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_7063735
_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      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-07-10
_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                90
_cell_angle_beta                 90.2665(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.24120(14)
_cell_length_b                   15.3376(2)
_cell_length_c                   20.8758(3)
_cell_measurement_reflns_used    13670
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7130
_cell_measurement_theta_min      4.2320
_cell_volume                     3279.04(8)
_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 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    -39.00  35.00   1.00    2.25    --  -33.50  57.00 150.00   74
  2  \w    -38.00 -12.00   1.00    2.25    --  -33.50  57.00  30.00   26
  3  \w    -72.00 -15.00   1.00    2.25    --  -33.50 -57.00   0.00   57
  4  \w     71.00 104.00   1.00    2.25    --   36.47  57.00  30.00   33
  5  \w     19.00  45.00   1.00    2.25    --   36.47  57.00  30.00   26
  6  \w      0.00  25.00   1.00    2.25    --   36.47  92.00 147.43   25
  7  \w     59.00  99.00   1.00    2.25    --   36.47  57.00-150.00   40
  8  \w     78.00 106.00   1.00    2.25    --   36.47  37.00-120.00   28
  9  \w     -1.00  24.00   1.00    2.25    --   36.47  93.00   0.75   25
 10  \w    -31.00  25.00   1.00    2.25    --   36.47 -57.00  90.00   56
 11  \w      9.00  34.00   1.00    2.25    --   36.47  77.00-152.47   25
 12  \w     63.00  94.00   1.00    2.25    --   36.47  37.00 -90.00   31
 13  \w     45.00 103.00   1.00    2.25    --   36.47  57.00-180.00   58
 14  \w      4.00  29.00   1.00    2.25    --   36.47  85.00-105.95   25
 15  \w     13.00  39.00   1.00    2.25    --   36.47  79.00 -28.46   26
 16  \w     67.00  95.00   1.00    2.25    --   36.47 178.00  30.00   28
 17  \w    -15.00  21.00   1.00    2.25    --   36.47 -57.00 -90.00   36
 18  \w      0.00  25.00   1.00    2.25    --   36.47  92.00 -73.26   25
 19  \w     20.00  67.00   1.00    2.25    --   36.47 -99.00  90.00   47
 20  \w     62.00 108.00   1.00    2.25    --   36.47 178.00 -60.00   46
 21  \w     25.00  52.00   1.00    2.25    --   36.47  57.00-150.00   27
 22  \w      5.00  34.00   1.00    2.25    --   36.47  86.00  21.38   29
 23  \w      9.00  34.00   1.00    2.25    --   36.47  75.00-110.00   25
 24  \w     73.00 102.00   1.00    2.25    --   36.47 178.00 -30.00   29
 25  \w     10.00  65.00   1.00    2.25    --   36.47 -77.00 -30.00   55
 26  \w     11.00  37.00   1.00    2.25    --   36.47  77.00-167.65   26
 27  \w     44.00  85.00   1.00   12.00    --  108.00 -94.00 -60.00   41
 28  \w    127.00 176.00   1.00   12.00    --  108.00  61.00-150.00   49
 29  \w     88.00 114.00   1.00   12.00    --  108.00  45.00 -60.00   26
 30  \w     88.00 114.00   1.00   12.00    --  108.00  61.00 -60.00   26
 31  \w     88.00 122.00   1.00   12.00    --  108.00  61.00-150.00   34
 32  \w     88.00 113.00   1.00   12.00    --  108.00  61.00-120.00   25
 33  \w    122.00 148.00   1.00   12.00    --  108.00  45.00-150.00   26
 34  \w    140.00 176.00   1.00   12.00    --  108.00  45.00-180.00   36
 35  \w     88.00 116.00   1.00   12.00    --  108.00  45.00-150.00   28
 36  \w     89.00 139.00   1.00   12.00    --  108.00  45.00-120.00   50
 37  \w    143.00 172.00   1.00   12.00    --  108.00  61.00  60.00   29
 38  \w    152.00 178.00   1.00   12.00    --  108.00  45.00 -30.00   26
 39  \w    126.00 175.00   1.00   12.00    --  108.00  77.00 -90.00   49
 40  \w     41.00 108.00   1.00   12.00    --  108.00-111.00   0.00   67
 41  \w     72.00  98.00   1.00   12.00    --  108.00 -94.00-180.00   26
 42  \w     83.00 117.00   1.00   12.00    --  108.00  30.00 -90.00   34
 43  \w     84.00 110.00   1.00   12.00    --  108.00  30.00-120.00   26
 44  \w     38.00  64.00   1.00   12.00    --  108.00 -94.00-180.00   26
