Synthesis of spiro-4H-pyrazole-oxindoles and fused 1H-pyrazoles via divergent, thermally induced tandem cyclization/migration of alkyne-tethered diazo compounds.
Zhang, Cheng; Dong, Shanliang; Zheng, Yang; He, Ciwang; Chen, Jiaolong; Zhen, Jingsen; Qiu, Lihua; Xu, Xinfang; Organic & biomolecular chemistry 16 (2018) 688–692; doi:10.1039/c7ob02802d

data_7156014
_publ_section_title
;
 Synthesis of spiro-4H-pyrazole-oxindoles and fused 1H-pyrazoles via
 divergent, thermally induced tandem cyclization/migration of
 alkyne-tethered diazo compounds.
;
_journal_issue                   5
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              688
_journal_page_last               692
_journal_paper_doi               10.1039/c7ob02802d
_journal_volume                  16
_journal_year                    2018
_chemical_formula_moiety         'C18 H12 N4 O'
_chemical_formula_sum            'C18 H12 N4 O'
_chemical_formula_weight         300.32
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-09-26
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.07.08 svn.r3312 for OlexSys, GUI svn.r5203)
;
_audit_update_record
;
2017-08-02 deposited with the CCDC.
2017-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.410(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.3723(14)
_cell_length_b                   8.7871(5)
_cell_length_c                   19.4970(14)
_cell_measurement_reflns_used    2282
_cell_measurement_temperature    295.3(7)
_cell_measurement_theta_max      22.9540
_cell_measurement_theta_min      3.9140
_cell_volume                     3130.3(4)
_computing_cell_refinement
;
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)
;
_computing_data_reduction
;
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)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      295.3(7)
_diffrn_detector_area_resol_mean 10.4471
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -15.00   69.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       15.2428   77.0000    0.0000 84

  2 omega   35.00   86.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       15.2428  178.0000  -60.0000 51

  3 omega  -87.00  -58.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.1803 -178.0000   60.0000 29

  4 omega  -25.00    4.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.1803  -99.0000  150.0000 29

  5 omega -105.00  -68.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.1803 -178.0000  120.0000 37

  6 omega  -39.00   38.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       15.2428  -88.0000   22.0000 77
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0375202000
_diffrn_orient_matrix_UB_12      -0.0114844000
_diffrn_orient_matrix_UB_13      -0.0201717000
_diffrn_orient_matrix_UB_21      0.0011392000
_diffrn_orient_matrix_UB_22      -0.0716760000
_diffrn_orient_matrix_UB_23      0.0170697000
_diffrn_orient_matrix_UB_31      -0.0099137000
_diffrn_orient_matrix_UB_32      0.0352417000
_diffrn_orient_matrix_UB_33      0.0281096000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0468
_diffrn_reflns_av_unetI/netI     0.0523
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10530
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.944
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97904
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.274
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.175
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3189
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.1056
_refine_ls_R_factor_gt           0.0503
_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^)+(0.0555P)^2^+0.3993P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1085
_refine_ls_wR_factor_ref         0.1377
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1819
_reflns_number_total             3189
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02802d2.cif
_cod_data_source_block           g160926a
_cod_depositor_comments
'Adding full bibliography for 7156014--7156016.cif.'
_cod_database_code               7156014
_chemical_oxdiff_formula         'C H N O'
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13), C14(H14)
2.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'