Stereoselective Assembly of Multifunctional Spirocyclohexene Pyrazolones That Induce Autophagy-Dependent Apoptosis in Colorectal Cancer Cells.
Li, Xiang; Chen, Fei-Yu; Kang, Jing-Wen; Zhou, Jin; Peng, Cheng; Huang, Wei; Zhou, Mu-Ke; He, Gu; Han, Bo; The Journal of organic chemistry 84 (2019) 9138–9150; doi:10.1021/acs.joc.9b01098

data_4034186
_publ_section_title
;
 Stereoselective Assembly of Multifunctional Spirocyclohexene Pyrazolones
 That Induce Autophagy-Dependent Apoptosis in Colorectal Cancer Cells.
;
_journal_issue                   14
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9138
_journal_page_last               9150
_journal_paper_doi               10.1021/acs.joc.9b01098
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H36 N2 O4 Si'
_chemical_formula_sum            'C29 H36 N2 O4 Si'
_chemical_formula_weight         504.69
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.96693(9)
_cell_length_b                   16.8380(2)
_cell_length_c                   18.4036(3)
_cell_measurement_reflns_used    5575
_cell_measurement_temperature    139.1(2)
_cell_measurement_theta_max      72.7090
_cell_measurement_theta_min      3.5390
_cell_volume                     2778.67(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      139.1(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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   -104.00 -20.00   1.00    1.32    --  -36.42 -57.00  60.00   84
  2  \w   -106.00 -18.00   1.00    1.32    --  -36.42 -38.00-180.00   88
  3  \w     23.00  90.00   1.00    1.32    --   36.42-125.00 -90.00   67
  4  \w      1.00  75.00   1.00    1.32    --   36.42 -99.00  60.00   74
  5  \w    100.00 178.00   1.00    5.27    --  108.71 111.00 -30.00   78
  6  \w     39.00 109.00   1.00    5.27    --  108.71 -94.00-120.00   70
  7  \w    100.00 178.00   1.00    5.27    --  108.71 111.00 -90.00   78
  8  \w     39.00 130.00   1.00    5.27    --  108.71 -30.00 -60.00   91
  9  \w    100.00 178.00   1.00    5.27    --  108.71 111.00 120.00   78
 10  \w    100.00 178.00   1.00    5.27    --  108.71 111.00  90.00   78
 11  \w     82.00 176.00   1.00    5.27    --  108.71  77.00  90.00   94
 12  \w     40.00  65.00   1.00    5.27    --  108.71 -45.00 -60.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0914042000
_diffrn_orient_matrix_UB_12      -0.0774367000
_diffrn_orient_matrix_UB_13      0.0028908000
_diffrn_orient_matrix_UB_21      -0.0185698000
_diffrn_orient_matrix_UB_22      -0.0098392000
_diffrn_orient_matrix_UB_23      -0.0826938000
_diffrn_orient_matrix_UB_31      0.1442235000
_diffrn_orient_matrix_UB_32      0.0478263000
_diffrn_orient_matrix_UB_33      -0.0125184000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0471
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            12506
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.958
_diffrn_reflns_theta_min         3.558
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.031
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71496
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.206
_exptl_crystal_description       plate
_exptl_crystal_F_000             1080
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.432
_refine_diff_density_min         -0.419
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 2050 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     332
_refine_ls_number_reflns         5418
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0582
_refine_ls_R_factor_gt           0.0552
_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^)+(0.0973P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1337
_refine_ls_wR_factor_ref         0.1371
_reflns_Friedel_coverage         0.747
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                5067
_reflns_number_total             5418
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01098_si_002.cif
_cod_data_source_block           lq-18012702-139k
_cod_original_cell_volume        2778.68(6)
_cod_database_code               4034186
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H00H), C11(H00M), C9(H00N)
2.b Secondary CH2 refined with riding coordinates:
 C24(H00U,H00V)
2.c Aromatic/amide H refined with riding coordinates:
 C19(H009), C15(H00D), C18(H00F), C1(H00I), C12(H00L), C16(H00O), C2(H00P),
 C5(H00Q), C3(H00T), C4(H00W)
2.d Idealised Me refined as rotating group:
 C21(H00A,H00B,H00C), C29(H00E,H00G,H00J), C22(H00K,H00R,H00S), C25(H00X,H00Y,
 H), C28(H00Z,HA,HB), C26(H00,HC,HD), C27(H01A,H01B,H01C)
;
_shelx_res_checksum              18712
_shelx_hkl_checksum              62239
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.388
_oxdiff_exptl_absorpt_empirical_full_min 0.808