Reductive Cyclization of o-Nitroarylated-α,β-unsaturated Aldehydes and Ketones with TiCl<sub>3</sub>/HCl or Fe/HCl Leading to 1,2,3,9-Tetrahydro-4 H-carbazol-4-ones and Related Heterocycles.
Qiu, Yun; Dlugosch, Michael; Liu, Xin; Khan, Faiyaz; Ward, Jas S.; Lan, Ping; Banwell, Martin G.; The Journal of organic chemistry 83 (2018) 12023–12033; doi:10.1021/acs.joc.8b01940

data_4035261
_publ_section_title
;
 Reductive Cyclization of o-Nitroarylated-\a,\b-unsaturated Aldehydes and
 Ketones with TiCl<sub>3</sub>/HCl or Fe/HCl Leading to
 1,2,3,9-Tetrahydro-4 H-carbazol-4-ones and Related Heterocycles.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12023
_journal_page_last               12033
_journal_paper_doi               10.1021/acs.joc.8b01940
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C20 H14 N2 O3'
_chemical_formula_sum            'C20 H14 N2 O3'
_chemical_formula_weight         330.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-05-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.865(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5226(3)
_cell_length_b                   12.7446(3)
_cell_length_c                   10.8100(2)
_cell_measurement_reflns_used    7319
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.7030
_cell_measurement_theta_min      5.5210
_cell_volume                     1642.04(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_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    -21.00  28.00   1.00    1.00    --  -36.95  57.00 -60.00   49
  2  \w    -50.00 -23.00   1.00    1.00    --  -36.95  57.00 -60.00   27
  3  \w    -14.00  38.00   1.00    1.00    --   36.95 -57.00  60.00   52
  4  \w     38.00  90.00   1.00    1.00    --   36.95-125.00-120.00   52
  5  \w     20.00  92.00   1.00    1.00    --   36.95  57.00  30.00   72
  6  \w     29.00  87.00   1.00    1.00    --   36.95-125.00 -30.00   58
  7  \w     30.00  76.00   1.00    1.00    --   36.95 -99.00  60.00   46
  8  \w     38.00 104.00   1.00    1.00    --   36.95  57.00 150.00   66
  9  \w      8.00 106.00   1.00    1.00    --   36.95  19.00 -90.00   98
 10  \w     69.00 105.00   1.00    2.00    --  111.00 -92.00-150.00   36
 11  \w     82.00 135.00   1.00    2.00    --  111.00 -77.00-120.00   53
 12  \w    101.00 168.00   1.00    2.00    --  111.00 111.00  60.00   67
 13  \w     42.00 130.00   1.00    2.00    --  111.00 -38.00   0.00   88
 14  \w     57.00 126.00   1.00    2.00    --  111.00 -64.00  30.00   69
 15  \w     70.00 177.00   1.00    2.00    --  111.00  12.00-150.00  107
 16  \w     43.00 126.00   1.00    2.00    --  111.00 -38.00 -90.00   83
 17  \w     83.00 109.00   1.00    2.00    --  111.00-111.00 -60.00   26
 18  \w     90.00 116.00   1.00    2.00    --  111.00-122.00 159.00   26
 19  \w     88.00 113.00   1.00    2.00    --  111.00-111.00   0.00   25
 20  \w     45.00 102.00   1.00    2.00    --  111.00 -92.00  30.00   57
 21  \w     47.00 127.00   1.00    2.00    --  111.00 -50.00 120.00   80
 22  \w     45.00  74.00   1.00    2.00    --  111.00 -77.00-120.00   29
 23  \w     44.00  69.00   1.00    2.00    --  111.00-111.00 -60.00   25
 24  \w     42.00 104.00   1.00    2.00    --  111.00 -92.00 150.00   62
 25  \w     41.00 146.00   1.00    2.00    --  111.00 -12.00-180.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0403582000
_diffrn_orient_matrix_UB_12      0.1125860000
_diffrn_orient_matrix_UB_13      0.0123785000
_diffrn_orient_matrix_UB_21      0.1180648000
_diffrn_orient_matrix_UB_22      0.0421212000
_diffrn_orient_matrix_UB_23      0.0118229000
_diffrn_orient_matrix_UB_31      -0.0338683000
_diffrn_orient_matrix_UB_32      0.0126630000
_diffrn_orient_matrix_UB_33      -0.1487106000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0280
_diffrn_reflns_av_unetI/netI     0.0232
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10949
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.800
_diffrn_reflns_theta_min         3.709
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.747
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.336
_exptl_crystal_description       needle
_exptl_crystal_F_000             688
_exptl_crystal_size_max          0.650
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.077
_refine_diff_density_max         0.196
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3297
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0819P)^2^+0.4521P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1250
_refine_ls_wR_factor_ref         0.1285
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3062
_reflns_number_total             3297
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01940_si_004.cif
_cod_data_source_block           MED-1153F2_scale
_cod_database_code               4035261
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C10(H12), C14(H14), C15(H15),
 C16(H16), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
;
_shelx_res_checksum              63626
_shelx_hkl_checksum              71616
_ins_header
;
TITL MED-1153F2_scale in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 1.54184  12.522563  12.744612  10.810002  90.0000 107.8645  90.0000
ZERR    4.00   0.000274   0.000269   0.000212   0.0000   0.0022   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H N O
UNIT 80.00 56.00 8.00 12.00
TREF
HKLF 4
END
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.695
_oxdiff_exptl_absorpt_empirical_full_min 0.611