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_7156016
_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         'C52 H43 Br Cu N3 O P2, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C52.5 H46 Br Cl Cu N3 O P2'
_chemical_formula_weight         975.76
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-08-25
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-08-25 deposited with the CCDC.
2017-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                101.537(7)
_cell_angle_beta                 91.712(5)
_cell_angle_gamma                108.106(6)
_cell_formula_units_Z            2
_cell_length_a                   10.2838(5)
_cell_length_b                   12.8459(10)
_cell_length_c                   20.2842(18)
_cell_measurement_reflns_used    2625
_cell_measurement_temperature    293
_cell_measurement_theta_max      23.3040
_cell_measurement_theta_min      3.3880
_cell_volume                     2483.3(3)
_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
;
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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      293
_diffrn_detector_area_resol_mean 10.4471
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_details
;
  1 omega  -59.00   40.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -       13.6514  -37.0000   90.0000 99

  2 omega   57.00  104.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -       13.6514  178.0000  120.0000 47

  3 omega   -5.00   94.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -       13.6514   19.0000  -90.0000 99

  4 omega  -25.00   27.00   1.0000   24.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.5889  -99.0000 -150.0000 52
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0157798000
_diffrn_orient_matrix_UB_12      -0.0021194000
_diffrn_orient_matrix_UB_13      -0.0346235000
_diffrn_orient_matrix_UB_21      -0.0192143000
_diffrn_orient_matrix_UB_22      -0.0594237000
_diffrn_orient_matrix_UB_23      -0.0070309000
_diffrn_orient_matrix_UB_31      -0.0685532000
_diffrn_orient_matrix_UB_32      -0.0033468000
_diffrn_orient_matrix_UB_33      0.0061699000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0581
_diffrn_reflns_av_unetI/netI     0.1240
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            17582
_diffrn_reflns_theta_full        26.37
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         2.92
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.402
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70693
_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    1.305
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1002
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.003
_refine_diff_density_min         -0.558
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     554
_refine_ls_number_reflns         9961
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1506
_refine_ls_R_factor_gt           0.0729
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0990P)^2^+0.0796P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1784
_refine_ls_wR_factor_ref         0.2325
_reflns_number_gt                5126
_reflns_number_total             9961
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c7ob02802d2.cif
_cod_data_source_block           g170824a
_cod_depositor_comments
'Adding full bibliography for 7156014--7156016.cif.'
_cod_original_formula_sum        'C52.50 H46 Br Cl Cu N3 O P2'
_cod_database_code               7156016
_reflns_odcompleteness_completeness 97.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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. Others
 Fixed Sof: Cl2(0.5) Cl1(0.5) C53(0.5) H53A(0.5) H53B(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C53(H53A,H53B)
3.b Aromatic/amide H refined with riding coordinates:
 C46(H46), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10), C11(H11), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19),
  C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27),
 C28(H28), C29(H29), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C43(H43),
  C44(H44), C45(H45), C48(H48), C49(H49), C50(H50), C51(H51)
3.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C)
;
_olex2_submission_special_instructions 'No special instructions were received'