-2-carbonyl Azides: Preparation and Use as N-Heterocyclic
 Building Blocks.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03367
_journal_year                    2020
_chemical_formula_moiety         'C14 H11 Br N4 O2'
_chemical_formula_sum            'C14 H11 Br N4 O2'
_chemical_formula_weight         347.18
_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     dual
_audit_creation_date             2019-09-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                85.0320(10)
_cell_angle_beta                 82.4330(10)
_cell_angle_gamma                80.6930(10)
_cell_formula_units_Z            4
_cell_length_a                   7.62280(10)
_cell_length_b                   13.76090(10)
_cell_length_c                   13.78060(10)
_cell_measurement_reflns_used    20909
_cell_measurement_temperature    100(3)
_cell_measurement_theta_max      70.3040
_cell_measurement_theta_min      3.2320
_cell_volume                     1410.93(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.50a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.50a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.50a (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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    -65.00 -30.00   0.50    0.20    --  -38.82  78.00 165.00   70
  2  \w     -8.00  24.00   0.50    0.20    --  -38.82  78.00 165.00   64
  3  \w     94.00 119.00   0.50    0.20    --  100.00  78.00 165.00   50
  4  \w     66.00 115.00   0.50    0.20    --  100.00 -78.00  40.00   98
  5  \w    -46.00 -18.00   0.50    0.20    --  -38.82 -54.00 150.00   56
  6  \w    -63.00  27.00   0.50    0.20    --  -38.82  77.00  90.00  180
  7  \w   -101.00 -23.00   0.50    0.20    --  -38.82 -43.00 -60.00  156
  8  \w    -52.00 -26.00   0.50    0.20    --  -38.82  43.00  30.00   52
  9  \w    -96.00 -36.00   0.50    0.20    --  -38.82 138.00-180.00  120
 10  \w   -102.00 -51.00   0.50    0.20    --  -38.82 -54.00 150.00  102
 11  \w     -7.00  23.00   0.50    0.20    --  -38.82  65.00  60.00   60
 12  \w    -53.00 -28.00   0.50    0.20    --  -38.82 138.00  60.00   50
 13  \w    -89.00 -57.00   0.50    0.20    --  -38.82 138.00  60.00   64
 14  \w     -6.00  26.00   0.50    0.20    --  -38.82  43.00  30.00   64
 15  \w    -35.00 -10.00   0.50    0.20    --  -38.82  65.00  60.00   50
 16  \w    -19.00  21.00   0.50    0.20    --   38.82 -77.00-120.00   80
 17  \w     72.00 100.00   0.50    0.20    --   38.82  43.00 -90.00   56
 18  \w     63.00  95.00   0.50    0.20    --   38.82  32.00-150.00   64
 19  \w     24.00  72.00   0.50    0.20    --   38.82  77.00 -90.00   96
 20  \w     26.00 100.00   0.50    0.20    --   38.82  32.00 120.00  148
 21  \w     15.00  50.00   0.50    0.20    --   38.82 -43.00 120.00   70
 22  \w     28.00  54.00   0.50    0.20    --   38.82  32.00-150.00   52
 23  \w     75.00 101.00   0.50    0.20    --   38.82  77.00 -90.00   52
 24  \w     33.00  59.00   0.50    0.20    --   38.82  43.00 -90.00   52
 25  \w     70.00 107.00   0.50    0.20    --   38.82  32.00-120.00   74
 26  \w     27.00  52.00   0.50    0.20    --   38.82 -77.00-120.00   50
 27  \w    -27.00  34.00   0.50    0.20    --   38.82 -78.00  40.00  122
 28  \w     49.00  81.00   0.50    0.20    --   38.82-138.00  30.00   64
 29  \w     29.00 113.00   0.50    0.20    --  100.00 -22.00-150.00  168
 30  \w     60.00 121.00   0.50    0.20    --  100.00-133.00 150.00  122
 31  \w     66.00 106.00   0.50    0.20    --  100.00 -53.00  60.00   80
 32  \w     33.00 115.00   0.50    0.20    --  100.00 -37.00 -60.00  164
