Orthogonal Strapping of o-Haloaryl Ynones with Pyrazolones: A One-Pot, Domino Process toward Spiropyrazolones
Beesu, Mallesh; Mehta, Goverdhan; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.0c02087

data_4038885
_publ_section_title
;
 Orthogonal Strapping of o-Haloaryl Ynones with Pyrazolones: A One-Pot,
 Domino Process toward Spiropyrazolones
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.0c02087
_journal_year                    2020
_chemical_formula_moiety         '2(C24 H20 N2 O2)'
_chemical_formula_sum            'C48.05 H40 N4 O4'
_chemical_formula_weight         737.44
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-12-31
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.18 svn.r3554 for Rigaku Oxford Diffraction, GUI svn.r1)
;
_cell_angle_alpha                62.893(4)
_cell_angle_beta                 87.319(3)
_cell_angle_gamma                78.993(3)
_cell_formula_units_Z            2
_cell_length_a                   7.7764(2)
_cell_length_b                   16.2542(6)
_cell_length_c                   17.3988(6)
_cell_measurement_reflns_used    10327
_cell_measurement_temperature    249.97(18)
_cell_measurement_theta_max      25.7920
_cell_measurement_theta_min      2.3270
_cell_volume                     1919.58(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      249.97(18)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.955
_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     31.00  57.00   0.50   15.63    --   16.22 -17.00 -32.00   52
  2  \w     60.00  85.00   0.50   15.63    --   16.22  45.00 -60.00   50
  3  \w     31.00  86.00   0.50   15.63    --   16.22  45.00 -90.00  110
  4  \w     32.00  58.00   0.50   15.63    --   16.22  45.00-120.00   52
  5  \w    -10.00  21.00   0.50   15.63    --   16.22  30.00-180.00   62
  6  \w     40.00  83.00   0.50   15.63    --   16.22  30.00-180.00   86
  7  \w     -8.00  24.00   0.50   15.63    --   16.22  45.00 -90.00   64
  8  \w     -1.00  39.00   0.50   15.63    --   16.22  45.00 -60.00   80
  9  \w     26.00  85.00   0.50   15.63    --   16.22  45.00 -30.00  118
 10  \w     -3.00  33.00   0.50   15.63    --   16.22 -94.00  30.00   72
 11  \w     11.00  65.00   0.50   15.63    --   16.22-125.00  30.00  108
 12  \w    -27.00  22.00   0.50   15.63    --  -14.97 -94.00   0.00   98
 13  \w    -37.00  10.00   0.50   15.63    --  -14.97 -30.00 -60.00   94
 14  \w    -37.00  -6.00   0.50   15.63    --   16.22 -94.00 -90.00   62
 15  \w     20.00  63.00   0.50   15.63    --   16.22-125.00 -60.00   86
 16  \w    -37.00  14.00   0.50   15.63    --  -14.97 -94.00-150.00  102
 17  \w     11.00  65.00   0.50   15.63    --   16.22-125.00-180.00  108
 18  \w    -54.00   4.00   0.50   15.63    --   16.22 -45.00-180.00  116
 19  \w    -84.00 -47.00   0.50   15.63    --  -14.97 -30.00 -60.00   74
 20  \w    -46.00 -21.00   0.50   15.63    --   16.22 -17.00 -32.00   50
 21  \w    -84.00 -55.00   0.50   15.63    --  -14.97 -17.00 -32.00   58
 22  \w    -53.00 -10.00   0.50   15.63    --  -14.97 125.00   0.00   86
 23  \w    -61.00 -34.00   0.50   15.63    --  -14.97 125.00  30.00   54
 24  \w     59.00  84.00   0.50   15.63    --   16.22  17.00 136.00   50
 25  \w    -40.00 -15.00   0.50   15.63    --   16.22 132.00-107.15   50
 26  \w    -66.00 -27.00   0.50   15.63    --  -14.97 125.00 -90.00   78
 27  \w    -33.00  14.00   0.50   15.63    --  -14.97 -94.00 120.00   94
 28  \w    -12.00  52.00   0.50   15.63    --   16.22  17.00 136.00  128
 29  \w     42.00  86.00   0.50   15.63    --   16.22  77.00 150.00   88
 30  \w     29.00  55.00   0.50   15.63    --  -14.97  17.00 136.00   52
 31  \w     -9.00  23.00   0.50   15.63    --   16.22  77.00 150.00   64
 32  \w    -36.00 -11.00   0.50   15.63    --  -14.97  17.00 136.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0828855000
_diffrn_orient_matrix_UB_12      0.0226977000
_diffrn_orient_matrix_UB_13      0.0063106000
_diffrn_orient_matrix_UB_21      0.0413077000
_diffrn_orient_matrix_UB_22      0.0308682000
_diffrn_orient_matrix_UB_23      0.0079579000
_diffrn_orient_matrix_UB_31      -0.0087370000
_diffrn_orient_matrix_UB_32      0.0320305000
_diffrn_orient_matrix_UB_33      -0.0447072000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0802
_diffrn_reflns_av_unetI/netI     0.0752
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            31927
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.015
_diffrn_reflns_theta_min         2.347
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.082
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41977
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
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    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             777
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     593
_refine_ls_number_reflns         8002
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.1243
_refine_ls_R_factor_gt           0.0618
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0901P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1579
_refine_ls_wR_factor_ref         0.1964
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4062
_reflns_number_total             8002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c02087_si_005.cif
_cod_data_source_block           gm09
_cod_database_code               4038885
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.984
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C00L(H00L), C00N(H00N), C00O(H00O), C00Q(H00Q), C00R(H00R), C00T(H00T),
 C00Y(H00Y), C00Z(H00Z), C011(H011), C013(H013), C015(H015), C016(H016),
 C018(H018), C01A(H01m), C01B(H01n), C01C(H01o), C01F(H01p), C01H(H01q)
2.b Idealised Me refined as rotating group:
 C00U(H00d,H00e,H00f), C00X(H00a,H00b,H00c)
;
_shelx_res_checksum              7698
_shelx_hkl_checksum              41796
_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 2.571
_oxdiff_exptl_absorpt_empirical_full_min 0.213