UV-assisted rearrangement of substituted 3-arylaminopyrazoles with an allomaltol fragment into tricyclic cyclopenta[4,5]pyrrolo[2,3-<i>c</i>]pyrazole derivatives.
Komogortsev, Andrey N.; Milyutin, Constantine V.; Lichitsky, Boris V.; Migulin, Vasily A.; Organic & biomolecular chemistry 23 (2025) 6738–6744; doi:10.1039/d5ob00796h

data_7160617
_publ_section_title
;
 UV-assisted rearrangement of substituted 3-arylaminopyrazoles with an
 allomaltol fragment into tricyclic
 cyclopenta[4,5]pyrrolo[2,3-<i>c</i>]pyrazole derivatives.
;
_journal_issue                   28
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6738
_journal_page_last               6744
_journal_paper_doi               10.1039/d5ob00796h
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C21 H16 F N3 O3'
_chemical_formula_sum            'C21 H16 F N3 O3'
_chemical_formula_weight         377.37
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-03-27
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2025-05-04 deposited with the CCDC.	2025-06-24 downloaded from the CCDC.
;
_cell_angle_alpha                63.9662(18)
_cell_angle_beta                 89.9415(12)
_cell_angle_gamma                81.1842(13)
_cell_formula_units_Z            4
_cell_length_a                   9.28605(11)
_cell_length_b                   14.2749(3)
_cell_length_c                   14.7953(3)
_cell_measurement_reflns_used    25197
_cell_measurement_temperature    99.97(15)
_cell_measurement_theta_max      79.9380
_cell_measurement_theta_min      4.8180
_cell_volume                     1736.56(6)
_computing_cell_refinement       'CrysAlisPro 1.171.44.99a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.99a 64-bit (release 17-03-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.99a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(15)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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    -82.00  -2.00   0.50    1.20    --  -40.70 111.00 -21.00  160
  2  \w     24.00  88.00   0.50    1.20    --   40.70-111.00-114.00  128
  3  \w    -82.00 -23.00   0.50    4.80    --  -98.00 111.00 -21.00  118
  4  \w   -173.00 -81.00   0.50    4.80    --  -98.00-111.00-114.00  184
  5  \w    103.00 178.00   0.50    4.80    --  119.50 111.00 -21.00  150
  6  \w     44.00 108.00   0.50    4.80    --  119.50-111.00-114.00  128
  7  \w   -115.00 -15.00   0.50    1.20    --  -40.70 -57.00-150.00  200
  8  \w    -43.00  39.00   0.50    1.20    --  -40.70  38.00  90.00  164
  9  \w    -43.00  39.00   0.50    1.20    --  -40.70  38.00-150.00  164
 10  \w    -27.00  42.00   0.50    1.20    --  -40.70  19.00   0.00  138
 11  \w   -115.00 -15.00   0.50    1.20    --  -40.70 -57.00-150.00  200
 12  \w    -43.00  39.00   0.50    1.20    --  -40.70  38.00 150.00  164
 13  \w    -43.00  39.00   0.50    1.20    --  -40.70  38.00 150.00  164
 14  \w     63.00 123.00   0.50    1.20    --   40.70 178.00   0.00  120
 15  \w     61.00 123.00   0.50    1.20    --   40.70-178.00  60.00  124
 16  \w   -172.00 -69.00   0.50    4.80    --  -98.00 -67.00 -38.30  206
 17  \w   -172.00 -69.00   0.50    4.80    --  -98.00 -67.00 -38.30  206
 18  \w    -71.00 -23.00   0.50    4.80    --  -98.00  61.00-180.00   96
 19  \w    -71.00 -23.00   0.50    4.80    --  -98.00  61.00  90.00   96
 20  \w    -51.00 -20.00   0.50    4.80    --  -98.00  45.00 -60.00   62
 21  \w    -82.00 -23.00   0.50    4.80    --  -98.00 111.00 -21.00  118
 22  \w     93.00 178.00   0.50    4.80    --  119.50  61.00  60.00  170
 23  \w     61.00 151.00   0.50    4.80    --  119.50-178.00  90.00  180
 24  \w     44.00 108.00   0.50    4.80    --  119.50-111.00 -30.00  128