 33  \w     81.00 107.00   0.50    0.20    --  100.00 -61.00 120.00   52
 34  \w     69.00 114.00   0.50    0.20    --  100.00 -30.00 120.00   90
 35  \w     31.00  64.00   0.50    0.20    --  100.00 -30.00 120.00   66
 36  \w     83.00 108.00   0.50    0.20    --  100.00 -93.00 120.00   50
 37  \w     80.00 129.00   0.50    0.20    --  100.00 -15.00-120.00   98
 38  \w     46.00  72.00   0.50    0.20    --  100.00 -15.00-120.00   52
 39  \w     34.00  89.00   0.50    0.20    --  100.00-111.00-180.00  110
 40  \w     41.00  88.00   0.50    0.20    --  100.00-111.00  30.00   94
 41  \w     35.00 118.00   0.50    0.20    --  100.00 -45.00-150.00  166
 42  \w     49.00 122.00   0.50    0.20    --  100.00-133.00 -90.00  146
 43  \w     40.00 122.00   0.50    0.20    --  100.00 -61.00 -30.00  164
 44  \w     64.00  90.00   0.50    0.20    --  100.00 -37.00   0.00   52
 45  \w     31.00 111.00   0.50    0.20    --  100.00-111.00 -90.00  160
 46  \w     36.00 131.00   0.50    0.20    --  100.00-144.00-123.05  190
 47  \w     33.00 103.00   0.50    0.20    --  100.00 -37.00  30.00  140
 48  \w     45.00  70.00   0.50    0.20    --  100.00 -86.00 120.00   50
 49  \w     87.00 153.00   0.50    0.20    --  100.00  30.00 120.00  132
 50  \w     71.00 121.00   0.50    0.20    --  100.00 -77.00-120.00  100
 51  \w     70.00 102.00   0.50    0.20    --  100.00-111.00  60.00   64
 52  \w     79.00 140.00   0.50    0.20    --  100.00  15.00  90.00  122
 53  \w     74.00 155.00   0.50    0.20    --  100.00  15.00-150.00  162
 54  \w    116.00 142.00   0.50    0.20    --  100.00  45.00  60.00   52
 55  \w     43.00 110.00   0.50    0.20    --  100.00-111.00-150.00  134
 56  \w     51.00  77.00   0.50    0.20    --  100.00-111.00   0.00   52
 57  \w     85.00 111.00   0.50    0.20    --  100.00-111.00   0.00   52
 58  \w     47.00 103.00   0.50    0.20    --  100.00 -93.00 -90.00  112
 59  \w     95.00 120.00   0.50    0.20    --  100.00 -61.00-150.00   50
 60  \w    100.00 145.00   0.50    0.20    --  100.00  30.00 150.00   90
 61  \w     79.00 129.00   0.50    0.20    --  100.00  61.00-150.00  100
 62  \w     73.00 145.00   0.50    0.20    --  100.00  15.00 -60.00  144
 63  \w     34.00  59.00   0.50    0.20    --   38.82  77.00 150.00   50
 64  \w    -39.00  -7.00   0.50    0.20    --   12.00 126.00 -29.29   64
 65  \w    -34.00  -9.00   0.50    0.20    --   12.00 117.00  84.86   50
 66  \w     -8.00  18.00   0.50    0.20    --   28.00 100.00 -76.43   52
 67  \w      0.00  25.00   0.50    0.20    --   32.00  91.00 107.27   50
 68  \w     -1.00  24.00   0.50    0.20    --   32.00  94.00 156.20   50
 69  \w      5.00  30.00   0.50    0.20    --   36.00  89.00  67.50   50
 70  \w      4.00  29.00   0.50    0.20    --   36.00  90.00-139.90   50
 71  \w      5.00  30.00   0.50    0.20    --   36.00  89.00   9.85   50
 72  \w      9.00  34.00   0.50    0.20    --   38.82  85.00 102.91   50
 73  \w     11.00  36.00   0.50    0.20    --   38.82  80.00 -15.12   50
 74  \w     11.00  36.00   0.50    0.20    --   40.00  84.00 -96.48   50
 75  \w     16.00  41.00   0.50    0.20    --   44.00  80.00 -55.95   50
 76  \w     16.00  41.00   0.50    0.20    --   44.00  81.00-165.22   50
 77  \w     16.00  41.00   0.50    0.20    --   44.00  80.00 167.84   50
 78  \w     16.00  41.00   0.50    0.20    --   44.00  82.00  65.57   50
 79  \w     16.00  41.00   0.50    0.20    --   44.00  82.00   6.31   50
 80  \w     16.00  41.00   0.50    0.20    --   44.00  81.00-102.39   50
 81  \w     65.00  91.00   0.50    0.20    --   52.00  74.00 -44.08   52
