Synthesis and Intramolecular Azo Coupling of 4-Diazopyrrole-2-carboxylates: Selective Approach to Benzo and Hetero [c]-Fused 6H-Pyrrolo[3,4-c]pyridazine-5-carboxylates.
Galenko, Ekaterina E.; Galenko, Alexey V.; Khlebnikov, Alexander F.; Novikov, Mikhail S.; Shakirova, Julia R.; The Journal of organic chemistry 81 (2016) 8495–8507; doi:10.1021/acs.joc.6b01662

data_4037181
_publ_section_title
;
 Synthesis and Intramolecular Azo Coupling of
 4-Diazopyrrole-2-carboxylates: Selective Approach to Benzo and Hetero
 [c]-Fused 6H-Pyrrolo[3,4-c]pyridazine-5-carboxylates.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8495
_journal_page_last               8507
_journal_paper_doi               10.1021/acs.joc.6b01662
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C22 H15 N3'
_chemical_formula_sum            'C22 H15 N3'
_chemical_formula_weight         321.37
_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             2016-05-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.515(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.67729(19)
_cell_length_b                   11.6060(3)
_cell_length_c                   18.3580(4)
_cell_measurement_reflns_used    8042
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.1650
_cell_measurement_theta_min      4.5070
_cell_volume                     1617.72(7)
_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)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3829
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega -118.00  -38.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354  -77.0000   90.0000 80

  2 omega  -50.00   33.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354   38.0000    0.0000 83

  3 omega   58.00   91.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       41.4354  178.0000  -60.0000 33

  4 omega   57.00   96.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       41.4354 -134.0000   22.0000 39

  5 omega   51.00   84.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000   30.0000 33

  6 omega   55.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000 -120.0000 43

  7 omega  123.00  171.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000   30.0000 48

  8 omega   40.00  113.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000 -150.0000 73

  9 omega   55.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000  -30.0000 53

 10 omega   87.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000    0.0000 25

 11 omega  133.00  160.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000    0.0000 27

 12 omega   70.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000 -120.0000 39

 13 omega   44.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000   90.0000 67

 14 omega   91.00  176.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -30.0000 85

 15 omega   85.00  133.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000    0.0000 48

 16 omega   88.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -61.0000 -120.0000 27

 17 omega   41.00   85.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -61.0000 -120.0000 44

 18 omega  141.00  169.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000    0.0000 28

 19 omega   81.00  141.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -61.0000  -90.0000 60

 20 omega   48.00   75.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  150.0000 27

 21 omega   95.00  156.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000    0.0000 61

 22 omega   97.00  122.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000  -60.0000 25

 23 omega  127.00  152.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000  -60.0000 25

 24 omega   95.00  130.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  125.0000  150.0000 35

 25 omega   42.00   69.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -77.0000 -150.0000 27

 26 omega   52.00   88.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -30.0000 36

 27 omega    8.00   33.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354   38.0000  150.0000 25

 28 omega  -45.00   -1.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354  -19.0000  120.0000 44

 29 omega  -53.00  -26.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354  -57.0000    0.0000 27

 30 omega -115.00  -54.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354  -57.0000    0.0000 61

 31 omega  -94.00  -67.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -      -41.4354 -145.0000  119.0000 27

 32 omega   82.00  128.00   1.0000    5.5000
omega____ theta____ kappa____ phi______ frames
    -       41.4354  178.0000  -90.0000 46

 33 omega   32.00   57.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000   90.0000 25

 34 omega  153.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000   30.0000 25

 35 omega   47.00   95.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -49.0000 -174.9375 48

 36 omega  106.00  133.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000   30.0000 27

 37 omega   89.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  150.0000 88

 38 omega   40.00   67.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -125.0000   60.0000 27

 39 omega   79.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000  -30.0000 27

 40 omega   75.00  102.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000 -150.0000 27

 41 omega   70.00  104.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000  120.0000 34

 42 omega   38.00   89.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000  -90.0000 51

 43 omega   36.00   65.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -95.0000  120.0000 29

 44 omega   56.00   83.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -150.0000 27

 45 omega  138.00  163.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000 -180.0000 25

 46 omega   91.00  119.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000 -150.0000 28

 47 omega  132.00  175.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000 -150.0000 43

 48 omega   55.00   97.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -90.0000 42

 49 omega  105.00  130.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -61.0000  -30.0000 25
;
_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      0.0333995000
_diffrn_orient_matrix_UB_12      0.1092504000
_diffrn_orient_matrix_UB_13      0.0476905000
_diffrn_orient_matrix_UB_21      0.0251149000
_diffrn_orient_matrix_UB_22      -0.0748292000
_diffrn_orient_matrix_UB_23      0.0700520000
_diffrn_orient_matrix_UB_31      0.1986154000
_diffrn_orient_matrix_UB_32      -0.0089026000
_diffrn_orient_matrix_UB_33      -0.0040320000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0191
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            18494
_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         72.479
_diffrn_reflns_theta_min         4.522
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.620
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42851
_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            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       needle
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.228
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3214
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0377
_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^)+(0.0587P)^2^+0.5367P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0991
_refine_ls_wR_factor_ref         0.1032
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2928
_reflns_number_total             3214
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01662_si_002.cif
_cod_data_source_block           cat_phn2
_cod_database_code               4037181
_chemical_oxdiff_formula         'C16 H13 N O4'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C6(H6), C8(H8), C11(H11), C13(H13), C14(H14),
 C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C24(H24), C25(H25)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'