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_4035268
_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         'C13 H15 N O'
_chemical_formula_sum            'C13 H15 N O'
_chemical_formula_weight         201.26
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.270(2)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   13.9326(3)
_cell_length_b                   31.3218(6)
_cell_length_c                   7.60130(10)
_cell_measurement_reflns_used    5775
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.6260
_cell_measurement_theta_min      5.2920
_cell_volume                     3282.67(11)
_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 0.983
_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   -105.00  29.00   1.00   15.00    --  -35.78   0.00-150.00  134
  2  \w     28.00 103.00   1.00   15.00    --   35.78  57.00  30.00   75
  3  \w     23.00  79.00   1.00   15.00    --   35.78-125.00 150.00   56
  4  \w     62.00  89.00   1.00   15.00    --   35.78-125.00   0.00   27
  5  \w     23.00  49.00   1.00   15.00    --   35.78-125.00   0.00   26
  6  \w     19.00 100.00   1.00   15.00    --   35.78  57.00-150.00   81
  7  \w     23.00  86.00   1.00   15.00    --   35.78-125.00 -60.00   63
  8  \w     39.00 121.00   1.00   70.00    --  107.33 -45.00-180.00   82
  9  \w     40.00 124.00   1.00   70.00    --  107.33 -45.00   0.00   84
 10  \w     89.00 175.00   1.00   70.00    --  107.33  77.00 150.00   86
 11  \w     39.00 125.00   1.00   70.00    --  107.33 -45.00  90.00   86
 12  \w     38.00 110.00   1.00   70.00    --  107.33 -95.00   0.00   72
 13  \w    104.00 177.00   1.00   70.00    --  107.33 111.00  90.00   73
 14  \w     43.00 112.00   1.00   70.00    --  107.33-111.00 150.00   69
 15  \w     44.00 110.00   1.00   70.00    --  107.33 -95.00-120.00   66
 16  \w     42.00 174.00   1.00   70.00    --  107.33   0.00 -60.00  132
;
_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      0.0944226000
_diffrn_orient_matrix_UB_12      0.0245738000
_diffrn_orient_matrix_UB_13      -0.0139461000
_diffrn_orient_matrix_UB_21      -0.0328113000
_diffrn_orient_matrix_UB_22      0.0359694000
_diffrn_orient_matrix_UB_23      0.1161426000
_diffrn_orient_matrix_UB_31      0.0500547000
_diffrn_orient_matrix_UB_32      -0.0228077000
_diffrn_orient_matrix_UB_33      0.1680308000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            18346
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.102
_diffrn_reflns_theta_min         4.272
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.605
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83905
_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    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.053
_refine_diff_density_max         0.592
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     487
_refine_ls_number_reflns         6363
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0739
_refine_ls_R_factor_gt           0.0576
_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^)+(0.0800P)^2^+1.1563P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1525
_refine_ls_wR_factor_ref         0.1634
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5008
_reflns_number_total             6363
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01940_si_007.cif
_cod_data_source_block           MED-1176_scale
_cod_database_code               4035268
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.90
_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, All C(H,H,H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 C87A, C94A, C93A, C92A, C91A, C90A, N95A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C87B, C94B, C93B, C92B, C91B, C90B, N95B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Others
 Sof(C41A)=Sof(H41A)=Sof(H41B)=Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(H43C)=
 Sof(H43D)=1-FVAR(1)
 Sof(C41B)=Sof(H41C)=Sof(H41D)=Sof(C42B)=Sof(H42C)=Sof(H42D)=Sof(H43A)=
 Sof(H43B)=FVAR(1)
 Sof(H1BC)=Sof(H1BD)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H3BC)=Sof(H3BD)=1-FVAR(2)
 Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H3AA)=Sof(H3AB)=FVAR(2)
 Sof(C87B)=Sof(C94B)=Sof(C93B)=Sof(H93B)=Sof(C92B)=Sof(H92B)=Sof(C91B)=
 Sof(H91B)=Sof(C90B)=Sof(H90B)=Sof(N95B)=Sof(H95C)=Sof(H95D)=1-FVAR(3)
 Sof(C87A)=Sof(C94A)=Sof(C93A)=Sof(H93A)=Sof(C92A)=Sof(H92A)=Sof(C91A)=
 Sof(H91A)=Sof(C90A)=Sof(H90A)=Sof(N95A)=Sof(H95A)=Sof(H95B)=FVAR(3)
4.a Rotating group:
 N15(H15A,H15B), N95A(H95A,H95B), N95B(H95C,H95D)
4.b Secondary CH2 refined with riding coordinates:
 C1(H1AA,H1AB), C1(H1BC,H1BD), C2A(H2AA,H2AB), C2B(H2BA,H2BB), C3(H3AA,H3AB),
 C3(H3BC,H3BD), C41A(H41A,H41B), C41B(H41C,H41D), C42A(H42A,H42B), C42B(H42C,
 H42D), C43(H43A,H43B), C43(H43C,H43D), C81(H81A,H81B), C82(H82A,H82B),
 C83(H83A,H83B)
4.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C50(H50), C51(H51), C52(H52),
 C53(H53), C93A(H93A), C92A(H92A), C91A(H91A), C90A(H90A), C93B(H93B),
 C92B(H92B), C91B(H91B), C90B(H90B)
4.d Fitted hexagon refined as free rotating group:
 C87A(C94A,C93A,C92A,C91A,C90A), C87B(C94B,C93B,C92B,C91B,C90B)
4.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C48(H48A,H48B,H48C), C88(H88A,H88B,H88C)
;
_shelx_res_checksum              58262
_shelx_hkl_checksum              44195
_ins_header
;
TITL MED-1176_scale in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 1.54184  13.932606  31.321751   7.601266  90.0000  98.2703  90.0000
ZERR   12.00   0.000260   0.000597   0.000112   0.0000   0.0016   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H N O
UNIT 156.00 180.00 12.00 12.00
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 1.316
_oxdiff_exptl_absorpt_empirical_full_min 0.718