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_4035266
_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         'C15 H11 N O'
_chemical_formula_sum            'C15 H11 N O'
_chemical_formula_weight         221.25
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.112(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.00720(10)
_cell_length_b                   22.2268(5)
_cell_length_c                   12.2592(3)
_cell_measurement_reflns_used    4162
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.5870
_cell_measurement_theta_min      5.3820
_cell_volume                     1087.55(5)
_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)'
_computing_structure_solution    'ShelXT (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 0.975
_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    -55.00 -16.00   1.00    1.00    --  -37.04  38.00-150.00   39
  2  \w      3.00  29.00   1.00    1.00    --  -37.04  38.00-150.00   26
  3  \w    -58.00 -21.00   1.00    1.00    --  -37.04 -57.00  60.00   37
  4  \w    -25.00  56.00   1.00    1.00    --   37.04 -38.00 -90.00   81
  5  \w     11.00  97.00   1.00    1.00    --   37.04  77.00-180.00   86
  6  \w     41.00 105.00   1.00    1.00    --   37.04  77.00-120.00   64
  7  \w    -30.00  50.00   1.00    1.00    --   37.04 -57.00  30.00   80
  8  \w     15.00  74.00   1.00    1.00    --   37.04 -99.00 -30.00   59
  9  \w     47.00 127.00   1.00    1.00    --  111.00 -50.00 -30.00   80
 10  \w     50.00 109.00   1.00    1.00    --  111.00 -50.00 150.00   59
 11  \w     99.00 128.00   1.00    1.00    --  111.00 -50.00  60.00   29
 12  \w    100.00 178.00   1.00    1.00    --  111.00  25.00 120.00   78
 13  \w     64.00 109.00   1.00    1.00    --  111.00 -92.00  60.00   45
 14  \w     78.00 108.00   1.00    1.00    --  111.00 -92.00 120.00   30
 15  \w     63.00 108.00   1.00    1.00    --  111.00 -92.00-150.00   45
 16  \w     41.00  66.00   1.00    1.00    --  111.00-111.00 -30.00   25
 17  \w     92.00 172.00   1.00    1.00    --  111.00  64.00 150.00   80
 18  \w     60.00 127.00   1.00    1.00    --  111.00 -25.00-180.00   67
 19  \w     48.00  96.00   1.00    1.00    --  111.00 -50.00  60.00   48
 20  \w     85.00 167.00   1.00    1.00    --  111.00  12.00-120.00   82
 21  \w     41.00 113.00   1.00    1.00    --  111.00-111.00   0.00   72
;
_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      -0.0434479000
_diffrn_orient_matrix_UB_12      0.0503537000
_diffrn_orient_matrix_UB_13      -0.0864709000
_diffrn_orient_matrix_UB_21      0.2335352000
_diffrn_orient_matrix_UB_22      -0.0340024000
_diffrn_orient_matrix_UB_23      -0.0719707000
_diffrn_orient_matrix_UB_31      -0.3041888000
_diffrn_orient_matrix_UB_32      -0.0333494000
_diffrn_orient_matrix_UB_33      -0.0571356000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0175
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            6055
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.217
_diffrn_reflns_theta_min         3.978
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.674
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71279
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_description       plate
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.53
_exptl_crystal_size_mid          0.337
_exptl_crystal_size_min          0.075
_refine_diff_density_max         0.236
_refine_diff_density_min         -0.338
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     157
_refine_ls_number_reflns         2147
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0521
_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^)+(0.1022P)^2^+0.2321P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1417
_refine_ls_wR_factor_ref         0.1441
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2026
_reflns_number_total             2147
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01940_si_006.cif
_cod_data_source_block           MED-1170_scale
_cod_database_code               4035266
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C14(H14), C15(H15), C16(H16),
 C17(H17)
;
_shelx_res_checksum              26186
_shelx_hkl_checksum              84966
_ins_header
;
TITL MED-1170_scale in P2(1)/n 
REM P2(1)/n (#14 in standard setting)
CELL 1.54184   4.007173  22.226754  12.259155  90.0000  95.1120  90.0000
ZERR    4.00   0.000087   0.000468   0.000278   0.0000   0.0020   0.0000
LATT  1
SYMM -x+1/2, y+1/2,-z+1/2 
SFAC C H N O
UNIT 60.00 44.00 4.00 4.00
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 1.805
_oxdiff_exptl_absorpt_empirical_full_min 0.510