 82  \w     25.00  51.00   0.50    0.20    --   52.00  77.00  29.78   52
 83  \w     67.00 109.00   0.50    0.20    --   52.00  77.00  29.78   84
 84  \w     31.00  57.00   0.50    0.20    --   52.00  74.00 -44.08   52
 85  \w     30.00  56.00   0.50    0.20    --   52.00  77.00-143.58   52
 86  \w     97.00 122.00   0.50    0.20    --   56.00  77.00 -80.40   50
 87  \w     30.00  66.00   0.50    0.20    --   56.00  77.00 -80.40   72
 88  \w     29.00  55.00   0.50    0.20    --   56.00  77.00 129.32   52
 89  \w     91.00 117.00   0.50    0.20    --   56.00  77.00 129.32   52
 90  \w     32.00  57.00   0.50    0.20    --   56.00  69.00-102.94   50
 91  \w     30.00  55.00   0.50    0.20    --   56.00  76.00 177.05   50
 92  \w     37.00  65.00   0.50    0.20    --   60.00  68.00  -9.34   56
 93  \w     34.00  60.00   0.50    0.20    --   60.00  76.00  64.12   52
 94  \w     96.00 130.00   0.50    0.20    --   64.00  77.00  83.68   68
 95  \w     37.00  62.00   0.50    0.20    --   64.00  77.00  83.68   50
 96  \w     42.00  68.00   0.50    0.20    --   64.00  73.00  16.41   52
 97  \w     44.00  77.00   0.50    0.20    --   68.00  77.00 174.50   66
 98  \w     42.00  83.00   0.50    0.20    --   68.00  76.00 -48.69   82
 99  \w     90.00 125.00   0.50    0.20    --   68.00  76.00 -48.69   70
100  \w     49.00  83.00   0.50    0.20    --   72.00  72.00 124.89   68
101  \w    113.00 138.00   0.50    0.20    --   72.00  72.00 124.89   50
102  \w     47.00  90.00   0.50    0.20    --   72.00  72.00-110.83   86
103  \w     45.00  70.00   0.50    0.20    --   72.00  77.00-146.94   50
104  \w     54.00  79.00   0.50    0.20    --   76.00  64.00 -53.18   50
105  \w    116.00 142.00   0.50    0.20    --   76.00  76.00 146.18   52
106  \w     50.00  76.00   0.50    0.20    --   76.00  76.00 146.18   52
107  \w     53.00 115.00   0.50    0.20    --   76.00  65.00   6.88  124
108  \w     54.00  87.00   0.50    0.20    --   80.00  76.00  29.40   66
109  \w     64.00  90.00   0.50    0.20    --   80.00  72.00  86.60   52
110  \w    118.00 144.00   0.50    0.20    --   80.00  76.00  29.40   52
111  \w     58.00  83.00   0.50    0.20    --   84.00  76.00  70.16   50
112  \w    100.00 127.00   0.50    0.20    --   84.00  77.00-127.19   54
113  \w     59.00  84.00   0.50    0.20    --   84.00  71.00-149.40   50
114  \w     59.00  93.00   0.50    0.20    --   84.00  77.00-127.19   68
115  \w     78.00 104.00   0.50    0.20    --  100.00  61.00-180.00   52
116  \w     73.00 105.00   0.50    0.20    --  100.00  77.00  60.00   64
117  \w     73.00 109.00   0.50    0.20    --  100.00  77.00  90.00   72
118  \w    129.00 156.00   0.50    0.20    --  100.00  61.00   0.00   54
119  \w     75.00 113.00   0.50    0.20    --  100.00  77.00 -30.00   76
120  \w     80.00 125.00   0.50    0.20    --  100.00  61.00   0.00   90
121  \w     74.00 137.00   0.50    0.20    --  100.00  77.00   0.00  126
122  \w     76.00 150.00   0.50    0.20    --  100.00  69.00 -30.00  148
123  \w     74.00 109.00   0.50    0.20    --  100.00  77.00 150.00   70
124  \w     73.00 108.00   0.50    0.20    --  100.00  77.00  30.00   70
125  \w     73.00  99.00   0.50    0.20    --  100.00  77.00 -90.00   52
126  \w    131.00 156.00   0.50    0.20    --  100.00  53.00-150.00   50
127  \w     89.00 145.00   0.50    0.20    --  100.00  45.00 -60.00  112
128  \w    110.00 150.00   0.50    0.20    --  100.00 111.00 -30.00   80
129  \w     76.00 115.00   0.50    0.20    --  100.00  69.00 120.00   78
130  \w    126.00 157.00   0.50    0.20    --  100.00  37.00  90.00   62
