Catalytic asymmetric [3 + 2] cycloaddition of pyrazolone-derived MBH carbonate: highly stereoselective construction of the bispiro-[pyrazolone-dihydropyrrole-oxindole] skeleton.
Tian, Zhou; Jiang, Jing; Yan, Zhen-Hui; Luo, Qing-Qing; Zhan, Gu; Huang, Wei; Li, Xiang; Han, Bo; Chemical communications (Cambridge, England) 58 (2022) 5363–5366; doi:10.1039/d2cc00618a

data_7129972
_publ_section_title
;
 Catalytic asymmetric [3 + 2] cycloaddition of pyrazolone-derived MBH
 carbonate: highly stereoselective construction of the
 bispiro-[pyrazolone-dihydropyrrole-oxindole] skeleton.
;
_journal_issue                   35
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              5363
_journal_page_last               5366
_journal_paper_doi               10.1039/d2cc00618a
_journal_volume                  58
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H35 N4 O8'
_chemical_formula_sum            'C32 H34 N4 O8'
_chemical_formula_weight         602.63
_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_block_doi                 10.5517/ccdc.csd.cc295f86
_audit_creation_date             2022-02-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-03-03 deposited with the CCDC.	2022-04-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4403(9)
_cell_length_b                   12.4980(11)
_cell_length_c                   27.612(2)
_cell_measurement_reflns_used    3644
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      22.9860
_cell_measurement_theta_min      3.4910
_cell_volume                     3257.8(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0874
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -46.00  -21.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773  109.0000 -167.0000 25

  2 omega   31.00   61.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -       17.5086 -109.0000   96.0000 30

  3 omega  -76.00  -35.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773 -178.0000  120.0000 41

  4 omega  -15.00   23.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773  -99.0000  -60.0000 38

  5 omega  -79.00  -52.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773 -178.0000 -180.0000 27

  6 omega  -81.00  -31.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773  -57.0000 -120.0000 50

  7 omega  -27.00   -1.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773  -57.0000 -120.0000 26

  8 omega  -73.00  -35.00   1.0000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -15.4773 -178.0000 -150.0000 38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0095799000
_diffrn_orient_matrix_UB_12      0.0336808000
_diffrn_orient_matrix_UB_13      -0.0204053000
_diffrn_orient_matrix_UB_21      0.0150938000
_diffrn_orient_matrix_UB_22      0.0453804000
_diffrn_orient_matrix_UB_23      0.0145227000
_diffrn_orient_matrix_UB_31      0.0730130000
_diffrn_orient_matrix_UB_32      -0.0050355000
_diffrn_orient_matrix_UB_33      -0.0056876000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_unetI/netI     0.0506
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            18281
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.081
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92481
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
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    1.229
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.512
_refine_diff_density_min         -0.557
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 1371 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(5)
_refine_ls_extinction_coef       0.0055(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         6615
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.1031
_refine_ls_R_factor_gt           0.0681
_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^)+(0.0867P)^2^+0.9873P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1637
_refine_ls_wR_factor_ref         0.1834
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                4442
_reflns_number_total             6615
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00618a2.cif
_cod_data_source_block           210316_s2_mj_hbtz0310
_cod_depositor_comments          'Adding full bibliography for 7129972.cif.'
_cod_database_code               7129972
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         c12h12n2o3
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.969
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C15-C16 = C15-C16A
 1.55 with sigma of 0.02
3. Rigid bond restraints
 C15, C18
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C15 \\sim C18: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(C17) = Uanis(C17A)
Uanis(C16) = Uanis(C16A)
Uanis(C16A) = Uanis(C16) = Uanis(C17A) = Uanis(C17)
5. Others
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=1-FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 N4(H4), C4(H4A), C5(H5), C6(H6), C7(H7), C13(H13), C28(H28), C29(H29),
 C30(H30), C31(H31), C32(H32)
6.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C16(H16A,H16B,H16C), C17(H17A,
 H17B,H17C), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              6478
_shelx_hkl_checksum              9519
_olex2_submission_special_instructions 'No special instructions were received'