Synthesis of 2-(Di/tri/tetraazolyl)-2 H-azirine-2-carboxylates by Halogen Substitution: Evidence for an S<sub>N</sub>2'-S<sub>N</sub>2' Cascade Mechanism.
Agafonova, Anastasiya V.; Rostovskii, Nikolai V.; Smetanin, Ilia A.; Starova, Galina L.; Khlebnikov, Alexander F.; Novikov, Mikhail S.; The Journal of organic chemistry 83 (2018) 13473–13480; doi:10.1021/acs.joc.8b02295

data_4035762
_publ_section_title
;
 Synthesis of 2-(Di/tri/tetraazolyl)-2 H-azirine-2-carboxylates by Halogen
 Substitution: Evidence for an S<sub>N</sub>2'-S<sub>N</sub>2' Cascade
 Mechanism.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13473
_journal_page_last               13480
_journal_paper_doi               10.1021/acs.joc.8b02295
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C13 H11 N3 O2'
_chemical_formula_sum            'C13 H11 N3 O2'
_chemical_formula_weight         241.25
_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     iterative
_audit_creation_date             2018-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
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_cell_measurement_reflns_used    9308
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.0090
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_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
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Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
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_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
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  2 omega   67.00   98.00   1.0000    7.5000
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  3 omega   65.00   90.00   1.0000    7.5000
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  4 omega   49.00   76.00   1.0000    7.5000
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  5 omega   47.00  103.00   1.0000    7.5000
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  6 omega   42.00   86.00   1.0000    7.5000
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  7 omega   85.00  126.00   1.0000    7.5000
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  8 omega  132.00  177.00   1.0000    7.5000
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  9 omega  150.00  177.00   1.0000    7.5000
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 10 omega   73.00  106.00   1.0000    2.5000
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 11 omega   64.00   97.00   1.0000    7.5000
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 12 omega -125.00    6.00   1.0000    2.5000
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 13 omega  -98.00  -71.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
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 14 omega   62.00  113.00   1.0000    2.5000
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 15 omega   55.00   87.00   1.0000    7.5000
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 16 omega   83.00  110.00   1.0000    7.5000
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 17 omega   44.00   81.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
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 18 omega   56.00  100.00   1.0000    7.5000
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 19 omega  153.00  178.00   1.0000    7.5000
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 20 omega   97.00  127.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
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 21 omega   83.00  132.00   1.0000    7.5000
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 22 omega   43.00   69.00   1.0000    7.5000
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 23 omega  103.00  142.00   1.0000    7.5000
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 24 omega   54.00   94.00   1.0000    7.5000
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 25 omega   57.00   88.00   1.0000    7.5000
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 26 omega  -46.00  -10.00   1.0000    2.5000
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 27 omega  -95.00  -68.00   1.0000    2.5000
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 28 omega  -26.00   34.00   1.0000    2.5000
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 29 omega -115.00  -75.00   1.0000    2.5000
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 30 omega  -71.00  -14.00   1.0000    2.5000
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 31 omega   81.00  107.00   1.0000    7.5000
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 32 omega   80.00  125.00   1.0000    7.5000
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 33 omega   82.00  108.00   1.0000    7.5000
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 34 omega   86.00  112.00   1.0000    7.5000
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 35 omega   80.00  105.00   1.0000    7.5000
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 36 omega  124.00  160.00   1.0000    7.5000
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 37 omega   86.00  113.00   1.0000    7.5000
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 38 omega  123.00  155.00   1.0000    7.5000
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 39 omega   79.00  105.00   1.0000    7.5000
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 40 omega   80.00  106.00   1.0000    7.5000
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 41 omega  137.00  165.00   1.0000    7.5000
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 42 omega   39.00   65.00   1.0000    7.5000
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 43 omega   83.00  128.00   1.0000    7.5000
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 44 omega   45.00   71.00   1.0000    7.5000
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 45 omega  145.00  171.00   1.0000    7.5000
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 46 omega   79.00  116.00   1.0000    7.5000
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 47 omega   79.00  105.00   1.0000    7.5000
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 48 omega   63.00   92.00   1.0000    7.5000
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 49 omega   88.00  119.00   1.0000    7.5000
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 50 omega   50.00   76.00   1.0000    7.5000
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 51 omega   86.00  115.00   1.0000    7.5000
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 52 omega  121.00  153.00   1.0000    7.5000
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 53 omega   50.00   89.00   1.0000    7.5000
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 54 omega   87.00  113.00   1.0000    7.5000
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 55 omega  135.00  160.00   1.0000    7.5000
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 56 omega   83.00  109.00   1.0000    7.5000
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 57 omega   87.00  121.00   1.0000    7.5000
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 58 omega   79.00  106.00   1.0000    7.5000
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 59 omega   58.00   84.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000 -120.0000 26

