<i>N</i>-Amino-7-azaindole as the <i>N</i>,<i>N</i>'-Bidentate Directing Group: Ruthenium-Catalyzed Oxidative Annulation of <i>N</i>-(7-Azaindole)benzamides with Alkynes via C-H Bond Activation.
Sagara, Prateep Singh; Siril, Prem Felix; Ravikumar, Ponneri Chandrababu; The Journal of organic chemistry 84 (2019) 12314–12323; doi:10.1021/acs.joc.9b01598

data_4033983
_publ_section_title
;
 <i>N</i>-Amino-7-azaindole as the <i>N</i>,<i>N</i>'-Bidentate Directing
 Group: Ruthenium-Catalyzed Oxidative Annulation of
 <i>N</i>-(7-Azaindole)benzamides with Alkynes via C-H Bond Activation.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12314
_journal_page_last               12323
_journal_paper_doi               10.1021/acs.joc.9b01598
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H26 Cl N3 O Ru'
_chemical_formula_sum            'C25 H26 Cl N3 O Ru'
_chemical_formula_weight         521.01
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-03-21
_audit_creation_method
;
Olex2 1.2-ac21
(compiled 2015.09.16 svn.r134, GUI svn.r4998)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.1000(4)
_cell_length_b                   14.3544(4)
_cell_length_c                   17.5769(7)
_cell_measurement_reflns_used    2078
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      66.9970
_cell_measurement_theta_min      3.1060
_cell_volume                     2295.98(15)
_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, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9974
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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     40.00 131.00   1.00    1.00    --   66.78  45.00 150.00   91
  2  \w    118.00 173.00   1.00    1.00    --  108.00 104.00 -30.00   55
  3  \w    139.00 173.00   1.00    1.00    --  108.00  65.00 -60.00   34
  4  \w     87.00 148.00   1.00    1.00    --   66.78 178.00-150.00   61
  5  \w     74.00 129.00   1.00    1.00    --  108.00  65.00 -60.00   55
  6  \w     72.00 140.00   1.00    1.00    --  108.00   0.00-150.00   68
  7  \w     49.00 116.00   1.00    1.00    --   66.78  61.00-180.00   67
  8  \w     27.00  60.00   1.00    1.00    --  108.00   0.00-150.00   33
  9  \w     36.00 108.00   1.00    1.00    --  108.00-104.00-180.00   72
 10  \w     29.00  84.00   1.00    1.00    --  108.00-104.00-150.00   55
 11  \w    -10.00 101.00   1.00    1.00    --   25.57  57.00-180.00  111
 12  \w     40.00  88.00   1.00    1.00    --  108.00-104.00 150.00   48
;
_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      -0.0442420000
_diffrn_orient_matrix_UB_12      -0.0151830000
_diffrn_orient_matrix_UB_13      0.0836902000
_diffrn_orient_matrix_UB_21      0.1609765000
_diffrn_orient_matrix_UB_22      -0.0225219000
_diffrn_orient_matrix_UB_23      0.0200385000
_diffrn_orient_matrix_UB_31      0.0282939000
_diffrn_orient_matrix_UB_32      0.1038494000
_diffrn_orient_matrix_UB_33      0.0164491000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            4575
_diffrn_reflns_theta_full        66.71
_diffrn_reflns_theta_max         66.71
_diffrn_reflns_theta_min         3.08
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.764
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.175
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.507
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       orthorhombic
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.404
_exptl_crystal_size_mid          0.241
_exptl_crystal_size_min          0.124
_refine_diff_density_max         0.397
_refine_diff_density_min         -0.735
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.05(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         2616
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0489
_refine_ls_R_factor_gt           0.0425
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0745P)^2^+0.3311P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1134
_refine_ls_wR_factor_ref         0.1236
_reflns_number_gt                2331
_reflns_number_total             2616
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo9b01598_si_003.cif
_cod_data_source_block           sps_04_348
_cod_original_cell_volume        2295.99(15)
_cod_database_code               4033983
_chemical_oxdiff_formula         'C100 H104 Cl4 N12 O4 Ru4'
_reflns_odcompleteness_completeness 98.27
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C23(H23)
2.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C16(H16), C4(H4), C6(H6), C17(H17), C19(H19), C9(H9), C7(H7),
 C14(H14), C13(H13), C10(H10), C12(H12), C3(H3)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C25(H25A,H25B,H25C), C24(H24A,H24B,H24C), C22(H22A,H22B,H22C)
;
_olex2_date_sample_data_collection 2018-10-29
_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 1.595
_oxdiff_exptl_absorpt_empirical_full_min 0.804