Rh-Catalyzed oxidative C-H activation/annulation: converting anilines to indoles using molecular oxygen as the sole oxidant
Guoying Zhang; Hui Yu; Guiping Qin; Hanmin Huang; Chem.Commun. 50 (2014) 4331–; doi:10.1039/C3CC49751H

data_7112244
_publ_section_title
;
 Rh-Catalyzed oxidative C-H activation/annulation: converting anilines to
 indoles using molecular oxygen as the sole oxidant
;
_journal_name_full               Chem.Commun.
_journal_page_first              4331
_journal_paper_doi               10.1039/C3CC49751H
_journal_volume                  50
_journal_year                    2014
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C H Cl3, C21 H14 N2'
_chemical_formula_sum            'C22 H15 Cl3 N2'
_chemical_formula_weight         413.71
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-13
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr  9 2013 14:06:00, GUI svn.r4458)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.4508(3)
_cell_length_b                   12.8668(5)
_cell_length_c                   17.0426(5)
_cell_measurement_reflns_used    1631
_cell_measurement_temperature    294.2(3)
_cell_measurement_theta_max      24.6820
_cell_measurement_theta_min      3.8230
_cell_volume                     2072.41(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      294.2(3)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9967
_diffrn_measured_fraction_theta_max 0.7716
_diffrn_measurement_details
;
  1 omega  -14.00   22.00   1.2000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -99.0000  -90.0000 30

  2 omega  -44.00   -9.20   1.2000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -77.0000  150.0000 29

  3 omega  -13.00   67.40   1.2000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -99.0000   30.0000 67
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0545302000
_diffrn_orient_matrix_UB_12      -0.0183756000
_diffrn_orient_matrix_UB_13      0.0249654000
_diffrn_orient_matrix_UB_21      -0.0478537000
_diffrn_orient_matrix_UB_22      0.0358933000
_diffrn_orient_matrix_UB_23      -0.0171548000
_diffrn_orient_matrix_UB_31      -0.0190528000
_diffrn_orient_matrix_UB_32      -0.0375982000
_diffrn_orient_matrix_UB_33      -0.0285683000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0216
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5052
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         2.93
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.451
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49761
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.326
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.259
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.1(2)
_refine_ls_extinction_coef       0.010(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3613
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0940
_refine_ls_R_factor_gt           0.0665
_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^)+(0.0899P)^2^+0.2739P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1652
_refine_ls_wR_factor_ref         0.1940
_reflns_number_gt                2490
_reflns_number_total             3613
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c3cc49751h2.cif
_cod_data_source_block           zhanggy0913
_cod_original_cell_volume        2072.40(12)
_cod_database_code               7112244
_reflns_odcompleteness_completeness 99.67
_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 C(H,H) groups, All N(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Cl2A) \\sim Ueq, Uanis(Cl2B) \\sim Ueq, Uanis(Cl3A) \\sim Ueq, Uanis(Cl3B) \\sim Ueq, Uanis(Cl1A) \\sim Ueq, Uanis(Cl1B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: Cl1A(0.5) Cl1B(0.5) Cl2A(0.5) Cl2B(0.5) Cl3A(0.5) Cl3B(0.5)
 H22(0.5) H22A(0.5)
4.a Ternary CH refined with riding coordinates:
 C22(H22), C22(H22A)
4.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C13(H13), C14(H14),
  C17(H17), C18(H18), C19(H19), C20(H20), C21(H21)
;