 25  \w     41.00 105.00   0.50    4.80    --  119.50 -95.00   0.00  128
 26  \w     93.00 178.00   0.50    4.80    --  119.50  45.00-180.00  170
 27  \w     46.00 105.00   0.50    4.80    --  119.50 -77.00-180.00  118
 28  \w    103.00 178.00   0.50    4.80    --  119.50 111.00 -60.00  150
 29  \w     41.00 105.00   0.50    4.80    --  119.50 -95.00-150.00  128
 30  \w     93.00 178.00   0.50    4.80    --  119.50  61.00 -60.00  170
 31  \w     93.00 178.00   0.50    4.80    --  119.50  61.00-120.00  170
 32  \w     93.00 178.00   0.50    4.80    --  119.50  61.00-120.00  170
 33  \w     45.00 155.00   0.50    4.80    --  119.50 -83.00 123.86  220
 34  \w     93.00 178.00   0.50    4.80    --  119.50  45.00 150.00  170
 35  \w     93.00 178.00   0.50    4.80    --  119.50  45.00 150.00  170
 36  \w     41.00 105.00   0.50    4.80    --  119.50 -95.00 120.00  128
 37  \w     93.00 178.00   0.50    4.80    --  119.50  61.00 120.00  170
 38  \w     41.00 105.00   0.50    4.80    --  119.50 -95.00  60.00  128
 39  \w     93.00 178.00   0.50    4.80    --  119.50  61.00   0.00  170
 40  \w     44.00 108.00   0.50    4.80    --  119.50-111.00 120.00  128
 41  \w     41.00 105.00   0.50    4.80    --  119.50 -95.00  30.00  128
 42  \w     87.00 178.00   0.50    4.80    --  119.50  30.00 120.00  182
 43  \w     46.00 105.00   0.50    4.80    --  119.50 -77.00  30.00  118
 44  \w     45.00 155.00   0.50    4.80    --  119.50 -83.00 -37.97  220
 45  \w    103.00 178.00   0.50    4.80    --  119.50 111.00 -30.00  150
 46  \w     42.00 178.00   0.50    4.80    --  119.50  15.00 -60.00  272
 47  \w     44.00 108.00   0.50    4.80    --  119.50-111.00  30.00  128
 48  \w     41.00 105.00   0.50    4.80    --  119.50 -95.00  60.00  128
 49  \w     46.00 105.00   0.50    4.80    --  119.50 -77.00 120.00  118
 50  \w     93.00 178.00   0.50    4.80    --  119.50  61.00 120.00  170
 51  \w     44.00 108.00   0.50    4.80    --  119.50-111.00 -90.00  128
 52  \w     93.00 178.00   0.50    4.80    --  119.50  45.00-180.00  170
 53  \w     46.00 105.00   0.50    4.80    --  119.50 -77.00 -90.00  118
 54  \w     93.00 178.00   0.50    4.80    --  119.50  45.00  90.00  170
 55  \w     87.00 178.00   0.50    4.80    --  119.50  77.00-150.00  182
 56  \w     63.00 146.00   0.50    4.80    --  119.50 178.00  60.00  166
 57  \w     63.00 146.00   0.50    4.80    --  119.50 178.00  60.00  166
 58  \w     63.00 146.00   0.50    4.80    --  119.50 178.00 120.00  166
 59  \w     93.00 178.00   0.50    4.80    --  119.50  45.00 -30.00  170
 60  \w     61.00 151.00   0.50    4.80    --  119.50-178.00  30.00  180
 61  \w     87.00 178.00   0.50    4.80    --  119.50  30.00 120.00  182
 62  \w    103.00 178.00   0.50    4.80    --  119.50 111.00 120.00  150
 63  \w    103.00 178.00   0.50    4.80    --  119.50 111.00 150.00  150
 64  \w     61.00 151.00   0.50    4.80    --  119.50-178.00-120.00  180
 65  \w     61.00 151.00   0.50    4.80    --  119.50-178.00 -90.00  180
 66  \w     61.00 151.00   0.50    4.80    --  119.50-178.00   0.00  180
 67  \w     96.00 148.00   0.50    4.80    --  119.50-178.00   0.00  104
 68  \w     58.00  84.00   0.50    4.80    --  119.50 -95.00-180.00   52
 69  \w     96.00 157.00   0.50    4.80    --  119.50  61.00 -30.00  122
 70  \w     50.00  76.00   0.50    4.80    --  119.50-111.00-120.00   52
 71  \w     79.00 106.00   0.50    4.80    --  119.50-111.00-150.00   54
 72  \w     90.00 157.00   0.50    4.80    --  119.50  30.00 -60.00  134
 73  \w     45.00  75.00   0.50    4.80    --  119.50-111.00  90.00   60
 74  \w     80.00 106.00   0.50    4.80    --  119.50-111.00  90.00   52
 75  \w     46.00  80.00   0.50    4.80    --  119.50 -77.00 -30.00   68
