[4 + 2] Annulation Reaction of <i>In Situ</i> Generated Azoalkenes with Azlactones: Access to 4,5-Dihydropyridazin-3(2<i>H</i>)-Ones.
Yuan, Wei-Cheng; Quan, Bao-Xue; Zhao, Jian-Qiang; You, Yong; Wang, Zhen-Hua; Zhou, Ming-Qiang; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01592

data_4038747
_publ_section_title
;
 [4 + 2] Annulation Reaction of <i>In Situ</i> Generated Azoalkenes with
 Azlactones: Access to 4,5-Dihydropyridazin-3(2<i>H</i>)-Ones.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01592
_journal_year                    2020
_chemical_formula_moiety         'C30 H25 N3 O4 S'
_chemical_formula_sum            'C30 H25 N3 O4 S'
_chemical_formula_weight         523.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-08-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.6255(16)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.4299(4)
_cell_length_b                   8.50556(7)
_cell_length_c                   22.1713(3)
_cell_measurement_reflns_used    4988
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8940
_cell_measurement_theta_min      4.2410
_cell_volume                     5296.81(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -73.00 -20.00   0.50    0.50    --  -33.50 -57.00 -90.00  106
  2  \w    -47.00  31.00   0.50    0.50    --  -33.50  37.00 -90.00  156
  3  \w    -68.00 -32.00   0.50    0.50    --  -33.50 178.00  30.00   72
  4  \w    -70.00 -24.00   0.50    0.50    --  -33.50 -57.00-120.00   92
  5  \w     59.00 109.00   0.50    0.50    --   36.47 178.00 -60.00  100
  6  \w     17.00  45.00   0.50    0.50    --   36.47 -57.00 -60.00   56
  7  \w    -32.00  34.00   0.50    0.50    --   36.47 -57.00  60.00  132
  8  \w     22.00 105.00   0.50    0.50    --   36.47  37.00 -60.00  166
  9  \w     73.00 104.00   0.50    0.50    --   36.47 178.00-120.00   62
 10  \w     50.00  75.00   0.50    0.50    --   36.47 -99.00-180.00   50
 11  \w      6.00  33.00   0.50    0.50    --   36.47 -99.00-180.00   54
 12  \w     76.00 103.00   0.50    0.50    --   36.47 178.00 -30.00   54
 13  \w     88.00 178.00   0.50    2.50    --  108.00  45.00-120.00  180
 14  \w     42.00 109.00   0.50    2.50    --  108.00 -94.00 -30.00  134
 15  \w     92.00 132.00   0.50    2.50    --  108.00 -30.00  60.00   80
 16  \w     41.00  69.00   0.50    2.50    --  108.00 -30.00  60.00   56
 17  \w     46.00 116.00   0.50    2.50    --  108.00 -45.00 -60.00  140
 18  \w     82.00 110.00   0.50    2.50    --  108.00 -94.00 150.00   56
 19  \w     71.00 105.00   0.50    2.50    --  108.00 -94.00  30.00   68
 20  \w     62.00  99.00   0.50    2.50    --  108.00-111.00 150.00   74
 21  \w     83.00 162.00   0.50    2.50    --  108.00  30.00-180.00  158
 22  \w    107.00 160.00   0.50    2.50    --  108.00 111.00  60.00  106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0093913300
_diffrn_orient_matrix_UB_12      -0.0696520677
_diffrn_orient_matrix_UB_13      0.0679940877
_diffrn_orient_matrix_UB_21      -0.0492896574
_diffrn_orient_matrix_UB_22      0.0573207736
_diffrn_orient_matrix_UB_23      -0.0049143706
_diffrn_orient_matrix_UB_31      -0.0221531891
_diffrn_orient_matrix_UB_32      -0.1570346586
_diffrn_orient_matrix_UB_33      -0.0319457309
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0235
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            11203
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         4.256
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.422
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87522
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.313
_exptl_crystal_description       block
_exptl_crystal_F_000             2192
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.473
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     340
_refine_ls_number_reflns         4716
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0517
_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^)+(0.0802P)^2^+3.4767P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1409
_refine_ls_wR_factor_ref         0.1518
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4002
_reflns_number_total             4716
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01592_si_002.cif
_cod_data_source_block           201908201a
_cod_original_cell_volume        5296.82(13)
_cod_database_code               4038747
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         c20h20n4o4s1
_shelx_estimated_absorpt_t_max   0.848
_shelx_estimated_absorpt_t_min   0.774
_reflns_odcompleteness_completeness 99.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O4A-C17A
 1.2 with sigma of 0.02
 C17-C18
 1.5 with sigma of 0.02
 C17A-C18A
 1.5 with sigma of 0.02
 C17A-N3
 1.4 with sigma of 0.02
 C17-N3
 1.4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C10) = Uanis(C10A)
Uanis(C9) = Uanis(C9A)
Uanis(C7) = Uanis(C7A)
Uanis(C6) = Uanis(C6A)
Uanis(C8) = Uanis(C8A)
Uanis(C18) = Uanis(C18A)
Uanis(C23) = Uanis(C23A)
Uanis(C22) = Uanis(C22A)
Uanis(C21) = Uanis(C21A)
Uanis(C20) = Uanis(C20A)
Uanis(C19) = Uanis(C19A)
Uanis(C17) = Uanis(C17A)
Uanis(O4) = Uanis(O4A)
Uanis(C5) = Uanis(C5A)
4. Others
 Sof(C5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=
 Sof(H9A)=Sof(C10A)=Sof(H10A)=1-FVAR(1)
 Sof(C5)=Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=Sof(C8)=Sof(H8)=Sof(C7)=Sof(H7)=
 Sof(C6)=Sof(H6)=FVAR(1)
 Sof(C17A)=Sof(C18A)=Sof(C23A)=Sof(H23A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=
 Sof(H21A)=Sof(C20A)=Sof(H20A)=Sof(C19A)=Sof(H19A)=Sof(H3BB)=Sof(O4A)=1-FVAR(2)
 Sof(C17)=Sof(C18)=Sof(C23)=Sof(H23)=Sof(C22)=Sof(H22)=Sof(C21)=Sof(H21)=
 Sof(C20)=Sof(H20)=Sof(C19)=Sof(H19)=Sof(H3AA)=Sof(O4)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
5.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C9(H9), C8(H8), C7(H7), C6(H6), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C23(H23), C22(H22), C21(H21), C20(H20), C19(H19),
 C23A(H23A), C22A(H22A), C21A(H21A), C20A(H20A), C19A(H19A), C25(H25), C26(H26),
  C28(H28), C29(H29), N3(H3AA), N3(H3BB), C6A(H6A), C7A(H7A), C8A(H8A),
 C9A(H9A), C10A(H10A)
5.c Fitted hexagon refined as free rotating group:
 C5(C10,C9,C8,C7,C6), C18(C23,C22,C21,C20,C19), C18A(C23A,C22A,C21A,C20A,C19A),
  C5A(C6A,C7A,C8A,C9A,C10A)
5.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C)
;
_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 1.264
_oxdiff_exptl_absorpt_empirical_full_min 0.870