Tricyclic Imidazolidin-4-ones by Witkop Oxidation of Tetrahydro-β-carbolines.
Leas, Derek Andrew; Dong, Yuxiang; Garrison, Jered C.; Wang, Xiaofang; Ezell, Edward L.; Stack, Douglas Edward; Vennerstrom, Jonathan L.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.9b03402

data_4037792
_publ_section_title
;
 Tricyclic Imidazolidin-4-ones by Witkop Oxidation of
 Tetrahydro-\b-carbolines.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03402
_journal_year                    2020
_chemical_formula_moiety         'C13 H16 N2 O2'
_chemical_formula_sum            'C13 H16 N2 O2'
_chemical_formula_weight         232.28
_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
_audit_creation_date             2019-04-08
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.9788(2)
_cell_length_b                   12.3213(2)
_cell_length_c                   19.5547(4)
_cell_measurement_reflns_used    5658
_cell_measurement_temperature    120
_cell_measurement_theta_max      75.4540
_cell_measurement_theta_min      4.2110
_cell_volume                     2404.29(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.2603
_diffrn_detector_type            Onyx
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_details
;
  1 omega  -68.00   20.00   1.0000   11.0350
omega____ theta____ kappa____ phi______ frames
    -      -43.9628   57.0000  -30.0000 88

  2 omega   22.00  109.00   1.0000   11.0350
omega____ theta____ kappa____ phi______ frames
    -       43.9628   38.0000 -180.0000 87

  3 omega   81.00  108.00   1.0000   11.0350
omega____ theta____ kappa____ phi______ frames
    -       43.9628   57.0000  -90.0000 27

  4 omega   46.00   77.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -45.0000 -180.0000 31

  5 omega   38.00   69.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -30.0000    0.0000 31

  6 omega   37.00   66.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -30.0000  150.0000 29

  7 omega   36.00   61.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -30.0000   30.0000 25

  8 omega   40.00   70.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -45.0000  120.0000 30

  9 omega   61.00  105.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -95.0000 -180.0000 44

 10 omega   40.00   77.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -45.0000  -60.0000 37

 11 omega   37.00   69.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -30.0000  120.0000 32

 12 omega   40.00  134.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000  -77.0000   30.0000 94

 13 omega  114.00  178.00   1.0000   44.1350
omega____ theta____ kappa____ phi______ frames
    -      109.0000   30.0000  -60.0000 64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Onyx, Ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0010249000
_diffrn_orient_matrix_UB_12      -0.1196445000
_diffrn_orient_matrix_UB_13      0.0229915000
_diffrn_orient_matrix_UB_21      -0.1424178000
_diffrn_orient_matrix_UB_22      0.0133809000
_diffrn_orient_matrix_UB_23      0.0293792000
_diffrn_orient_matrix_UB_31      -0.0598238000
_diffrn_orient_matrix_UB_32      -0.0340044000
_diffrn_orient_matrix_UB_33      -0.0692869000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0454
_diffrn_reflns_av_unetI/netI     0.0480
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            9895
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.155
_diffrn_reflns_theta_min         4.241
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.710
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39367
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.277
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 1775 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.15(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         4832
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0473
_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^)+(0.0796P)^2^+0.3509P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1276
_refine_ls_wR_factor_ref         0.1339
_reflns_Friedel_coverage         0.730
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.934
_reflns_number_gt                4490
_reflns_number_total             4832
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03402_si_002.cif
_cod_data_source_block           vennerstrom-mc14
_cod_database_code               4037792
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         C13H16N2O2
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C2(H2A,H2B), C14(H14A,H14B), C1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C8(H8), N4(H4), C5(H5), C20(H20), C21(H21), C18(H18), C19(H19),
 C6(H6), C7(H7)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C26(H26A,H26B,H26C), C25(H25A,H25B,
 H25C)
;
_shelx_res_checksum              78284
_shelx_hkl_checksum              47752
_olex2_date_sample_data_collection 2019-03-14
_olex2_exptl_crystal_mounting_method 'Mounted on a Kryoloop in paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'