Silver(I)-Catalyzed Tandem Sigamatropic Rearrangement/1,3-H Shift/6π Aza-electrocyclization of N-Propargylic Hydrazones: A Mild Synthetic Route to 1,6-Dihydropyridazines.
Ding, Zong-Cang; Ju, Lu-Chuan; Yang, Ying; An, Xiao-Ming; Zhou, Yun-Bing; Li, Ren-Hao; Tang, Hai-Tao; Ding, Cheng-Ke; Zhan, Zhuang-Ping; The Journal of organic chemistry 81 (2016) 3936–3941; doi:10.1021/acs.joc.6b00428

data_4036764
_publ_section_title
;
 Silver(I)-Catalyzed Tandem Sigamatropic Rearrangement/1,3-H Shift/6\p
 Aza-electrocyclization of N-Propargylic Hydrazones: A Mild Synthetic
 Route to 1,6-Dihydropyridazines.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3936
_journal_page_last               3941
_journal_paper_doi               10.1021/acs.joc.6b00428
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C19 H16 Br2 N2 O2'
_chemical_formula_sum            'C19 H16 Br2 N2 O2'
_chemical_formula_weight         464.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-08-21
_audit_creation_method
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Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.491(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.5666(3)
_cell_length_b                   7.77628(17)
_cell_length_c                   11.6785(3)
_cell_measurement_reflns_used    2168
_cell_measurement_temperature    174(2)
_cell_measurement_theta_max      60.2700
_cell_measurement_theta_min      4.4360
_cell_volume                     904.62(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      174(2)
_diffrn_detector_area_resol_mean 16.1903
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   70.00  102.20   0.7000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       32.3584   19.0000   90.0000 46

  2 omega  -29.00   64.10   0.7000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       32.3584   19.0000   90.0000 133

  3 omega   56.00  102.20   0.7000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       32.3584   57.0000  -60.0000 66

  4 omega   18.00   54.40   0.7000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       32.3584   57.0000  -60.0000 52

  5 omega -149.00 -121.70   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      -75.0000 -112.0000 -150.0000 39

  6 omega   18.00   62.10   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -38.0000   60.0000 63

  7 omega   23.00   64.30   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -25.0000    0.0000 59

  8 omega   22.00  109.50   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -64.0000    0.0000 125

  9 omega   18.00   73.30   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000 -112.0000    0.0000 79

 10 omega   45.00   87.70   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000 -112.0000   30.0000 61

 11 omega   28.00   58.10   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -38.0000   30.0000 43

 12 omega   48.00   74.60   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000   25.0000 -150.0000 38

 13 omega   95.00  161.50   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000   25.0000 -150.0000 95

 14 omega   46.00   71.20   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  178.0000   30.0000 36

 15 omega  100.00  131.50   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  178.0000   30.0000 45

 16 omega   34.00   59.20   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -25.0000  150.0000 36

 17 omega   29.00   59.10   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -25.0000  -60.0000 43

 18 omega   19.00   54.00   0.7000   27.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -38.0000  120.0000 50
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0829278000
_diffrn_orient_matrix_UB_12      -0.0390585000
_diffrn_orient_matrix_UB_13      -0.1333884000
_diffrn_orient_matrix_UB_21      0.1257814000
_diffrn_orient_matrix_UB_22      0.0280224000
_diffrn_orient_matrix_UB_23      -0.0364274000
_diffrn_orient_matrix_UB_31      0.0352003000
_diffrn_orient_matrix_UB_32      -0.1921430000
_diffrn_orient_matrix_UB_33      0.0216078000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0150
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            2869
_diffrn_reflns_point_group_measured_fraction_full 0.642
_diffrn_reflns_point_group_measured_fraction_max 0.642
_diffrn_reflns_theta_full        60.038
_diffrn_reflns_theta_max         60.038
_diffrn_reflns_theta_min         4.015
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.809
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47781
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
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    1.704
_exptl_crystal_description       plate
_exptl_crystal_F_000             460
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.443
_refine_diff_density_min         -0.444
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 265 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         1724
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0242
_refine_ls_R_factor_gt           0.0241
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0470P)^2^+0.1294P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0649
_refine_ls_wR_factor_ref         0.0649
_reflns_Friedel_coverage         0.185
_reflns_Friedel_fraction_full    0.219
_reflns_Friedel_fraction_max     0.219
_reflns_number_gt                1717
_reflns_number_total             1724
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b00428_si_002.cif
_cod_data_source_block           exp_10612
_cod_database_code               4036764
_reflns_odcompleteness_completeness 97.01
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_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:
 C1(H1A,H1B), C6(H6A,H6B)
2.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C15(H15), C18(H18), C13(H13), C16(H16), C2(H2), C12(H12), C9(H9),
 C10(H10)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              57211
_shelx_hkl_checksum              58144
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'