Synthesis of Spirobidihydropyrazole through Double 1,3-Dipolar Cycloaddition of Nitrilimines with Allenoates.
Liu, Honglei; Jia, Hao; Wang, Bo; Xiao, Yumei; Guo, Hongchao; Organic letters 19 (2017) 4714–4717; doi:10.1021/acs.orglett.7b01961

data_1547564
_publ_section_title
;
 Synthesis of Spirobidihydropyrazole through Double 1,3-Dipolar
 Cycloaddition of Nitrilimines with Allenoates.
;
_journal_issue                   18
_journal_name_full               'Organic letters'
_journal_page_first              4714
_journal_page_last               4717
_journal_paper_doi               10.1021/acs.orglett.7b01961
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C39 H34 N4 O2'
_chemical_formula_sum            'C39 H34 N4 O2'
_chemical_formula_weight         590.70
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-17
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.647(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.704(3)
_cell_length_b                   18.770(5)
_cell_length_c                   17.000(4)
_cell_measurement_reflns_used    9326
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4521
_cell_measurement_theta_min      2.4093
_cell_volume                     3021.3(14)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution
;
'SHELXT (Sheldrick, 2014)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
scan:
    Number of images: 354
               Slice: -110.0000 - 67.0000
         Image width: 0.5000
            Exp time: 35.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 40.1364
              2theta: -20.4839
scan:
    Number of images: 240
               Slice: -80.0000 - 40.0000
         Image width: 0.5000
            Exp time: 35.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 40.1364
              2theta: -20.4839
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.0379
_diffrn_orient_matrix_UB_12      0.0014
_diffrn_orient_matrix_UB_13      0.0986
_diffrn_orient_matrix_UB_21      -0.0278
_diffrn_orient_matrix_UB_22      0.0443
_diffrn_orient_matrix_UB_23      0.0101
_diffrn_orient_matrix_UB_31      -0.0408
_diffrn_orient_matrix_UB_32      -0.0325
_diffrn_orient_matrix_UB_33      0.0303
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0533
_diffrn_reflns_av_unetI/netI     0.0613
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            21291
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.459
_diffrn_reflns_theta_min         2.481
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.081
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89974
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.299
_exptl_crystal_description       Plate
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.435
_exptl_crystal_size_mid          0.243
_exptl_crystal_size_min          0.087
_refine_diff_density_max         0.219
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.208
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     418
_refine_ls_number_reflns         6889
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.208
_refine_ls_R_factor_all          0.1030
_refine_ls_R_factor_gt           0.0785
_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^)+(0.0198P)^2^+1.7016P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1164
_refine_ls_wR_factor_ref         0.1241
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5487
_reflns_number_total             6889
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01961_si_002.cif
_cod_data_source_block           sa4894a
_cod_original_cell_volume        3021.2(13)
_cod_database_code               1547564
_diffrn_number_total             7109
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=1-FVAR(1)
 Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C38(H38A,H38B), C38(H38C,H38D)
3.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26),
  C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34),
 C35(H35), C36(H36)
3.c Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C39A(H39D,H39E,H39F)
;
_shelx_res_checksum              76366
_shelx_hkl_checksum              86833
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'