 45  \w    133.00 160.00   1.00   12.00    --  108.00 111.00 150.00   27
 46  \w     82.00 122.00   1.00   12.00    --  108.00  30.00 -30.00   40
 47  \w     89.00 131.00   1.00   12.00    --  108.00  45.00 -30.00   42
 48  \w     88.00 123.00   1.00   12.00    --  108.00  61.00 -30.00   35
 49  \w     63.00  89.00   1.00   12.00    --  108.00 178.00-150.00   26
 50  \w     88.00 129.00   1.00   12.00    --  108.00  45.00-180.00   41
 51  \w     62.00 128.00   1.00   12.00    --  108.00 -61.00  60.00   66
 52  \w     67.00 108.00   1.00   12.00    --  108.00-111.00  30.00   41
 53  \w     41.00  66.00   1.00   12.00    --  108.00 -61.00 -30.00   25
 54  \w     78.00 120.00   1.00   12.00    --  108.00 -61.00 -30.00   42
 55  \w     78.00 105.00   1.00   12.00    --  108.00 -94.00  30.00   27
 56  \w     88.00 113.00   1.00   12.00    --  108.00  61.00 -90.00   25
 57  \w    139.00 177.00   1.00   12.00    --  108.00  45.00 -90.00   38
 58  \w    133.00 159.00   1.00   12.00    --  108.00  30.00 -60.00   26
 59  \w     38.00  79.00   1.00   12.00    --  108.00 -94.00-150.00   41
 60  \w     74.00  99.00   1.00   12.00    --  108.00 178.00 -90.00   25
 61  \w    118.00 144.00   1.00   12.00    --  108.00 178.00 -90.00   26
 62  \w     88.00 117.00   1.00   12.00    --  108.00  45.00 -90.00   29
 63  \w     66.00  94.00   1.00   12.00    --  108.00  15.00 -90.00   28
 64  \w     82.00 115.00   1.00   12.00    --  108.00  30.00 -60.00   33
 65  \w    131.00 176.00   1.00   12.00    --  108.00  61.00-120.00   45
 66  \w     46.00 101.00   1.00   12.00    --  108.00-111.00 120.00   55
 67  \w    147.00 173.00   1.00   12.00    --  108.00  77.00-180.00   26
 68  \w     88.00 114.00   1.00   12.00    --  108.00  30.00   0.00   26
 69  \w    127.00 176.00   1.00   12.00    --  108.00  30.00   0.00   49
;
_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      0.0528125000
_diffrn_orient_matrix_UB_12      0.0019809000
_diffrn_orient_matrix_UB_13      -0.0689849000
_diffrn_orient_matrix_UB_21      -0.1161526000
_diffrn_orient_matrix_UB_22      -0.0562171000
_diffrn_orient_matrix_UB_23      -0.0224801000
_diffrn_orient_matrix_UB_31      -0.0796508000
_diffrn_orient_matrix_UB_32      0.0831991000
_diffrn_orient_matrix_UB_33      -0.0135707000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0387
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            33751
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.065
_diffrn_reflns_theta_max         67.065
_diffrn_reflns_theta_min         3.576
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.573
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84915
_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    1.160
_exptl_crystal_description       block
_exptl_crystal_F_000             1224
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.273
_refine_diff_density_min         -0.260
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     393
_refine_ls_number_reflns         5848
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0966P)^2^+0.5699P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1462
_refine_ls_wR_factor_ref         0.1560
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4925
_reflns_number_total             5848
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00814j2.cif
_cod_data_source_block           202407259_auto
_cod_depositor_comments
'Adding full bibliography for 7063735--7063737.cif.'
_cod_database_code               7063735
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H2N2O4S1
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.904
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
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:
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              14329
_shelx_hkl_checksum              68609
_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 1.217
_oxdiff_exptl_absorpt_empirical_full_min 0.868