131  \w     90.00 116.00   0.50    0.20    --  100.00  37.00  90.00   52
132  \w     76.00 102.00   0.50    0.20    --  100.00  69.00  90.00   52
133  \w    118.00 144.00   0.50    0.20    --  100.00  77.00-150.00   52
134  \w    128.00 153.00   0.50    0.20    --  100.00  69.00  30.00   50
135  \w     76.00 102.00   0.50    0.20    --  100.00  69.00  30.00   52
136  \w     73.00 109.00   0.50    0.20    --  100.00  77.00-150.00   72
137  \w    119.00 145.00   0.50    0.20    --  100.00  69.00  90.00   52
138  \w    127.00 153.00   0.50    0.20    --  100.00  77.00-180.00   52
139  \w     73.00 123.00   0.50    0.20    --  100.00  77.00-120.00  100
140  \w     73.00 113.00   0.50    0.20    --  100.00  77.00-180.00   80
141  \w     76.00 103.00   0.50    0.20    --  100.00  69.00 150.00   54
142  \w     25.00 129.00   0.50    0.20    --  100.00 -15.00  30.00  208
143  \w     76.00 101.00   0.50    0.20    --  100.00  69.00 -60.00   50
144  \w     73.00 134.00   0.50    0.20    --  100.00  77.00 -60.00  122
145  \w    -43.00 -18.00   0.50    0.20    --  -38.82  78.00 165.00   50
146  \w     54.00  80.00   0.50    0.20    --   76.00  59.00-161.94   52
147  \w     63.00  89.00   0.50    0.20    --   88.00  73.00 -86.82   52
;
_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      -0.0902096000
_diffrn_orient_matrix_UB_12      -0.0932996000
_diffrn_orient_matrix_UB_13      0.0208048000
_diffrn_orient_matrix_UB_21      0.1083228000
_diffrn_orient_matrix_UB_22      -0.0433259000
_diffrn_orient_matrix_UB_23      -0.0929758000
_diffrn_orient_matrix_UB_31      0.1505951000
_diffrn_orient_matrix_UB_32      -0.0484303000
_diffrn_orient_matrix_UB_33      0.0608085000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            28135
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.445
_diffrn_reflns_theta_min         3.242
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.073
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46441
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.50a (Rigaku Oxford Diffraction, 2019)
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    1.634
_exptl_crystal_description       prism
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.678
_refine_diff_density_min         -1.076
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     383
_refine_ls_number_reflns         5390
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0347
_refine_ls_R_factor_gt           0.0344
_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^)+(0.0478P)^2^+2.0883P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0896
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5321
_reflns_number_total             5390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03367_si_003.cif
_cod_data_source_block           13780_lia-727
_cod_database_code               4038042
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C14H11BrN4O2
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.385
_reflns_odcompleteness_completeness 96.20
_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 Aromatic/amide H refined with riding coordinates:
 N1(H1), N1A(H1AA), C11(H11), C13(H13), C10(H10), C11A(H11A), C14(H14),
 C14A(H14A), C10A(H10A), C13A(H13A)
2.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C1A(H1AB,H1AC,H1AD), C5(H5A,H5B,H5C), C5A(H5AA,H5AB,H5AC)
;
_shelx_res_checksum              8006
_shelx_hkl_checksum              48454
_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 2.828
_oxdiff_exptl_absorpt_empirical_full_min 0.618