Unexpected dearomatization of <i>N</i>-protected 5-aminopyrazoles at ambient temperature: a simple route to highly functionalized pyrazolines.
Natarajan, Pradeep; Chatterjee, Arpita; J, Siddharth Jaya Sajeevan; Peruncheralathan, Saravanan; Organic & biomolecular chemistry 22 (2024) 6288–6293; doi:10.1039/d4ob00879k

data_7160056
_publ_section_title
;
 Unexpected dearomatization of <i>N</i>-protected 5-aminopyrazoles at
 ambient temperature: a simple route to highly functionalized pyrazolines.
;
_journal_issue                   31
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6288
_journal_page_last               6293
_journal_paper_doi               10.1039/d4ob00879k
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C19 H16 N2 O3'
_chemical_formula_sum            'C19 H16 N2 O3'
_chemical_formula_weight         320.350
_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_Int_Tables_number      14
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-05-23
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-24 deposited with the CCDC.	2024-07-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.284(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3207(4)
_cell_length_b                   5.5406(2)
_cell_length_c                   22.9882(8)
_cell_measurement_reflns_used    12383
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      30.6150
_cell_measurement_theta_min      3.7800
_cell_volume                     1513.76(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9985
_diffrn_measured_fraction_theta_max 0.8603
_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    -21.00  36.00   0.50   46.20    --    3.35 -94.00  23.00  114
  2  \w    -21.00  29.00   0.50   46.20    --   -3.98 -94.00  23.00  100
  3  \w     -7.00  63.00   0.50   46.20    --   -3.98  37.00-120.00  140
  4  \w     -7.00  63.00   0.50   46.20    --   -3.98  37.00   0.00  140
  5  \w    -15.00  32.00   0.50   46.20    --   -3.98 -99.00 150.00   94
  6  \w    -10.00  18.00   0.50   46.20    --   -3.98 -99.00 -60.00   56
  7  \w    -42.00  18.00   0.50   46.20    --   -3.98 -77.00 120.00  120
  8  \w      2.00  28.00   0.50   46.20    --   -3.98 -99.00-120.00   52
  9  \w    -42.00  18.00   0.50   46.20    --   -3.98 -77.00-150.00  120
 10  \w    -11.00  14.00   0.50   46.20    --   -3.98 -99.00 120.00   50
 11  \w     -7.00  63.00   0.50   46.20    --   -3.98  37.00 120.00  140
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0585172000
_diffrn_orient_matrix_UB_12      -0.0229185000
_diffrn_orient_matrix_UB_13      0.0058389000
_diffrn_orient_matrix_UB_21      0.0005157000
_diffrn_orient_matrix_UB_22      -0.0463720000
_diffrn_orient_matrix_UB_23      0.0288337000
_diffrn_orient_matrix_UB_31      -0.0116754000
_diffrn_orient_matrix_UB_32      -0.1171077000
_diffrn_orient_matrix_UB_33      -0.0125624000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 0.9985
_diffrn_reflns_Laue_measured_fraction_max 0.8603
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            25833
_diffrn_reflns_point_group_measured_fraction_full 0.9985
_diffrn_reflns_point_group_measured_fraction_max 0.8603
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         30.34
_diffrn_reflns_theta_min         3.43
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80624
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       needle
_exptl_crystal_F_000             672.453
_exptl_crystal_recrystallization_method 'Slow diffusion method'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.4003
_refine_diff_density_min         -0.2081
_refine_diff_density_rms         0.0494
_refine_ls_d_res_high            0.7035
_refine_ls_d_res_low             5.9425
_refine_ls_goodness_of_fit_ref   1.0367
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    28
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3916
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0367
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0359
_refine_ls_shift/su_max          0.0001
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0451P)^2^+0.6618P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0922
_refine_ls_wR_factor_ref         0.0957
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              7
_reflns_limit_k_min              0
_reflns_limit_l_max              32
_reflns_limit_l_min              0
_reflns_number_gt                3460
_reflns_number_total             3916
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4ob00879k2.cif
_cod_data_source_block           12b
_cod_depositor_comments
'Adding full bibliography for 7160054--7160057.cif.'
_cod_original_cell_volume        1513.76(10)
_cod_database_code               7160056
_chemical_oxdiff_formula         'C H N O'
_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.a Secondary CH2 refined with riding coordinates:
 C17(H17a,H17b), C18(H18a,H18b)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C6(H6), C12(H12), C5(H5), C13(H13), C8(H8), C9(H9), C15(H15),
 C14(H14)
2.c Idealised Me refined as rotating group:
 C10(H10a,H10b,H10c)
;
_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 1.496
_oxdiff_exptl_absorpt_empirical_full_min 0.443