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_4037797
_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         'C16 H18 N2 O4'
_chemical_formula_sum            'C16 H18 N2 O4'
_chemical_formula_weight         302.32
_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   geom
_audit_creation_date             2019-08-07
_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            4
_cell_length_a                   8.77594(11)
_cell_length_b                   10.37922(11)
_cell_length_c                   16.1674(2)
_cell_measurement_reflns_used    5234
_cell_measurement_temperature    100
_cell_measurement_theta_max      75.5880
_cell_measurement_theta_min      5.0480
_cell_volume                     1472.65(3)
_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      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.2603
_diffrn_detector_type            Onyx
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_details
;
  1 omega -114.00  -20.00   1.0000    6.5750
omega____ theta____ kappa____ phi______ frames
    -      -44.1816  -57.0000    0.0000 94

  2 omega  -25.00   68.00   1.0000    6.5750
omega____ theta____ kappa____ phi______ frames
    -       44.1816  -57.0000 -120.0000 93

  3 omega   36.00  121.00   1.0000   26.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0049 -125.0000  120.0000 85

  4 omega   27.00  109.00   1.0000   26.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0049  -95.0000 -120.0000 82

  5 omega   34.00  178.00   1.0000   26.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0049    0.0000 -180.0000 144

  6 omega   35.00   69.00   1.0000   26.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0049  -30.0000 -150.0000 34

  7 omega -115.00  -22.00   1.0000    6.5750
omega____ theta____ kappa____ phi______ frames
    -      -44.1816  -38.0000 -120.0000 93

  8 omega -114.00  -20.00   1.0000    6.5750
omega____ theta____ kappa____ phi______ frames
    -      -44.1816  -57.0000  150.0000 94

  9 omega   35.00   69.00   1.0000   26.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0049  -30.0000   60.0000 34

 10 omega   85.00  118.00   1.0000   26.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0049   30.0000 -120.0000 33

 11 omega   35.00   69.00   1.0000   26.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0049  -30.0000  120.0000 34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Onyx, Ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1616947000
_diffrn_orient_matrix_UB_12      -0.0368873000
_diffrn_orient_matrix_UB_13      -0.0286953000
_diffrn_orient_matrix_UB_21      0.0349209000
_diffrn_orient_matrix_UB_22      0.1428793000
_diffrn_orient_matrix_UB_23      -0.0177226000
_diffrn_orient_matrix_UB_31      0.0589435000
_diffrn_orient_matrix_UB_32      0.0165467000
_diffrn_orient_matrix_UB_33      0.0890390000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0422
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            7998
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.617
_diffrn_reflns_theta_min         5.064
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.818
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91728
_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_density_diffrn    1.364
_exptl_crystal_description       irregular
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 984 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.24(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         2825
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0421
_refine_ls_R_factor_gt           0.0373
_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^)+(0.0584P)^2^+0.0866P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0954
_refine_ls_wR_factor_ref         0.0984
_reflns_Friedel_coverage         0.645
_reflns_Friedel_fraction_full    0.931
_reflns_Friedel_fraction_max     0.864
_reflns_number_gt                2638
_reflns_number_total             2825
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03402_si_002.cif
_cod_data_source_block           jv-dl-nolabel
_cod_database_code               4037797
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         C10H10N2O2
_reflns_odcompleteness_completeness 99.94
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C8(H8), C7(H7), C9(H9)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              1050
_shelx_hkl_checksum              59252
_olex2_date_sample_data_collection 2019-08-06
_olex2_exptl_crystal_mounting_method 'Mounted on a Kryoloop using paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'