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_7063737
_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             2024-09-03
_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                 106.7707(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.96514(19)
_cell_length_b                   10.31317(10)
_cell_length_c                   19.1239(2)
_cell_measurement_reflns_used    5886
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7680
_cell_measurement_theta_min      4.8260
_cell_volume                     3203.69(6)
_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    -43.00 -15.00   0.70    2.20    --  -33.50 -37.00  60.00   40
  2  \w   -104.00 -55.70   0.70    2.20    --  -33.50 -37.00  60.00   69
  3  \w    -97.00 -15.80   0.70    2.20    --  -33.50 -57.00 -30.00  116
  4  \w     78.00 104.60   0.70    2.20    --   36.47  19.00 -60.00   38
  5  \w      2.00  53.10   0.70    2.20    --   36.47  19.00 -60.00   73
  6  \w     70.00 109.20   0.70    2.20    --   36.47 178.00-120.00   56
  7  \w     53.00  95.70   0.70    2.20    --   36.47  19.00 120.00   61
  8  \w    -30.00   1.50   0.70    2.20    --   36.47 -37.00 -30.00   45
  9  \w     74.00 100.60   0.70    2.20    --   36.47 178.00-180.00   38
 10  \w     61.00 110.00   0.70    2.20    --   36.47 178.00  60.00   70
 11  \w     21.00  47.60   0.70    2.20    --   36.47 -37.00 -30.00   38
 12  \w     96.00 127.50   0.70   12.00    --  108.00 -61.00  30.00   45
 13  \w    104.00 174.00   0.70   12.00    --  108.00 111.00 -60.00  100
 14  \w    138.00 163.90   0.70   12.00    --  108.00  61.00-120.00   37
 15  \w     89.00 121.20   0.70   12.00    --  108.00  61.00-120.00   46
 16  \w     63.00 100.10   0.70   12.00    --  108.00-111.00 120.00   53
 17  \w    112.00 161.00   0.70   12.00    --  108.00  45.00 150.00   70
 18  \w    133.00 172.90   0.70   12.00    --  108.00  77.00 -30.00   57
 19  \w     44.00 127.30   0.70   12.00    --  108.00 -45.00-150.00  119
 20  \w     54.00 105.10   0.70   12.00    --  108.00 -94.00-150.00   73
 21  \w     59.00 104.50   0.70   12.00    --  108.00 -94.00 -60.00   65
 22  \w    101.00 176.60   0.70   12.00    --  108.00  77.00   0.00  108
;
_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      0.0441904000
_diffrn_orient_matrix_UB_12      0.0256337000
_diffrn_orient_matrix_UB_13      -0.0586178000
_diffrn_orient_matrix_UB_21      0.0819702000
_diffrn_orient_matrix_UB_22      -0.0446192000
_diffrn_orient_matrix_UB_23      0.0536370000
_diffrn_orient_matrix_UB_31      -0.0180118000
_diffrn_orient_matrix_UB_32      -0.1401822000
_diffrn_orient_matrix_UB_33      -0.0277677000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0268
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            12908
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.068
_diffrn_reflns_theta_max         67.068
_diffrn_reflns_theta_min         4.127
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.587
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94013
_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    1.187
_exptl_crystal_description       block
_exptl_crystal_F_000             1224
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.325
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     395
_refine_ls_number_reflns         5723
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0874P)^2^+0.3638P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1398
_refine_ls_wR_factor_ref         0.1511
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4638
_reflns_number_total             5723
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00814j2.cif
_cod_data_source_block           202409296_auto
_cod_depositor_comments
'Adding full bibliography for 7063735--7063737.cif.'
_cod_original_cell_volume        3203.68(7)
_cod_database_code               7063737
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C22H21N3O3
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.922
_reflns_odcompleteness_completeness 99.95
_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), C28(H28), C29(H29),
 C30(H30), C31(H31), C32(H32), 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), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              4754
_shelx_hkl_checksum              75049
_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 1.123
_oxdiff_exptl_absorpt_empirical_full_min 0.927