Combinatorial synthesis of substituted pyrazolo-fused quinazolines by the Rh(III)-catalyzed [5 + 1] annulation of phenyl-1<i>H</i>-pyrazol-5-amine with alkynoates and alkynamides.
Chiu, Wei-Jung; Chu, Ting-Yen; Sun, Chung-Ming; Organic & biomolecular chemistry 22 (2024) 6841–6846; doi:10.1039/d4ob00516c

data_7160083
_publ_section_title
;
 Combinatorial synthesis of substituted pyrazolo-fused quinazolines by the
 Rh(III)-catalyzed [5 + 1] annulation of phenyl-1<i>H</i>-pyrazol-5-amine
 with alkynoates and alkynamides.
;
_journal_issue                   33
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6841
_journal_page_last               6846
_journal_paper_doi               10.1039/d4ob00516c
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C19 H25 N3 O2'
_chemical_formula_sum            'C19 H25 N3 O2'
_chemical_formula_weight         327.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-08
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-03-11 deposited with the CCDC.	2024-08-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.2955(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.83365(16)
_cell_length_b                   14.19083(19)
_cell_length_c                   11.90925(15)
_cell_measurement_reflns_used    10562
_cell_measurement_temperature    103(6)
_cell_measurement_theta_max      74.4700
_cell_measurement_theta_min      4.8480
_cell_volume                     1816.09(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      103(6)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -76.00 -36.00   0.50    0.22    --  -77.70 125.00-150.00   80
  2  \w    -87.00 -62.00   0.50    0.22    --  -74.55 106.00-174.00   50
  3  \w    -90.00 -65.00   0.50    0.22    --  -77.70 106.00-174.00   50
  4  \w    -80.00 -25.00   0.50    0.22    --  -64.95 106.00-174.00  110
  5  \w   -118.00 -77.00   0.50    0.22    --  -74.55-125.00 -60.00   82
  6  \w   -100.00 -75.00   0.50    0.22    --  -74.55-125.00 -90.00   50
  7  \w   -115.00 -74.00   0.50    0.22    --  -77.70-125.00  90.00   82
  8  \w   -113.00 -82.00   0.50    0.22    --  -77.70-125.00 150.00   62
  9  \w   -118.00 -64.00   0.50    0.22    --  -74.55 -15.00  90.00  108
 10  \w     35.00  98.00   0.50    0.22    --   61.89   0.00-120.00  126
 11  \w     78.00 103.00   0.50    0.22    --   74.76-125.00-180.00   50
 12  \w     74.00  99.00   0.50    0.22    --   74.76-125.00-150.00   50
 13  \w     28.00  70.00   0.50    0.22    --   61.89 -95.00 -90.00   84
 14  \w     40.00  78.00   0.50    0.22    --   74.76-106.00  86.00   76
 15  \w     33.00  98.00   0.50    0.22    --   74.76-125.00 150.00  130
 16  \w     39.00  76.00   0.50    0.22    --   73.73 -95.00 150.00   74
 17  \w     35.00  70.00   0.50    0.22    --   61.89 -95.00 120.00   70
 18  \w     25.00  60.00   0.50    0.22    --   61.89-106.00  86.00   70
 19  \w     24.00  65.00   0.50    0.22    --   61.89 -95.00   0.00   82
 20  \w     43.00  70.00   0.50    0.22    --   74.76 -95.00 -60.00   54
 21  \w     32.00  63.00   0.50    0.22    --   61.89 -95.00-180.00   62
 22  \w     58.00 107.00   0.50    0.22    --   61.89  15.00  60.00   98
 23  \w     42.00  68.00   0.50    0.22    --   74.76   0.00  90.00   52
 24  \w     23.00  49.00   0.50    0.22    --   61.89-125.00  90.00   52
 25  \w     43.00  69.00   0.50    0.22    --   70.61 -95.00  30.00   52
 26  \w     37.00  62.00   0.50    0.22    --   74.76 -95.00-150.00   50
 27  \w     89.00 119.00   0.50    0.22    --   80.10 125.00 -90.00   60
 28  \w     79.00 104.00   0.50    0.22    --   80.10 125.00  90.00   50
 29  \w     47.00  85.00   0.50    0.22    --   61.89   0.00 150.00   76
 30  \w     30.00  88.00   0.50    0.22    --   61.89   0.00  30.00  116
 31  \w     24.00  49.00   0.50    0.22    --   61.89 -95.00 150.00   50
 32  \w     68.00  93.00   0.50    0.22    --   62.00  72.00 139.01   50
 33  \w     35.00  79.00   0.50    0.22    --   70.61 -95.00 -30.00   88
 34  \w     42.00  68.00   0.50    0.22    --   70.61  15.00 -90.00   52
