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_7160618
_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         'C22 H18 F N3 O4, C2 H6 O S'
_chemical_formula_sum            'C24 H24 F N3 O5 S'
_chemical_formula_weight         485.52
_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             2025-01-30
_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                95.717(2)
_cell_angle_beta                 91.608(2)
_cell_angle_gamma                110.539(3)
_cell_formula_units_Z            2
_cell_length_a                   10.4253(3)
_cell_length_b                   10.7006(3)
_cell_length_c                   11.1367(3)
_cell_measurement_reflns_used    16770
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      79.3630
_cell_measurement_theta_min      3.9700
_cell_volume                     1154.97(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_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)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.984
_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   -121.00 -32.00   0.50    0.25    --  -46.47 -27.00  30.00  178
  2  \w     32.00 121.00   0.50    0.25    --   46.47  27.00-167.00  178
  3  \w     32.00 121.00   0.50    0.25    --   46.47  27.00-167.00  178
  4  \w    -28.00  33.00   0.50    0.25    --   46.47 -27.00  30.00  122
  5  \w   -167.00 -77.00   0.50    1.00    --  -91.75 -27.00  30.00  180
  6  \w     99.00 178.00   0.50    1.00    --  113.25  27.00-167.00  158
  7  \w    -33.00  29.00   0.50    0.25    --  -46.47  27.00-167.00  124
  8  \w    -29.00  27.00   0.50    0.25    --   46.47 -19.00-120.00  112
  9  \w     34.00  93.00   0.50    0.25    --   46.47-125.00  60.00  118
 10  \w    -29.00  27.00   0.50    0.25    --   46.47 -19.00 -60.00  112
 11  \w    -25.00  63.00   0.50    0.25    --   46.47 -57.00-180.00  176
 12  \w    -71.00 -19.00   0.50    1.00    --  -91.75  61.00-180.00  104
 13  \w    -85.00 -22.00   0.50    1.00    --  -91.75 125.00-120.00  126
 14  \w    -51.00 -19.00   0.50    1.00    --  -91.75  45.00   0.00   64
 15  \w    -51.00 -19.00   0.50    1.00    --  -91.75  45.00-180.00   64
 16  \w     43.00 111.00   0.50    1.00    --  113.25-125.00   0.00  136
 17  \w     96.00 178.00   0.50    1.00    --  113.25  15.00 -30.00  164
 18  \w     41.00 106.00   0.50    1.00    --  113.25 -95.00  60.00  130
 19  \w     96.00 178.00   0.50    1.00    --  113.25  15.00-120.00  164
 20  \w     95.00 178.00   0.50    1.00    --  113.25 125.00 150.00  166
 21  \w     96.00 178.00   0.50    1.00    --  113.25  15.00 120.00  164
 22  \w     41.00 106.00   0.50    1.00    --  113.25 -95.00 120.00  130
 23  \w    121.00 171.00   0.50    1.00    --  113.25  30.00  60.00  100
 24  \w     71.00 101.00   0.50    1.00    --  113.25 -95.00-150.00   60
 25  \w     43.00  69.00   0.50    1.00    --  113.25 -95.00-150.00   52
 26  \w     41.00  68.00   0.50    1.00    --  113.25 -61.00 -30.00   54
 27  \w     99.00 132.00   0.50    1.00    --  113.25  30.00  30.00   66
 28  \w     78.00 106.00   0.50    1.00    --  113.25 -95.00   0.00   56
 29  \w     78.00 111.00   0.50    1.00    --  113.25-125.00 -30.00   66
 30  \w    116.00 142.00   0.50    1.00    --  113.25  15.00 150.00   52
 31  \w    102.00 178.00   0.50    1.00    --  113.25  77.00 -30.00  152
 32  \w     43.00  75.00   0.50    1.00    --  113.25-125.00  30.00   64
 33  \w     79.00 111.00   0.50    1.00    --  113.25-125.00  30.00   64
 34  \w     95.00 173.00   0.50    1.00    --  113.25 125.00   0.00  156
 35  \w     81.00 106.00   0.50    1.00    --  113.25 -95.00-120.00   50
 36  \w     95.00 141.00   0.50    1.00    --  113.25 125.00  30.00   92
 37  \w     76.00 111.00   0.50    1.00    --  113.25-125.00  60.00   70
 38  \w     43.00  69.00   0.50    1.00    --  113.25 -61.00 120.00   52
 39  \w     41.00  95.00   0.50    1.00    --  113.25 -77.00 -60.00  108
 40  \w     84.00 111.00   0.50    1.00    --  113.25-125.00 -90.00   54
 41  \w     42.00  67.00   0.50    1.00    --  113.25 -61.00 -90.00   50
 42  \w     64.00 111.00   0.50    1.00    --  113.25-125.00 -60.00   94
 43  \w     85.00 111.00   0.50    1.00    --  113.25-125.00 150.00   52
 44  \w     96.00 157.00   0.50    1.00    --  113.25 125.00  90.00  122
 45  \w     55.00  80.00   0.50    1.00    --  113.25-125.00 -90.00   50
 46  \w     43.00  69.00   0.50    1.00    --  113.25 -61.00 150.00   52
 47  \w     42.00  67.00   0.50    1.00    --  113.25 -82.00  15.63   50
 48  \w     96.00 123.00   0.50    1.00    --  113.25 -82.00  15.63   54
