Regio- and Stereoselective Synthesis of the Core Structure of Hexahydrobenzo[<i>c</i>]phenanthridine Alkaloids via Redox-Neutral Cp*Rh(III)-Catalyzed C-H/N-H Annulation of Cyclic Alkenes with Benzamides.
Das Adhikari, Gopal Krushna; Chebolu, Rajesh; Ravikumar, Ponneri Chandrababu; ACS omega 5 (2020) 24033–24044; doi:10.1021/acsomega.0c03434

data_4518036
_publ_section_title
;
 Regio- and Stereoselective Synthesis of the Core Structure of
 Hexahydrobenzo[<i>c</i>]phenanthridine Alkaloids via Redox-Neutral
 Cp*Rh(III)-Catalyzed C-H/N-H Annulation of Cyclic Alkenes with
 Benzamides.
;
_journal_issue                   37
_journal_name_full               'ACS omega'
_journal_page_first              24033
_journal_page_last               24044
_journal_paper_doi               10.1021/acsomega.0c03434
_journal_volume                  5
_journal_year                    2020
_chemical_formula_moiety         'C17 H15 N O'
_chemical_formula_sum            'C17 H15 N O'
_chemical_formula_weight         249.30
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-06-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                105.516(2)
_cell_angle_beta                 102.852(3)
_cell_angle_gamma                102.045(3)
_cell_formula_units_Z            4
_cell_length_a                   9.3640(4)
_cell_length_b                   12.4629(4)
_cell_length_c                   12.6747(3)
_cell_measurement_reflns_used    11079
_cell_measurement_temperature    298
_cell_measurement_theta_max      75.3420
_cell_measurement_theta_min      3.7960
_cell_volume                     1331.73(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (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_temperature      298.0
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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 -35.00   0.50    1.00    --  -38.50 -36.00 104.00  140
  2  \w    -42.00  28.00   0.50    1.00    --  -38.50  36.00 -98.00  140
  3  \w     46.00 116.00   0.50    1.00    --   49.31  36.00 -98.00  140
  4  \w    -17.00  53.00   0.50    1.00    --   49.31 -36.00 104.00  140
  5  \w    100.00 169.00   0.50    3.00    --  102.63  36.00 -98.00  138
  6  \w     36.00 106.00   0.50    3.00    --  102.63 -36.00 104.00  140
  7  \w    -89.00  -2.00   0.50    1.00    --  -38.50 125.00 -90.00  174
  8  \w   -108.00 -33.00   0.50    1.00    --  -38.50 -19.00 150.00  150
  9  \w   -101.00 -27.00   0.50    1.00    --  -38.50 -57.00  90.00  148
 10  \w     24.00 100.00   0.50    1.00    --   49.31-125.00 -30.00  152
 11  \w     34.00 110.00   0.50    3.00    --  102.63 -94.00-150.00  152
 12  \w     34.00 111.00   0.50    3.00    --  102.63 -15.00  60.00  154
 13  \w     35.00 106.00   0.50    3.00    --  102.63 -30.00-120.00  142
 14  \w     35.00 106.00   0.50    3.00    --  102.63 -30.00  30.00  142
 15  \w     38.00 118.00   0.50    3.00    --  102.63-125.00  30.00  160
 16  \w     40.00 116.00   0.50    3.00    --  102.63 -61.00 120.00  152
 17  \w     34.00 110.00   0.50    3.00    --  102.63 -94.00 -90.00  152
 18  \w     90.00 165.00   0.50    3.00    --  102.63  61.00  60.00  150
 19  \w     90.00 165.00   0.50    3.00    --  102.63  61.00-150.00  150
 20  \w     40.00 116.00   0.50    3.00    --  102.63 -61.00  60.00  152
 21  \w     38.00 126.00   0.50    3.00    --  102.63 -77.00-150.00  176
 22  \w     95.00 171.00   0.50    3.00    --  102.63  15.00  30.00  152
 23  \w     40.00 116.00   0.50    3.00    --  102.63 -61.00 -30.00  152
 24  \w     34.00 110.00   0.50    3.00    --  102.63 -94.00  90.00  152
 25  \w     38.00 107.00   0.50    3.00    --  102.63 -45.00-120.00  138
 26  \w     98.00 167.00   0.50    3.00    --  102.63  45.00-120.00  138
 27  \w     38.00 118.00   0.50    3.00    --  102.63-125.00 150.00  160
 28  \w     34.00 110.00   0.50    3.00    --  102.63 -94.00  30.00  152
 29  \w     94.00 168.00   0.50    3.00    --  102.63 125.00 150.00  148
 30  \w     26.00 114.00   0.50    1.00    --   49.31  77.00-180.00  176
 31  \w     26.00 114.00   0.50    1.00    --   49.31  77.00 -90.00  176
 32  \w     26.00 114.00   0.50    1.00    --   49.31  77.00 -30.00  176
 33  \w     26.00 114.00   0.50    1.00    --   49.31  77.00 120.00  176
 34  \w     26.00 114.00   0.50    1.00    --   49.31  77.00  60.00  176
 35  \w     26.00 114.00   0.50    1.00    --   49.31  77.00-120.00  176
 36  \w     26.00 114.00   0.50    1.00    --   49.31  77.00  30.00  176
 37  \w     80.00 165.00   0.50    3.00    --  102.63  77.00 -60.00  170
 38  \w     95.00 171.00   0.50    3.00    --  102.63  15.00 150.00  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0835
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            4749
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         67.000
_diffrn_reflns_theta_min         3.788
_exptl_absorpt_coefficient_mu    0.605
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60172
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (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    1.243
_exptl_crystal_description       cube
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.283
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         4749
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.1021
_refine_ls_R_factor_gt           0.0892
_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^)+(0.1264P)^2^+0.5678P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2384
_refine_ls_wR_factor_ref         0.2479
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3827
_reflns_number_total             4749
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao0c03434_si_002.cif
_cod_data_source_block           pcr-gkd-23-8-18
_cod_depositor_comments
;
Adding full bibliography for 4518035--4518036.cif.

2025-09-12
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C68 H60 N4 O4'
_cod_original_formula_weight         997.20
_cod_original_formula_moiety         '4(C17 H15 N O)'
_cod_original_formula_units_Z            1
_cod_original_cell_volume        1331.73(8)
_cod_database_code               4518036
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.863
_shelx_estimated_absorpt_t_min   0.859
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.813(7)
 0.187(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
3.a Ternary CH refined with riding coordinates:
 C26(H26), C9(H9), C8(H8), C25(H25)
3.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C16(H16A,H16B), C17(H17A,H17B), C33(H33A,H33B)
3.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N1(H1), C28(H28), C6(H6), C3(H3), C29(H29), C11(H11), C31(H31),
 C23(H23), C20(H20), C5(H5), C30(H30), C4(H4), C14(H14), C21(H21), C22(H22),
 C13(H13), C12(H12)
;
_shelx_res_checksum              87285
_shelx_hkl_checksum              31703
_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
;