Chemoselective and diastereodivergent synthesis of new spirooxindolo-pyrrolizidines and pyrrolidines stemming from unsymmetrical 1,3-bis(arylidene)tetral-2-ones: a combined experimental and theoretical study
Gazzeh, Houda; Rouatbi, Fadwa; Chniti, Sami; Askri, Moheddine; Knorr, Michael; Strohmann, Carsten; Golz, Christopher; Lamsabhi, Al Mokhtar; New Journal of Chemistry 46 (2022) 19198–19212; doi:10.1039/D2NJ03887K

data_7061947
_publ_section_title
;
 Chemoselective and diastereodivergent synthesis of new
 spirooxindolo-pyrrolizidines and pyrrolidines stemming from unsymmetrical
 1,3-bis(arylidene)tetral-2-ones: a combined experimental and theoretical
 study
;
_journal_issue                   40
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              19198
_journal_page_last               19212
_journal_paper_doi               10.1039/D2NJ03887K
_journal_volume                  46
_journal_year                    2022
_chemical_formula_moiety         'C36 H27 F2 N3 O4, 0.5(C4 H8 O2)'
_chemical_formula_sum            'C38 H31 F2 N3 O5'
_chemical_formula_weight         647.66
_chemical_name_systematic
4''-((E)-4-fluorobenzylidene)-1'-(4-fluorophenyl)-5-nitro-1'',4'',5',6',7',7a'-hexahydro-1'H,3''H-dispiro[indoline-3,3'-pyrrolizine-2',2''-naphthalene]-2,3''-dione
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-19 deposited with the CCDC.	2022-09-08 downloaded from the CCDC.
;
_cell_angle_alpha                75.195(19)
_cell_angle_beta                 80.54(2)
_cell_angle_gamma                77.813(17)
_cell_formula_units_Z            2
_cell_length_a                   8.244(4)
_cell_length_b                   12.956(6)
_cell_length_c                   15.359(8)
_cell_measurement_reflns_used    9146
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.72
_cell_measurement_theta_min      2.54
_cell_volume                     1539.7(13)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            'CMOS PHOTON100 area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.921
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0439
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.921
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            20681
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.616
_diffrn_reflns_theta_min         2.778
_exptl_absorpt_coefficient_mu    0.101
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6757
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1392 before and 0.0436 after correction.
The Ratio of minimum to maximum transmission is 0.9060.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_description       block
_exptl_crystal_F_000             676
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Ethylacetate and cyclohexane'
_exptl_crystal_size_max          0.395
_exptl_crystal_size_mid          0.207
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.446
_refine_diff_density_min         -0.379
_refine_diff_density_rms         0.056
_refine_ls_extinction_coef       0.0081(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     463
_refine_ls_number_reflns         8000
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0470
_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^)+(0.0578P)^2^+0.6962P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1160
_refine_ls_wR_factor_ref         0.1271
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6154
_reflns_number_total             8000
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj03887k2.cif
_cod_data_source_block           mo_b0419_0m
_cod_depositor_comments          'Adding full bibliography for 7061947.cif.'
_cod_original_cell_volume        1539.6(13)
_cod_database_code               7061947
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.961
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O6-C37
 1.32 with sigma of 0.02
 O6-C39
 1.46 with sigma of 0.02
 O5-C37
 1.22 with sigma of 0.02
 C38-C37
 1.49 with sigma of 0.02
 C39-C40
 1.5 with sigma of 0.02
 O6-C38
 2.35 with sigma of 0.04
 O5-C38
 2.4 with sigma of 0.04
 O6-O5
 2.24 with sigma of 0.04
 O6-C40
 2.38 with sigma of 0.04
3. Rigid body (RIGU) restrains
 C37, C38, O5, O6, C39, C40
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: O5(0.5) O6(0.5) C37(0.5) C38(0.5) H38A(0.5) H38B(0.5) H38C(0.5)
 C39(0.5) H39A(0.5) H39B(0.5) C40(0.5) H40A(0.5) H40B(0.5) H40C(0.5)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C11(H11)
5.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C25(H25A,H25B), C39(H39A,H39B)
5.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C5(H5), C6(H6), C8(H8), C16(H16), C17(H17), C19(H19), C20(H20),
 C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C35(H35),
  C36(H36)
5.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              63999
_olex2_submission_special_instructions 'No special instructions were received'