 35  \w     76.00 113.00   0.50    0.22    --   70.61  15.00 -90.00   74
 36  \w    -61.00 -31.00   0.50    0.22    --  -74.55 125.00 120.00   60
 37  \w     81.00 120.00   0.50    0.22    --   74.76  15.00 -60.00   78
 38  \w     78.00 103.00   0.50    0.22    --   74.76-125.00 -30.00   50
 39  \w     31.00  57.00   0.50    0.22    --   74.76-125.00 -30.00   52
 40  \w   -105.00 -75.00   0.50    0.22    --  -77.70 125.00-150.00   60
 41  \w   -108.00 -74.00   0.50    0.22    --  -77.70-125.00  30.00   68
 42  \w   -106.00 -74.00   0.50    0.22    --  -77.70-125.00   0.00   64
 43  \w    -73.00 -47.00   0.50    0.22    --  -77.70 125.00   0.00   52
 44  \w   -105.00 -79.00   0.50    0.22    --  -77.70 125.00   0.00   52
 45  \w     88.00 121.00   0.50    0.22    --   80.10 125.00 150.00   66
 46  \w     84.00 109.00   0.50    0.22    --   80.10-125.00 120.00   50
 47  \w     37.00  62.00   0.50    0.22    --   80.10-125.00-120.00   50
 48  \w     98.00 124.00   0.50    0.22    --   80.10 125.00-120.00   52
 49  \w     40.00  66.00   0.50    0.22    --   80.10-125.00 120.00   52
 50  \w     44.00  69.00   0.50    0.22    --   80.10-125.00  60.00   50
 51  \w     84.00 109.00   0.50    0.22    --   80.10-125.00-180.00   50
 52  \w     44.00  70.00   0.50    0.22    --   80.10-125.00-180.00   52
 53  \w     98.00 124.00   0.50    0.22    --   80.10 125.00-150.00   52
 54  \w     87.00 112.00   0.50    0.22    --   80.10 125.00 -60.00   50
 55  \w     84.00 109.00   0.50    0.22    --   80.10-125.00-120.00   50
 56  \w     78.00 107.00   0.50    0.22    --   80.10-125.00  60.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1007120000
_diffrn_orient_matrix_UB_12      0.0770954000
_diffrn_orient_matrix_UB_13      0.0183612000
_diffrn_orient_matrix_UB_21      0.0988951000
_diffrn_orient_matrix_UB_22      -0.0716752000
_diffrn_orient_matrix_UB_23      -0.0268666000
_diffrn_orient_matrix_UB_31      -0.0250851000
_diffrn_orient_matrix_UB_32      0.0265599000
_diffrn_orient_matrix_UB_33      -0.1262705000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0243
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13765
_diffrn_reflns_point_group_measured_fraction_full 0.843
_diffrn_reflns_point_group_measured_fraction_max 0.843
_diffrn_reflns_theta_full        67.060
_diffrn_reflns_theta_max         67.060
_diffrn_reflns_theta_min         4.871
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.628
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92096
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
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    1.198
_exptl_crystal_description       plate
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.137
_refine_diff_density_min         -0.153
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 1051 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(11)
_refine_ls_extinction_coef       0.0017(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     225
_refine_ls_number_reflns         2734
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0265
_refine_ls_R_factor_gt           0.0259
_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^)+(0.0426P)^2^+0.3553P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0686
_refine_ls_wR_factor_ref         0.0690
_reflns_Friedel_coverage         0.682
_reflns_Friedel_fraction_full    0.686
_reflns_Friedel_fraction_max     0.686
_reflns_number_gt                2674
_reflns_number_total             2734
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00516c2.cif
_cod_data_source_block           230307lt_auto
_cod_depositor_comments          'Adding full bibliography for 7160083.cif.'
_cod_database_code               7160083
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.906
_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:
 C14(H14A,H14B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C12(H12)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              31685
_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 1.156
_oxdiff_exptl_absorpt_empirical_full_min 0.802