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_4035262
_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         'C12 H11 N O2'
_chemical_formula_sum            'C12 H11 N O2'
_chemical_formula_weight         201.22
_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   mixed
_audit_creation_date             2018-05-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.602(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.6966(2)
_cell_length_b                   12.4116(4)
_cell_length_c                   21.1857(7)
_cell_measurement_reflns_used    2964
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.6250
_cell_measurement_theta_min      4.1360
_cell_volume                     2271.59(12)
_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 0.999
_diffrn_measured_fraction_theta_max 0.982
_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    -53.00  11.00   1.00   15.00    --  -36.03  57.00  90.00   64
  2  \w   -105.00  26.00   1.00   15.00    --  -36.03   0.00-120.00  131
  3  \w     32.00  99.00   1.00   15.00    --   36.03  57.00-120.00   67
  4  \w     23.00  89.00   1.00   15.00    --   36.03-125.00-150.00   66
  5  \w     23.00  64.00   1.00   15.00    --   36.03-125.00 -30.00   41
  6  \w     28.00  83.00   1.00   15.00    --   36.03-125.00  30.00   55
  7  \w    101.00 171.00   1.00  100.00    --  107.33 111.00  60.00   70
  8  \w     55.00 134.00   1.00  100.00    --  107.33 -77.00 120.00   79
  9  \w     37.00 112.00   1.00  100.00    --  107.33-111.00 -90.00   75
 10  \w     41.00 125.00   1.00  100.00    --  107.33 -45.00  90.00   84
 11  \w     53.00 110.00   1.00  100.00    --  107.33 -95.00  60.00   57
 12  \w     90.00 153.00   1.00  100.00    --  107.33  45.00 120.00   63
 13  \w     40.00 122.00   1.00  100.00    --  107.33 -45.00 -90.00   82
 14  \w     39.00 118.00   1.00  100.00    --  107.33 -45.00   0.00   79
 15  \w     61.00 107.00   1.00  100.00    --  107.33 -95.00 -30.00   46
 16  \w     59.00 177.00   1.00  100.00    --  107.33   0.00-120.00  118
;
_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      0.0059471000
_diffrn_orient_matrix_UB_12      -0.0321571000
_diffrn_orient_matrix_UB_13      0.0704745000
_diffrn_orient_matrix_UB_21      -0.0061854000
_diffrn_orient_matrix_UB_22      0.1197870000
_diffrn_orient_matrix_UB_23      0.0186517000
_diffrn_orient_matrix_UB_31      -0.1780872000
_diffrn_orient_matrix_UB_32      -0.0051368000
_diffrn_orient_matrix_UB_33      -0.0067510000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0474
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            12569
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.999
_diffrn_reflns_theta_min         4.135
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.658
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87813
_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    1.177
_exptl_crystal_description       needle
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.153
_exptl_crystal_size_mid          0.051
_exptl_crystal_size_min          0.029
_platon_squeeze_details
;
TITL xl-3-142_scale_a.res in P2(1)/c
CELL    8.6966   12.4116   21.1857     90.00     96.60     90.00
SPGR P21/c
C101 0.500 0.500 0.500 !       4.79 eA-3
C102 0.312 0.462 0.467 !       2.28 eA-3
C103 0.254 0.046 0.982 !       2.15 eA-3
C104 0.746 0.954 0.018 !       2.15 eA-3
C105 0.226 0.019 0.997 !       2.11 eA-3
C106 0.316 0.928 0.032 !       2.02 eA-3
C107 1.000 1.000 0.000 !       0.56 eA-3
;
_refine_diff_density_max         0.277
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         4391
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0780
_refine_ls_R_factor_gt           0.0568
_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^)+(0.0819P)^2^+0.2715P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1492
_refine_ls_wR_factor_ref         0.1637
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3120
_reflns_number_total             4391
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01940_si_002.cif
_cod_data_source_block           XL-3-142_scale_sq
_cod_database_code               4035262
_shelxl_version_number           2014/6
_diffrn_oxdiff_ac3_digest_frames
;
01d394cd5a0c9425768e71ad93b471d7ba012276bd7
;
_diffrn_oxdiff_ac3_digest_hkl
;
01f9666a4db4a56f4ea33f292f62a62a6f4631
;
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 O31-H31
 0.95 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C21(H21A,H21B), C22(H22A,H22B),
 C23(H23A,H23B)
3.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C32(H32), C33(H33), C34(H34), C35(H35)
;
_platon_squeeze_void_probe_radius 1.20
_ins_header
;
TITL XL-3-142_scale in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 1.54184   8.696625  12.411586  21.185713  90.0000  96.6019  90.0000
ZERR    8.00   0.000214   0.000371   0.000688   0.0000   0.0027   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H N O
UNIT 96.00 88.00 8.00 16.00
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 1.171
_oxdiff_exptl_absorpt_empirical_full_min 0.838