 49  \w     75.00 101.00   0.50    1.00    --  113.25 -95.00 150.00   52
 50  \w    147.00 172.00   0.50    1.00    --  113.25  30.00  30.00   50
 51  \w     72.00 101.00   0.50    1.00    --  113.25 -95.00-180.00   58
 52  \w     48.00  81.00   0.50    1.00    --  113.25-125.00-150.00   66
 53  \w     86.00 111.00   0.50    1.00    --  113.25-125.00-150.00   50
 54  \w     49.00  75.00   0.50    1.00    --  113.25 -82.00-132.84   52
 55  \w     81.00 107.00   0.50    1.00    --  113.25 -82.00-132.84   52
 56  \w    144.00 178.00   0.50    1.00    --  113.25  30.00-180.00   68
 57  \w     41.00  74.00   0.50    1.00    --  113.25 -95.00 150.00   66
 58  \w     46.00  74.00   0.50    1.00    --  113.25 -77.00  90.00   56
 59  \w    105.00 163.00   0.50    1.00    --  113.25  45.00 150.00  116
 60  \w    131.00 177.00   0.50    1.00    --  113.25  45.00-120.00   92
 61  \w     48.00  79.00   0.50    1.00    --  113.25 -81.00-156.77   62
 62  \w     84.00 110.00   0.50    1.00    --  113.25 -81.00-156.77   52
 63  \w    138.00 178.00   0.50    1.00    --  113.25  45.00 120.00   80
 64  \w     45.00  71.00   0.50    1.00    --  113.25 -77.00 -90.00   52
 65  \w     82.00 108.00   0.50    1.00    --  113.25-125.00  90.00   52
 66  \w     85.00 111.00   0.50    1.00    --  113.25-125.00-180.00   52
 67  \w     63.00 111.00   0.50    1.00    --  113.25-125.00 120.00   96
 68  \w    110.00 136.00   0.50    1.00    --  113.25  45.00 -30.00   52
 69  \w     42.00  69.00   0.50    1.00    --  113.25 -61.00  60.00   54
 70  \w     41.00  71.00   0.50    1.00    --  113.25 -61.00  30.00   60
 71  \w    115.00 141.00   0.50    1.00    --  113.25  61.00 -90.00   52
 72  \w    103.00 129.00   0.50    1.00    --  113.25  61.00  30.00   52
 73  \w     97.00 124.00   0.50    1.00    --  113.25  61.00 120.00   54
 74  \w    135.00 175.00   0.50    1.00    --  113.25  15.00 -60.00   80
 75  \w    101.00 162.00   0.50    1.00    --  113.25 125.00-180.00  122
 76  \w    101.00 140.00   0.50    1.00    --  113.25  77.00-120.00   78
 77  \w     83.00 109.00   0.50    1.00    --  113.25 -82.00 -88.85   52
 78  \w     43.00  71.00   0.50    1.00    --  113.25-125.00  60.00   56
;
_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      0.1537846000
_diffrn_orient_matrix_UB_12      0.0229305000
_diffrn_orient_matrix_UB_13      0.0200144000
_diffrn_orient_matrix_UB_21      0.0369521000
_diffrn_orient_matrix_UB_22      0.1387475000
_diffrn_orient_matrix_UB_23      -0.0457953000
_diffrn_orient_matrix_UB_31      0.0008047000
_diffrn_orient_matrix_UB_32      0.0647132000
_diffrn_orient_matrix_UB_33      0.1300713000
_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  0.0308
_diffrn_reflns_av_unetI/netI     0.0232
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            25240
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.018
_diffrn_reflns_theta_min         3.998
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.676
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.349
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.396
_exptl_crystal_description       prism
_exptl_crystal_F_000             508
_exptl_crystal_size_max          0.63
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.331
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     323
_refine_ls_number_reflns         4966
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0373
_refine_ls_R_factor_gt           0.0360
_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^)+(0.0453P)^2^+0.5190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.0975
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4711
_reflns_number_total             4966
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00796h2.cif
_cod_data_source_block           780
_cod_depositor_comments
'Adding full bibliography for 7160617--7160618.cif.'
_cod_database_code               7160618
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C24H24FN3O5S
_chemical_oxdiff_usercomment     780
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.418
_reflns_odcompleteness_completeness 97.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.50
_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:
 C11(H11), C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22),
 C24(H24), C25(H25)
2.b Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C13(H13A,H13B,H13C), C26(H26A,H26B,
 H26C)
;
_shelx_res_checksum              53037
_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 1.531
_oxdiff_exptl_absorpt_empirical_full_min 0.863