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_4035270
_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         'C18 H21 N O'
_chemical_formula_sum            'C18 H21 N O'
_chemical_formula_weight         267.36
_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             2018-06-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.696(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.0667(3)
_cell_length_b                   10.0284(2)
_cell_length_c                   14.0170(3)
_cell_measurement_reflns_used    5665
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.6500
_cell_measurement_theta_min      4.3410
_cell_volume                     1435.17(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)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.986
_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      3.00  75.00   1.00    1.50    --   36.95 -99.00  90.00   72
  2  \w     19.00  76.00   1.00    1.50    --   36.95 -99.00-180.00   57
  3  \w     27.00 103.00   1.00    1.50    --   36.95  57.00  30.00   76
  4  \w    -28.00  65.00   1.00    1.50    --   36.95 -19.00  90.00   93
  5  \w      3.00  71.00   1.00    1.50    --   36.95 -99.00 -30.00   68
  6  \w    -23.00  53.00   1.00    1.50    --   36.95 -57.00-150.00   76
  7  \w     18.00  95.00   1.00    1.50    --   36.95  19.00 150.00   77
  8  \w     71.00 171.00   1.00   10.00    --  111.00  12.00 -90.00  100
  9  \w     42.00  89.00   1.00   10.00    --  111.00 -38.00-150.00   47
 10  \w    107.00 134.00   1.00   10.00    --  111.00 -77.00   0.00   27
 11  \w     48.00 113.00   1.00   10.00    --  111.00-111.00  90.00   65
 12  \w     94.00 130.00   1.00   10.00    --  111.00 -38.00-150.00   36
 13  \w     41.00 112.00   1.00   10.00    --  111.00 -25.00  60.00   71
 14  \w     85.00 113.00   1.00   10.00    --  111.00-111.00 -30.00   28
 15  \w     52.00 130.00   1.00   10.00    --  111.00 -64.00-120.00   78
 16  \w     71.00 173.00   1.00   10.00    --  111.00  12.00   0.00  102
 17  \w     44.00 112.00   1.00   10.00    --  111.00-111.00 -90.00   68
 18  \w     42.00  86.00   1.00   10.00    --  111.00 -38.00  30.00   44
 19  \w     41.00 128.00   1.00   10.00    --  111.00 -25.00 -60.00   87
 20  \w     43.00 107.00   1.00   10.00    --  111.00 -92.00 150.00   64
 21  \w     47.00  89.00   1.00   10.00    --  111.00 -77.00   0.00   42
 22  \w     43.00 104.00   1.00   10.00    --  111.00 -50.00 150.00   61
;
_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      0.0156889000
_diffrn_orient_matrix_UB_12      0.0263715000
_diffrn_orient_matrix_UB_13      -0.1028999000
_diffrn_orient_matrix_UB_21      0.1052261000
_diffrn_orient_matrix_UB_22      0.1058905000
_diffrn_orient_matrix_UB_23      0.0534858000
_diffrn_orient_matrix_UB_31      0.1071163000
_diffrn_orient_matrix_UB_32      -0.1079877000
_diffrn_orient_matrix_UB_33      0.0273867000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            9507
_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         74.029
_diffrn_reflns_theta_min         4.361
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.588
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91005
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       plate
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.360
_exptl_crystal_size_mid          0.204
_exptl_crystal_size_min          0.054
_refine_diff_density_max         0.230
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2883
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0507
_refine_ls_R_factor_gt           0.0466
_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^)+(0.0783P)^2^+0.4028P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1276
_refine_ls_wR_factor_ref         0.1315
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2635
_reflns_number_total             2883
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01940_si_011.cif
_cod_data_source_block           MED-1186_scale
_cod_original_cell_volume        1435.16(6)
_cod_database_code               4035270
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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 Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C16(H16A,H16B), C17(H17A,H17B),
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12)
;
_shelx_res_checksum              8745
_shelx_hkl_checksum              61895
_ins_header
;
TITL MED-1186_scale in P2(1)/n 
REM P2(1)/n (#14 in standard setting)
CELL 1.54184  11.066713  10.028395  14.016970  90.0000 112.6956  90.0000
ZERR    4.00   0.000274   0.000176   0.000335   0.0000   0.0029   0.0000
LATT  1
SYMM -x+1/2, y+1/2,-z+1/2 
SFAC C H N O
UNIT 72.00 84.00 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 1.328
_oxdiff_exptl_absorpt_empirical_full_min 0.456