Iridium(III)-catalysed annulation of pyrazolidinones with propiolates: a facile route to pyrazolo[1,2-a] indazoles
Yang, Zi; Song, Zhenyu; Jie, Lianghua; Wang, Lianhui; Cui, Xiuling; Chemical Communications  (2019) –; doi:10.1039/C9CC02232E

data_7123363
_publ_section_title
;
 Iridium(III)-catalysed annulation of pyrazolidinones with propiolates: a
 facile route to pyrazolo[1,2-a] indazoles
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC02232E
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H20 F2 N2 O3'
_chemical_formula_sum            'C17 H20 F2 N2 O3'
_chemical_formula_weight         338.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-06-28 deposited with the CCDC.    2019-04-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6208(15)
_cell_length_b                   11.2655(7)
_cell_length_c                   9.9974(8)
_cell_measurement_reflns_used    3766
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      24.7890
_cell_measurement_theta_min      4.1300
_cell_volume                     1759.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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 16.1213
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.916
_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     25.00  51.00   1.00    2.50    --  -16.43  38.00  90.00   26
  2  \w    -11.00  80.00   1.00    2.50    --   15.65  77.00  30.00   91
  3  \w    -23.00  19.00   1.00    2.50    --  -16.43 -99.00  60.00   42
  4  \w    -19.00   7.00   1.00    2.50    --  -16.43 -99.00 120.00   26
  5  \w    -52.00  42.00   1.00    2.50    --   15.65 -77.00 -90.00   94
  6  \w    -19.00  17.00   1.00    2.50    --  -16.43 -99.00-180.00   36
  7  \w    -34.00  53.00   1.00    2.50    --  -16.43  38.00-180.00   87
;
_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      0.0020393000
_diffrn_orient_matrix_UB_12      -0.0111008000
_diffrn_orient_matrix_UB_13      0.0697187000
_diffrn_orient_matrix_UB_21      -0.0454014000
_diffrn_orient_matrix_UB_22      -0.0007138000
_diffrn_orient_matrix_UB_23      0.0031419000
_diffrn_orient_matrix_UB_31      0.0001295000
_diffrn_orient_matrix_UB_32      -0.0619609000
_diffrn_orient_matrix_UB_33      -0.0124884000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.916
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            15610
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.875
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.426
_diffrn_reflns_theta_min         3.617
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.102
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42106
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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    1.277
_exptl_crystal_description       prism
_exptl_crystal_F_000             712
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 822 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.3(5)
_refine_ls_extinction_coef       0.034(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         4261
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0981
_refine_ls_R_factor_gt           0.0553
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1483
_refine_ls_wR_factor_ref         0.1764
_reflns_Friedel_coverage         0.687
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.822
_reflns_number_gt                2573
_reflns_number_total             4261
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc02232e2.cif
_cod_data_source_block           exp_5657
_cod_database_code               7123363
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.985
_reflns_odcompleteness_completeness 99.52
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 C16-C17
 1.55 with sigma of 0.02
 C16A-C17A
 1.55 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C16) = Uanis(C16A)
Uanis(C17) = Uanis(C17A)
4. Others
 Sof(C16A)=Sof(H16C)=Sof(H16D)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C14(H14A,H14B), C16(H16A,H16B), C16A(H16C,H16D)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3)
5.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C17(H17A,H17B,
 H17C), C17A(H17D,H17E,H17F)
;
_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 1.517
_oxdiff_exptl_absorpt_empirical_full_min 0.449