Solvent- and temperature-controlled diastereodivergent [4+2] cyclization of p-QMs and 4-benzylidene-pyrazolones
Xiang, Min; Lu, Lin-Mu; Feng, Guang-Yuan; Zhu, Shen-Xin; Luo, Si-Si; Wang, Guang-Wei; Jia, Yun-Qing; Shen, Li-Wen; New Journal of Chemistry 49 (2025) 7293–7296; doi:10.1039/D5NJ00814J

data_7063736
_publ_section_title
;
 Solvent- and temperature-controlled diastereodivergent [4+2] cyclization
 of p-QMs and 4-benzylidene-pyrazolones
;
_journal_issue                   18
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              7293
_journal_page_last               7296
_journal_paper_doi               10.1039/D5NJ00814J
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C38 H40 N2 O3'
_chemical_formula_sum            'C38 H40 N2 O3'
_chemical_formula_weight         572.72
_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     direct
_audit_creation_date             2024-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-01-24 deposited with the CCDC.	2025-04-03 downloaded from the CCDC.
;
_cell_angle_alpha                116.752(4)
_cell_angle_beta                 93.454(4)
_cell_angle_gamma                108.491(4)
_cell_formula_units_Z            2
_cell_length_a                   12.1444(5)
_cell_length_b                   12.4946(5)
_cell_length_c                   12.6801(6)
_cell_measurement_reflns_used    9709
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8760
_cell_measurement_theta_min      3.9510
_cell_volume                     1581.91(15)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     -9.00  29.00   1.00    1.00    --    0.00 -77.00 -30.00   38
  2  \w    -15.00  18.00   1.00    1.00    --    0.00 -77.00-150.00   33
  3  \w    -20.00  33.00   1.00    1.25    --  -33.50  37.00 150.00   53
  4  \w   -101.00 -73.00   1.00    1.25    --  -33.50 -57.00 150.00   28
  5  \w    -95.00 -51.00   1.00    1.25    --  -33.50 -57.00 -30.00   44
  6  \w    -56.00 -30.00   1.00    1.25    --  -33.50  37.00 150.00   26
  7  \w    -46.00 -15.00   1.00    1.25    --  -33.50 -57.00 -30.00   31
  8  \w    -55.00 -15.00   1.00    1.25    --  -33.50 -57.00 150.00   40
  9  \w     -2.00  23.00   1.00    1.25    --   36.47  95.00  29.70   25
 10  \w      1.00  71.00   1.00    1.25    --   36.47 -99.00 -60.00   70
 11  \w     10.00  60.00   1.00    1.25    --   36.47 -99.00-150.00   50
 12  \w     61.00 109.00   1.00    1.25    --   36.47 178.00  90.00   48
 13  \w      6.00  31.00   1.00    1.25    --   36.47  80.00-128.58   25
 14  \w     34.00  73.00   1.00    1.25    --   36.47 -99.00 120.00   39
 15  \w     63.00 106.00   1.00    1.25    --   36.47 178.00-180.00   43
 16  \w     -1.00  24.00   1.00    1.25    --   36.47  93.00 141.38   25
 17  \w      9.00  34.00   1.00    1.25    --   44.00  88.00-115.71   25
 18  \w      9.00  34.00   1.00    1.25    --   44.00  88.00  72.83   25
 19  \w     17.00  42.00   1.00    1.25    --   48.00  82.00  82.01   25
 20  \w     17.00  42.00   1.00    1.25    --   48.00  81.00 159.70   25
 21  \w     16.00  41.00   1.00    1.25    --   48.00  84.00  -5.69   25
 22  \w     17.00  43.00   1.00    1.25    --   48.00  82.00 -74.87   26
 23  \w     17.00  42.00   1.00    1.25    --   48.00  81.00-122.08   25
 24  \w     34.00  60.00   1.00    1.25    --   52.00  71.00 101.72   26
 25  \w     30.00  61.00   1.00    1.25    --   52.00  71.00 163.96   31
 26  \w     26.00  51.00   1.00    1.25    --   52.00  72.00 -35.89   25