 76  \w     96.00 123.00   0.50    4.80    --  119.50  61.00  90.00   54
 77  \w     47.00  79.00   0.50    4.80    --  119.50 -77.00-120.00   64
 78  \w    107.00 153.00   0.50    4.80    --  119.50 111.00-180.00   92
 79  \w    103.00 129.00   0.50    4.80    --  119.50-178.00 120.00   52
 80  \w     95.00 130.00   0.50    4.80    --  119.50  77.00  90.00   70
 81  \w     87.00 178.00   0.50    4.80    --  119.50  30.00-150.00  182
 82  \w    121.00 148.00   0.50    4.80    --  119.50 -80.00 -41.72   54
 83  \w    117.00 143.00   0.50    4.80    --  119.50 -85.00 -34.82   52
 84  \w     60.00  86.00   0.50    4.80    --  119.50 -84.00 111.67   52
 85  \w    116.00 150.00   0.50    4.80    --  119.50 -84.00 111.67   68
 86  \w    102.00 128.00   0.50    4.80    --  119.50  15.00 -60.00   52
 87  \w     69.00 108.00   0.50    4.80    --  119.50-111.00-180.00   78
 88  \w     81.00 107.00   0.50    4.80    --  119.50-111.00 -60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0153087000
_diffrn_orient_matrix_UB_12      0.0792264000
_diffrn_orient_matrix_UB_13      0.0426500000
_diffrn_orient_matrix_UB_21      0.0287989000
_diffrn_orient_matrix_UB_22      0.0821424000
_diffrn_orient_matrix_UB_23      -0.1055590000
_diffrn_orient_matrix_UB_31      -0.1651638000
_diffrn_orient_matrix_UB_32      0.0427947000
_diffrn_orient_matrix_UB_33      -0.0232900000
_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  0.0680
_diffrn_reflns_av_unetI/netI     0.0123
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            13773
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.035
_diffrn_reflns_theta_min         3.334
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.882
_exptl_absorpt_correction_T_max  0.973
_exptl_absorpt_correction_T_min  0.772
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.99a (Rigaku Oxford Diffraction, 2025)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.53
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.334
_refine_diff_density_min         -0.301
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     532
_refine_ls_number_reflns         13773
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0487
_refine_ls_R_factor_gt           0.0460
_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^)+(0.0930P)^2^+0.2767P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1304
_refine_ls_wR_factor_ref         0.1333
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12677
_reflns_number_total             13773
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9844\% 
around [0.97 0.23 -0.00] (reciprocal) or [1.00 0.00 -0.00] (direct)
;
_cod_data_source_file            d5ob00796h2.cif
_cod_data_source_block           VM-AK-THF-EtOH
_cod_depositor_comments
'Adding full bibliography for 7160617--7160618.cif.'
_cod_original_cell_volume        1736.55(6)
_cod_database_code               7160617
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C19H20N3O3F1
_chemical_oxdiff_usercomment     VM-AK-THF-EtOH
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.652
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6839(8)
 0.3161(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C7A(H7A), C13A(H13A), C14A(H14A), C16A(H16A), C17A(H17A), C20A(H20A),
 C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C7B(H7B), C13B(H13B),
 C14B(H14B), C16B(H16B), C17B(H17B), C20B(H20B), C21B(H21B), C22B(H22B),
 C23B(H23B), C24B(H24B)
3.b Idealised Me refined as rotating group:
 C18A(H18A,H18B,H18C), C18B(H18D,H18E,H18F)
;
_shelx_res_checksum              60475
_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 1.424
_oxdiff_exptl_absorpt_empirical_full_min 0.510
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2