Solvent-specific, DAST-mediated intramolecular Friedel-Crafts reaction: access to dibenzoxepine-fused spirooxindoles.
Samikannu, Ramesh; Sethuraman, Sankaranarayanan; Akula, Nagaraja; Radhakrishnan, Vignesh; Kamisetti, Srinivasarao; Banu, Shabana; Vetrichelvan, Muthalagu; Gupta, Anuradha; Li, Jianqing; Rampulla, Richard; Mathur, Arvind; Organic & biomolecular chemistry 19 (2021) 1760–1768; doi:10.1039/d0ob02461a

data_7157860
_publ_section_title
;
 Solvent-specific, DAST-mediated intramolecular Friedel-Crafts reaction:
 access to dibenzoxepine-fused spirooxindoles.
;
_journal_issue                   8
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1760
_journal_page_last               1768
_journal_paper_doi               10.1039/d0ob02461a
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C23 H15 Cl F3 N O3'
_chemical_formula_sum            'C23 H15 Cl F3 N O3'
_chemical_formula_weight         445.81
_chemical_name_common            Compound-3f
_chemical_name_systematic
2-Chloro-8-methoxy-6'-(trifluoromethyl)-6H-spiro[dibenzo[b,e]oxepine-11,3'-indolin]-2'-one
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-07-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2020-07-15 deposited with the CCDC.	2021-01-28 downloaded from the CCDC.
;
_cell_angle_alpha                111.955(2)
_cell_angle_beta                 97.653(2)
_cell_angle_gamma                98.734(2)
_cell_formula_units_Z            2
_cell_length_a                   7.8400(4)
_cell_length_b                   11.8374(6)
_cell_length_c                   11.9176(6)
_cell_measurement_reflns_used    9965
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      65.19
_cell_measurement_theta_min      4.09
_cell_volume                     991.91(9)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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      296.15
_diffrn_detector                 'Bruker APEX II area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            28674
_diffrn_reflns_theta_full        65.19
_diffrn_reflns_theta_max         65.19
_diffrn_reflns_theta_min         4.09
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.197
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.4460
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1491 before and 0.0633 after correction. The Ratio of minimum to maximum transmission is 0.5926. The \l/2 correction factor is Not present.'
_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    1.493
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             456
_exptl_crystal_recrystallization_method
'obtained from clear solution of methanol by solvent evaporation at RT'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.302
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         3296
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0437
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0686P)^2^+0.3161P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1213
_refine_ls_wR_factor_ref         0.1233
_reflns_number_gt                3146
_reflns_number_total             3296
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d0ob02461a2.cif
_cod_data_source_block           Compound-3f
_cod_depositor_comments          'Adding full bibliography for 7157860.cif.'
_cod_database_code               7157860
_shelx_shelxl_version_number     2016/6
_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. Others
 Fixed Sof: F1B(0.5) F2B(0.5) F3B(0.5) F1A(0.5) F2A(0.5) F3A(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
3.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C7(H7), C12(H12), C14(H14), C15(H15), C19(H19),
 C20(H20), C22(H22)
3.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_olex2_exptl_crystal_mounting_method
'mounted on nylon cryoloop with paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'