 27  \w     94.00 120.00   1.00    1.25    --   52.00  71.00 163.96   26
 28  \w     77.00 103.00   1.00    1.25    --   52.00  71.00 101.72   26
 29  \w     85.00 124.00   1.00    1.25    --   56.00  73.00 -14.99   39
 30  \w     98.00 124.00   1.00    1.25    --   56.00  70.00-164.25   26
 31  \w     32.00  69.00   1.00    1.25    --   56.00  70.00-164.25   37
 32  \w     33.00  59.00   1.00    1.25    --   56.00  73.00 -14.99   26
 33  \w     36.00  62.00   1.00    1.25    --   60.00  68.00  13.59   26
 34  \w     90.00 128.00   1.00    1.25    --   60.00  70.00  42.46   38
 35  \w     37.00  82.00   1.00    1.25    --   60.00  70.00  42.46   45
 36  \w     36.00 127.00   1.00    1.25    --   60.00  69.00-109.83   91
 37  \w    101.00 128.00   1.00    1.25    --   60.00  73.00 119.51   27
 38  \w     34.00  81.00   1.00    1.25    --   60.00  73.00 119.51   47
 39  \w     82.00 109.00   1.00    1.25    --   60.00  47.00 -30.04   27
 40  \w    101.00 127.00   1.00    1.25    --   60.00  68.00  13.59   26
 41  \w     40.00  72.00   1.00    1.25    --   60.00  47.00 -30.04   32
 42  \w    115.00 141.00   1.00    6.00    --   76.00  58.00 177.76   26
 43  \w     58.00  95.00   1.00    6.00    --   76.00  58.00 177.76   37
 44  \w    135.00 165.00   1.00    6.00    --   96.00  53.00 138.00   30
 45  \w     77.00 111.00   1.00    6.00    --   96.00  53.00 138.00   34
 46  \w    136.00 173.00   1.00    6.00    --  108.00  61.00  90.00   37
 47  \w    135.00 167.00   1.00    6.00    --  108.00  61.00-150.00   32
 48  \w     88.00 116.00   1.00    6.00    --  108.00  61.00  90.00   28
 49  \w     88.00 114.00   1.00    6.00    --  108.00  61.00-150.00   26
 50  \w    131.00 176.00   1.00    6.00    --  108.00  61.00 -90.00   45
 51  \w     41.00 109.00   1.00    6.00    --  108.00-111.00  30.00   68
 52  \w     88.00 117.00   1.00    6.00    --  108.00  61.00 -90.00   29
 53  \w    135.00 175.00   1.00    6.00    --  108.00 111.00 150.00   40
 54  \w     90.00 119.00   1.00    6.00    --  108.00  45.00 -60.00   29
 55  \w    125.00 176.00   1.00    6.00    --  108.00  61.00-180.00   51
 56  \w    130.00 176.00   1.00    6.00    --  108.00  61.00  60.00   46
 57  \w     88.00 121.00   1.00    6.00    --  108.00  61.00-180.00   33
 58  \w     88.00 123.00   1.00    6.00    --  108.00  61.00  60.00   35
 59  \w    131.00 176.00   1.00    6.00    --  108.00  61.00 -60.00   45
 60  \w     89.00 117.00   1.00    6.00    --  108.00  45.00  90.00   28
 61  \w     88.00 123.00   1.00    6.00    --  108.00  61.00 150.00   35
 62  \w    138.00 166.00   1.00    6.00    --  108.00  61.00 150.00   28
 63  \w     88.00 119.00   1.00    6.00    --  108.00  61.00 -60.00   31
 64  \w    105.00 137.00   1.00    6.00    --  108.00 -77.00  60.00   32
 65  \w    134.00 174.00   1.00    6.00    --  108.00  61.00-120.00   40
 66  \w     88.00 126.00   1.00    6.00    --  108.00  61.00-120.00   38
 67  \w     40.00  85.00   1.00    6.00    --  108.00 -77.00  60.00   45
 68  \w     89.00 120.00   1.00    6.00    --  108.00  45.00  60.00   31
 69  \w     38.00 101.00   1.00    6.00    --  108.00 -94.00 -90.00   63
 70  \w     46.00 109.00   1.00    6.00    --  108.00-111.00 150.00   63
 71  \w     90.00 116.00   1.00    6.00    --  108.00  45.00-150.00   26
 72  \w     43.00  69.00   1.00    6.00    --  108.00 -94.00 -30.00   26
