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_4035269
_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         'C16 H17 N O'
_chemical_formula_sum            'C16 H17 N O'
_chemical_formula_weight         239.30
_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             2018-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.645(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3856(3)
_cell_length_b                   12.2110(3)
_cell_length_c                   12.1822(4)
_cell_measurement_reflns_used    4350
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      73.1150
_cell_measurement_theta_min      5.2460
_cell_volume                     1322.90(8)
_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 0.998
_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     20.00  98.00   1.00    1.00    --   37.04  57.00 -60.00   78
  2  \w     25.00  77.00   1.00    1.00    --   37.04-125.00  30.00   52
  3  \w    -31.00  64.00   1.00    1.00    --   37.04 -77.00 150.00   95
  4  \w    -29.00 104.00   1.00    1.00    --   37.04  -5.00 -51.00  133
  5  \w      5.00  75.00   1.00    1.00    --   37.04 -99.00  90.00   70
  6  \w     24.00  90.00   1.00    1.00    --   37.04-125.00 -90.00   66
  7  \w    142.00 170.00   1.00    3.50    --  111.00  64.00  90.00   28
  8  \w     99.00 126.00   1.00    3.50    --  111.00  64.00  90.00   27
  9  \w     52.00 128.00   1.00    3.50    --  111.00 -64.00 120.00   76
 10  \w     77.00 109.00   1.00    3.50    --  111.00 -92.00-180.00   32
 11  \w     46.00 135.00   1.00    3.50    --  111.00 -25.00 -90.00   89
 12  \w     42.00  99.00   1.00    3.50    --  111.00 -92.00 -60.00   57
 13  \w     65.00 136.00   1.00    3.50    --  111.00 -25.00 150.00   71
 14  \w     88.00 122.00   1.00    3.50    --  111.00  25.00-120.00   34
 15  \w     56.00 128.00   1.00    3.50    --  111.00 -50.00 -30.00   72
 16  \w     55.00 113.00   1.00    3.50    --  111.00-111.00  30.00   58
 17  \w    129.00 167.00   1.00    3.50    --  111.00  25.00-120.00   38
 18  \w     43.00 130.00   1.00    3.50    --  111.00 -38.00  60.00   87
 19  \w     43.00  99.00   1.00    3.50    --  111.00 -50.00 -90.00   56
 20  \w     52.00 107.00   1.00    3.50    --  111.00 -92.00  90.00   55
 21  \w     67.00 160.00   1.00    3.50    --  111.00  12.00-180.00   93
 22  \w     42.00  95.00   1.00    3.50    --  111.00 -92.00 -90.00   53
;
_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      -0.1412074000
_diffrn_orient_matrix_UB_12      0.0065215000
_diffrn_orient_matrix_UB_13      0.0381294000
_diffrn_orient_matrix_UB_21      -0.0997282000
_diffrn_orient_matrix_UB_22      0.0046618000
_diffrn_orient_matrix_UB_23      -0.1278748000
_diffrn_orient_matrix_UB_31      -0.0112439000
_diffrn_orient_matrix_UB_32      -0.1259154000
_diffrn_orient_matrix_UB_33      -0.0027894000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0169
_diffrn_reflns_av_unetI/netI     0.0143
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8644
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.636
_diffrn_reflns_theta_min         5.219
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.583
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72088
_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    1.202
_exptl_crystal_description       plate
_exptl_crystal_F_000             512
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.355
_exptl_crystal_size_min          0.119
_refine_diff_density_max         0.870
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         2640
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0872
_refine_ls_R_factor_gt           0.0822
_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^)+(0.1412P)^2^+0.6491P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2368
_refine_ls_wR_factor_ref         0.2436
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2373
_reflns_number_total             2640
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01940_si_010.cif
_cod_data_source_block           MED-1184_scale
_cod_original_cell_volume        1322.90(7)
_cod_database_code               4035269
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.60
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H18A)=Sof(H18)=Sof(H18B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=1-FVAR(1)
 Sof(H16)=Sof(H16B)=Sof(H16A)=Sof(C17)=Sof(H17A)=Sof(H17C)=Sof(H17B)=FVAR(1)
 Sof(N19)=Sof(H19)=1-FVAR(2)
 Sof(N14)=Sof(H14)=FVAR(2)
 Fixed X: H16(0.389589) H16B(0.376089) H16A(0.52002) H18A(0.125211)
 H18(0.122681) H18B(0.15414)
 Fixed Y: H16(0.687381) H16B(0.79916) H16A(0.726489) H18A(0.7187)
 H18(0.622251) H18B(0.598321)
 Fixed Z: H16(0.914929) H16B(0.8491) H16A(0.869881) H18A(0.721161)
 H18(0.63563) H18B(0.76771)
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B)
3.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12)
3.c Idealised Me refined as rotating group:
 C17(H17A,H17C,H17B), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              10970
_shelx_hkl_checksum              6072
_ins_header
;
TITL MED-1184_scale in P2(1)/n 
REM P2(1)/n (#14 in standard setting)
CELL 1.54184   9.385572  12.211028  12.182159  90.0000 108.6447  90.0000
ZERR    4.00   0.000347   0.000293   0.000428   0.0000   0.0040   0.0000
LATT  1
SYMM -x+1/2, y+1/2,-z+1/2 
SFAC C H N O
UNIT 64.00 76.00 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 1.598
_oxdiff_exptl_absorpt_empirical_full_min 0.662