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_4035267
_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_absolute_configuration ad
_chemical_formula_moiety         'C12 H9 N O3'
_chemical_formula_sum            'C12 H9 N O3'
_chemical_formula_weight         215.20
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.72830(10)
_cell_length_b                   9.5441(2)
_cell_length_c                   15.1689(4)
_cell_measurement_reflns_used    4155
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      73.5460
_cell_measurement_theta_min      5.4610
_cell_volume                     974.08(4)
_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      150.01(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 0.995
_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    -94.00 -27.00   1.00    1.00    --  -37.04 -57.00 -60.00   67
  2  \w     25.00 103.00   1.00    1.00    --   37.04  38.00 120.00   78
  3  \w      2.00  73.00   1.00    1.00    --   37.04 -99.00  30.00   71
  4  \w      2.00  75.00   1.00    1.00    --   37.04 -99.00 150.00   73
  5  \w     10.00  92.00   1.00    1.00    --   37.04  77.00 -90.00   82
  6  \w     21.00 107.00   1.00    1.00    --   37.04  19.00-120.00   86
  7  \w     50.00 108.00   1.00    3.00    --  111.00 -92.00 150.00   58
  8  \w     92.00 178.00   1.00    3.00    --  111.00  38.00 120.00   86
  9  \w     52.00 107.00   1.00    3.00    --  111.00 -50.00 120.00   55
 10  \w     43.00 130.00   1.00    3.00    --  111.00 -38.00  30.00   87
 11  \w     41.00 133.00   1.00    3.00    --  111.00 -25.00 120.00   92
 12  \w     59.00 103.00   1.00    3.00    --  111.00 -50.00-180.00   44
 13  \w     69.00 112.00   1.00    3.00    --  111.00-111.00 -90.00   43
 14  \w     44.00 118.00   1.00    3.00    --  111.00 -64.00 -90.00   74
 15  \w     47.00 123.00   1.00    3.00    --  111.00 -25.00 -60.00   76
 16  \w    102.00 136.00   1.00    3.00    --  111.00 -25.00-150.00   34
 17  \w     45.00 112.00   1.00    3.00    --  111.00 -77.00  30.00   67
 18  \w     85.00 113.00   1.00    3.00    --  111.00-111.00   0.00   28
 19  \w     41.00  93.00   1.00    3.00    --  111.00 -25.00-150.00   52
;
_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      0.0144034000
_diffrn_orient_matrix_UB_12      0.1273898000
_diffrn_orient_matrix_UB_13      -0.0620544000
_diffrn_orient_matrix_UB_21      0.2205501000
_diffrn_orient_matrix_UB_22      -0.0337733000
_diffrn_orient_matrix_UB_23      -0.0172531000
_diffrn_orient_matrix_UB_31      -0.0598988000
_diffrn_orient_matrix_UB_32      -0.0930980000
_diffrn_orient_matrix_UB_33      -0.0785579000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            5805
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.704
_diffrn_reflns_theta_min         5.476
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.891
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79199
_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    1.467
_exptl_crystal_description       plate
_exptl_crystal_F_000             448
_exptl_crystal_size_max          0.333
_exptl_crystal_size_mid          0.151
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.167
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 761 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.15(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     148
_refine_ls_number_reflns         1951
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0383
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0774P)^2^+0.0435P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1001
_refine_ls_wR_factor_ref         0.1021
_reflns_Friedel_coverage         0.678
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                1890
_reflns_number_total             1951
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01940_si_003.cif
_cod_data_source_block           MED-1177_scale
_cod_database_code               4035267
_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 C(H,H) groups, All N(H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15)
;
_shelx_res_checksum              17014
_shelx_hkl_checksum              54626
_ins_header
;
TITL MED-1177_scale in P2(1)2(1)2(1) 
REM P2(1)2(1)2(1) (#19 in standard setting)
CELL 1.54184   6.728268   9.544087  15.168946  90.0000  90.0000  90.0000
ZERR    3.00   0.000147   0.000237   0.000384   0.0000   0.0000   0.0000
LATT -1
SYMM -x+1/2,-y, z+1/2 
SYMM -x, y+1/2,-z+1/2 
SYMM  x+1/2,-y+1/2,-z 
SFAC C H N O
UNIT 36.00 27.00 3.00 9.00
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 1.302
_oxdiff_exptl_absorpt_empirical_full_min 0.741