Fe(II)-Catalyzed Isomerization of 5-Chloroisoxazoles to 2 H-Azirine-2-carbonyl Chlorides as a Key Stage in the Synthesis of Pyrazole-Nitrogen Heterocycle Dyads.
Mikhailov, Kirill I.; Galenko, Ekaterina E.; Galenko, Alexey V.; Novikov, Mikhail S.; Ivanov, Alexander Yu; Starova, Galina L.; Khlebnikov, Alexander F.; The Journal of organic chemistry 83 (2018) 3177–3187; doi:10.1021/acs.joc.8b00069

data_4035166
_publ_section_title
;
 Fe(II)-Catalyzed Isomerization of 5-Chloroisoxazoles to 2
 H-Azirine-2-carbonyl Chlorides as a Key Stage in the Synthesis of
 Pyrazole-Nitrogen Heterocycle Dyads.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3177
_journal_page_last               3187
_journal_paper_doi               10.1021/acs.joc.8b00069
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C16 H15 N3 O'
_chemical_formula_sum            'C16 H15 N3 O'
_chemical_formula_weight         265.31
_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     direct
_audit_creation_date             2017-04-19
_audit_creation_method
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Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
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_cell_length_b                   8.0055(3)
_cell_length_c                   11.3689(5)
_cell_measurement_reflns_used    2736
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.6460
_cell_measurement_theta_min      3.2690
_cell_volume                     1330.39(10)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 16.2096
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -64.00  -32.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241  178.0000  150.0000 32

  2 omega  -88.00  -16.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241  -57.0000  -60.0000 72

  3 omega  -86.00  -10.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241  -38.0000    0.0000 76

  4 omega   40.00   89.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       23.3616 -178.0000  -90.0000 49

  5 omega  -98.00  -37.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241 -178.0000  -90.0000 61

  6 omega  -93.00  -38.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241  147.0000  162.0000 55

  7 omega  -77.00  -36.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241 -178.0000 -150.0000 41

  8 omega  -71.00  -44.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241 -178.0000  -30.0000 27

  9 omega   10.00   44.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       23.3616   57.0000 -150.0000 34
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
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_diffrn_orient_matrix_UB_11      -0.0353428000
_diffrn_orient_matrix_UB_12      0.0374492000
_diffrn_orient_matrix_UB_13      0.0252304000
_diffrn_orient_matrix_UB_21      0.0330496000
_diffrn_orient_matrix_UB_22      0.0318632000
_diffrn_orient_matrix_UB_23      0.0477000000
_diffrn_orient_matrix_UB_31      0.0036612000
_diffrn_orient_matrix_UB_32      0.0737166000
_diffrn_orient_matrix_UB_33      -0.0333743000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            10687
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.496
_diffrn_reflns_theta_min         2.901
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86902
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             560
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_refine_diff_density_max         0.292
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
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_refine_ls_number_parameters     181
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_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0321P)^2^+0.7041P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0894
_refine_ls_wR_factor_ref         0.0958
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2510
_reflns_number_total             3051
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00069_si_003.cif
_cod_data_source_block           1614hind
_cod_original_cell_volume        1330.39(9)
_cod_database_code               4035166
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C16 H12 N2 O1'
_reflns_odcompleteness_completeness 99.86
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_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:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B), C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C3(H3), C20(H20), C4(H4), C2(H2), C5(H5)
;
_shelx_res_checksum              42179
_shelx_hkl_checksum              74494
_olex2_submission_special_instructions 'No special instructions were received'