B(C6F5)3-Catalyzed Dehydrogenative Cyclization of N-Tosylhydrazones and Anilines via a Lewis Adduct: A Combined Experimental and Computational Investigations
Guru, Murali Mohan; De, Sriman; Dutta, Sayan; Koley, Debasis; Maji, Biplab; Chemical Science  (2019) –; doi:10.1039/C9SC02492A

data_1551986
_publ_section_title
;
 B(C6F5)3-Catalyzed Dehydrogenative Cyclization of N-Tosylhydrazones and
 Anilines via a Lewis Adduct: A Combined Experimental and Computational
 Investigations
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02492A
_journal_year                    2019
_chemical_formula_moiety         'C27 H20 Cl N3 O'
_chemical_formula_sum            'C27 H20 Cl N3 O'
_chemical_formula_weight         437.91
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-10 deposited with the CCDC.    2019-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.153(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3302(3)
_cell_length_b                   24.2725(8)
_cell_length_c                   11.2388(5)
_cell_measurement_reflns_used    6888
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      27.4550
_cell_measurement_theta_min      2.0580
_cell_volume                     2159.32(15)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9580
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.926
_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    -11.00 103.00   1.00   40.00    --   26.72  57.00  60.00  114
  2  \w    -58.00  70.00   1.00   40.00    --   26.72 -77.00-150.00  128
  3  \w    -61.00  52.00   1.00   40.00    --  -23.50  57.00 150.00  113
  4  \w    -20.00  32.00   1.00   40.00    --  -23.50 -99.00  90.00   52
  5  \w     35.00 121.00   1.00   40.00    --   26.72 178.00 120.00   86
  6  \w    -49.00 -11.00   1.00   40.00    --   26.72 -57.00 -60.00   38
  7  \w    -29.00 108.00   1.00   40.00    --   26.72  38.00 -90.00  137
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0354771000
_diffrn_orient_matrix_UB_12      -0.0267842000
_diffrn_orient_matrix_UB_13      0.0116422000
_diffrn_orient_matrix_UB_21      0.0579130000
_diffrn_orient_matrix_UB_22      0.0069169000
_diffrn_orient_matrix_UB_23      -0.0324559000
_diffrn_orient_matrix_UB_31      0.0584717000
_diffrn_orient_matrix_UB_32      0.0094029000
_diffrn_orient_matrix_UB_33      0.0567610000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.926
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            20055
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.926
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.576
_diffrn_reflns_theta_min         1.678
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.202
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62600
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.347
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.274
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.172
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         4629
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.172
_refine_ls_R_factor_all          0.0595
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0419P)^2^+1.9399P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1193
_refine_ls_wR_factor_ref         0.1279
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4003
_reflns_number_total             4629
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02492a2.cif
_cod_data_source_block           mmg80
_cod_database_code               1551986
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N O Cl'
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.947
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.63
_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
2.a Aromatic/amide H refined with riding coordinates:
 C25(H25), C24(H24), C21(H21), C9(H9), C13(H13), C22(H22), C4(H4), C12(H12),
 C10(H10), C27(H27), C5(H5), C19(H19), C15(H15), C16(H16), C18(H18), C17(H17),
 C7(H7)
2.b Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C)
;
_shelx_res_checksum              97535
_olex2_date_sample_data_collection 2018-09-07
_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 1.419
_oxdiff_exptl_absorpt_empirical_full_min 0.442