 73  \w     92.00 118.00   1.00    6.00    --  108.00  45.00   0.00   26
 74  \w    133.00 171.00   1.00    6.00    --  108.00  61.00   0.00   38
 75  \w     91.00 121.00   1.00    6.00    --  108.00  45.00  30.00   30
 76  \w     88.00 119.00   1.00    6.00    --  108.00  61.00   0.00   31
 77  \w     91.00 118.00   1.00    6.00    --  108.00  45.00 -30.00   27
 78  \w    133.00 178.00   1.00    6.00    --  108.00  45.00 120.00   45
 79  \w     88.00 127.00   1.00    6.00    --  108.00  45.00 120.00   39
 80  \w     89.00 117.00   1.00    6.00    --  108.00  45.00 -90.00   28
 81  \w     88.00 122.00   1.00    6.00    --  108.00  45.00-120.00   34
 82  \w     90.00 125.00   1.00    6.00    --  108.00  45.00-180.00   35
 83  \w     45.00 109.00   1.00    6.00    --  108.00-111.00-120.00   64
 84  \w    134.00 167.00   1.00    6.00    --  108.00  61.00  30.00   33
 85  \w     88.00 119.00   1.00    6.00    --  108.00  61.00  30.00   31
 86  \w     88.00 171.00   1.00    6.00    --  108.00  61.00 -30.00   83
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0355071000
_diffrn_orient_matrix_UB_12      -0.1435283000
_diffrn_orient_matrix_UB_13      -0.0968668000
_diffrn_orient_matrix_UB_21      -0.1278130000
_diffrn_orient_matrix_UB_22      -0.0309408000
_diffrn_orient_matrix_UB_23      0.0196301000
_diffrn_orient_matrix_UB_31      -0.0372179000
_diffrn_orient_matrix_UB_32      0.0291600000
_diffrn_orient_matrix_UB_33      -0.0993565000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            21981
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.066
_diffrn_reflns_theta_max         67.066
_diffrn_reflns_theta_min         3.953
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.594
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92597
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
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    1.202
_exptl_crystal_description       block
_exptl_crystal_F_000             612
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.353
_refine_diff_density_min         -0.429
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     395
_refine_ls_number_reflns         5642
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0631
_refine_ls_R_factor_gt           0.0540
_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^)+(0.1004P)^2^+0.1926P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1498
_refine_ls_wR_factor_ref         0.1614
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4673
_reflns_number_total             5642
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00814j2.cif
_cod_data_source_block           202407271a
_cod_depositor_comments
'Adding full bibliography for 7063735--7063737.cif.'
_cod_original_cell_volume        1581.92(13)
_cod_database_code               7063736
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H2N2O4
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.895
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups
2.a Riding coordinates:
 O1(H1)
2.b Ternary CH refined with riding coordinates:
 C21(H21), C23(H23)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C15(H15), C16(H16), C17(H17), C18(H18), C25(H25), C26(H26),
 C27(H27), C28(H28), C29(H29), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              92359
_shelx_hkl_checksum              24936
_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 1.334
_oxdiff_exptl_absorpt_empirical_full_min 0.892