 60 omega  124.00  167.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   68.0000   48.6894 43

 61 omega   86.00  132.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
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 62 omega  137.00  163.00   1.0000    7.5000
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 63 omega   83.00  110.00   1.0000    7.5000
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 64 omega  102.00  128.00   1.0000    2.5000
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 65 omega   75.00  101.00   1.0000    2.5000
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 66 omega   73.00  126.00   1.0000    2.5000
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 67 omega   47.00  102.00   1.0000    7.5000
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 68 omega   95.00  120.00   1.0000    7.5000
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 69 omega   87.00  115.00   1.0000    7.5000
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 70 omega   53.00   79.00   1.0000    7.5000
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 71 omega   81.00  121.00   1.0000    7.5000
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 72 omega   90.00  116.00   1.0000    7.5000
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 73 omega   83.00  109.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
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 74 omega   96.00  121.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000 -150.0000 25

 75 omega   44.00   70.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000   30.0000 26

 76 omega   82.00  119.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000   30.0000 37

 77 omega   79.00  105.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000  -90.0000 26

 78 omega  135.00  161.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000  -90.0000 26

 79 omega   75.00  106.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000 -180.0000 31

 80 omega   96.00  128.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000  -90.0000 32

 81 omega   63.00   89.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -61.0000 -150.0000 26

 82 omega  140.00  165.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000  -30.0000 25

 83 omega   79.00  105.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000   30.0000 26

 84 omega   72.00  102.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -15.0000  -30.0000 30

 85 omega   96.00  122.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   36.0000  -49.0000 26

 86 omega    5.00   32.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       38.0000   82.0000   13.2593 27

 87 omega  -53.00  -18.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354  -38.0000 -180.0000 35

 88 omega  -48.00   22.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354   38.0000    0.0000 70

 89 omega -113.00  -62.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354  -38.0000 -180.0000 51

 90 omega    7.00   32.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       42.0000   86.0000  120.7851 25

 91 omega   17.00   42.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   80.0000 -174.4820 25

 92 omega   21.00   46.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000  -90.8461 25

 93 omega   21.00   47.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000  126.0054 26

 94 omega   21.00   46.00   1.0000    2.5000
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 95 omega   21.00   46.00   1.0000    2.5000
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 96 omega   21.00   46.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
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 97 omega   34.00   61.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
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 98 omega   33.00   59.00   1.0000    2.5000
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 99 omega   34.00   59.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
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;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0651373000
_diffrn_orient_matrix_UB_12      0.0222722000
_diffrn_orient_matrix_UB_13      -0.1986999000
_diffrn_orient_matrix_UB_21      -0.1720062000
_diffrn_orient_matrix_UB_22      0.0297451000
_diffrn_orient_matrix_UB_23      -0.0029882000
_diffrn_orient_matrix_UB_31      0.0914464000
_diffrn_orient_matrix_UB_32      0.0718379000
_diffrn_orient_matrix_UB_33      0.0627928000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
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_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            22585
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.999
_diffrn_reflns_theta_min         4.642
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.780
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65999
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       prizm
_exptl_crystal_F_000             504
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.226
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     164
_refine_ls_number_reflns         2244
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0357
_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^)+(0.0560P)^2^+0.3558P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0945
_refine_ls_wR_factor_ref         0.0987
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2035
_reflns_number_total             2244
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02295_si_002.cif
_cod_data_source_block           103-137-4929_rnv23
_cod_original_cell_volume        1181.51(10)
_cod_database_code               4035762
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C13 H11 N3 O2'
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C12(H12), C4(H4), C13(H13), C5(H5), C11(H11), C7(H7)
2.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              20342
_shelx_hkl_checksum              50340
_olex2_submission_special_instructions 'No special instructions were received'