Synthesis of the 5/5-spiroindimicin alkaloids: development of a general synthetic approach and biological investigations.
Banerjee, Ankush; Brisco, Tiffany A.; Ray, Sneha; Datta, Arani; Zhang, Xiaoyu; Zhang, Zhen; Busse, Alexander A.; Niederstrasser, Hanspeter; Sumida, Krissty; Posner, Bruce A.; Wetzel, Dawn M.; Phillips, Margaret A.; Smith, Myles W.; Organic & biomolecular chemistry 22 (2024) 9413–9425; doi:10.1039/d4ob01552e

data_7160196
_publ_section_title
;
 Synthesis of the 5/5-spiroindimicin alkaloids: development of a general
 synthetic approach and biological investigations.
;
_journal_issue                   48
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9413
_journal_page_last               9425
_journal_paper_doi               10.1039/d4ob01552e
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C17 H15 I N2 O6'
_chemical_formula_sum            'C17 H15 I N2 O6'
_chemical_formula_weight         470.21
_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   mixed
_audit_block_doi                 10.5517/ccdc.csd.cc2g0wgv
_audit_creation_date             2023-05-23
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6380)
;
_audit_update_record
;
2023-05-23 deposited with the CCDC.	2024-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                96.120(4)
_cell_angle_beta                 91.980(3)
_cell_angle_gamma                96.465(4)
_cell_formula_units_Z            4
_cell_length_a                   10.8128(4)
_cell_length_b                   11.8787(6)
_cell_length_c                   13.9111(5)
_cell_measurement_reflns_used    10217
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      76.3520
_cell_measurement_theta_min      3.2090
_cell_volume                     1763.33(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Shelxtl-Plus/XP, Bruker AXS, Inc. 2009'
_computing_publication_material  'Shelxtl-Plus, Bruker AXS, Inc. 2009'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.956
_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   -119.00 -35.00   0.50    4.50    --  -48.08 -53.00  28.00  168
  2  \w     36.00 120.00   0.50    4.50    --   48.08  53.00 172.00  168
  3  \w    -23.00  57.00   0.50    4.50    --   48.08 -53.00  28.00  160
  4  \w   -176.00 -92.00   0.50   20.00    -- -105.11 -53.00  28.00  168
  5  \w    -63.00 -33.00   0.50   20.00    -- -105.11  53.00 172.00   60
  6  \w     93.00 176.00   0.50   20.00    --  105.11  53.00 172.00  166
  7  \w    -26.00  26.00   0.50    4.50    --  -48.08  19.00 120.00  104
  8  \w    -61.00  24.00   0.50    4.50    --  -48.08  53.00 172.00  170
  9  \w    -92.00 -13.00   0.50    4.50    --  -48.08 125.00 -60.00  158
 10  \w    -25.00  20.00   0.50    4.50    --   48.08 -19.00-120.00   90
 11  \w    -24.00  39.00   0.50    4.50    --   48.08 -38.00-150.00  126
 12  \w    -25.00  20.00   0.50    4.50    --   48.08 -19.00  90.00   90
 13  \w   -174.00 -87.00   0.50   20.00    -- -105.11-125.00 150.00  174
 14  \w   -176.00 -90.00   0.50   20.00    -- -105.11 -61.00 -30.00  172
 15  \w   -111.00 -36.00   0.50   20.00    -- -105.11 125.00   0.00  150
 16  \w   -174.00 -87.00   0.50   20.00    -- -105.11-125.00  90.00  174
 17  \w   -125.00 -33.00   0.50   20.00    -- -105.11 143.00  84.79  184
 18  \w   -176.00 -90.00   0.50   20.00    -- -105.11 -61.00 -41.44  172
 19  \w   -176.00-100.00   0.50   20.00    -- -105.11 -95.00 120.00  152
 20  \w    -75.00 -33.00   0.50   20.00    -- -105.11  61.00  90.00   84
 21  \w   -109.00 -37.00   0.50   20.00    -- -105.11 115.00  52.19  144
 22  \w   -116.00 -33.00   0.50   20.00    -- -105.11  77.00 120.00  166
 23  \w   -177.00 -95.00   0.50   20.00    -- -105.11 -15.00   0.00  164
 24  \w   -111.00 -36.00   0.50   20.00    -- -105.11 125.00-120.00  150
 25  \w   -111.00 -36.00   0.50   20.00    -- -105.11 125.00 150.00  150
 26  \w    -75.00 -33.00   0.50   20.00    -- -105.11  61.00  30.00   84
 27  \w    -90.00 -35.00   0.50   20.00    -- -105.11 104.00-121.59  110
 28  \w     33.00 105.00   0.50   20.00    --  105.11 -95.00   0.00  144
 29  \w     94.00 176.00   0.50   20.00    --  105.11  45.00  30.00  164
 30  \w     33.00 105.00   0.50   20.00    --  105.11 -95.00 -60.00  144
 31  \w     36.00 112.00   0.50   20.00    --  105.11-125.00-180.00  152
 32  \w     36.00 120.00   0.50    4.50    --   48.08  52.00 125.81  168
 33  \w     35.00 120.00   0.50    4.50    --   48.08  56.00  -6.17  170
 34  \w     36.00 120.00   0.50    4.50    --   48.08  53.00 -56.93  168
 35  \w     35.00 120.00   0.50    4.50    --   48.08  54.00-150.17  170
 36  \w     35.00 120.00   0.50    4.50    --   48.08  56.00-114.34  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0463695000
_diffrn_orient_matrix_UB_12      0.1184245000
_diffrn_orient_matrix_UB_13      0.0126135000
_diffrn_orient_matrix_UB_21      -0.1122626000
_diffrn_orient_matrix_UB_22      -0.0446662000
_diffrn_orient_matrix_UB_23      -0.0702860000
_diffrn_orient_matrix_UB_31      -0.0765030000
_diffrn_orient_matrix_UB_32      -0.0350725000
_diffrn_orient_matrix_UB_33      0.0856359000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0765
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            28722
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.890
_diffrn_reflns_theta_min         3.199
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.611
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50779
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.88a (Rigaku Oxford Diffraction, 2023)
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    1.771
_exptl_crystal_description       prism
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.519
_refine_diff_density_min         -1.428
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         7208
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0530
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0895P)^2^+5.9843P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1424
_refine_ls_wR_factor_ref         0.1437
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6969
_reflns_number_total             7208
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01552e2.cif
_cod_data_source_block           1-ab-40bx3
_cod_depositor_comments
'Adding full bibliography for 7160196--7160199.cif.'
_cod_original_cell_volume        1763.32(13)
_cod_database_code               7160196
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C17H15N2O4I
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N3-H3 = N1-H1
 0.84 with sigma of 0.02
 O5-H5 = O11-H11
 0.84 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C29(H29), C30(H30), C31(H31), C32(H32)
3.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C17(H17A,H17B,H17C), C23(H23A,H23B,H23C),
 C25(H25A,H25B,H25C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              62928
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.322
_oxdiff_exptl_absorpt_empirical_full_min 0.491