Unexpected amine-triggered skeletal modification of fascaplysin and its derivatives: rapid access to δ,γ-biscarbolines.
Wang, Zizhen; Wang, Huanhuan; Xu, Mei; Wang, Liping; Liu, Sheng; Organic & biomolecular chemistry 23 (2025) 2096–2100; doi:10.1039/d4ob02014f

data_7160339
_publ_section_title
;
 Unexpected amine-triggered skeletal modification of fascaplysin and its
 derivatives: rapid access to &#x3b4;,&#x3b3;-biscarbolines.
;
_journal_issue                   9
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2096
_journal_page_last               2100
_journal_paper_doi               10.1039/d4ob02014f
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'O4 S, 2(C25 H20 N3 O), C H4 O, H2 O'
_chemical_formula_sum            'C51 H46 N6 O8 S'
_chemical_formula_weight         903.00
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-04
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-12-12 deposited with the CCDC.	2025-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                91.030(2)
_cell_angle_beta                 102.388(2)
_cell_angle_gamma                112.335(2)
_cell_formula_units_Z            2
_cell_length_a                   11.8728(3)
_cell_length_b                   13.2500(3)
_cell_length_c                   14.9033(4)
_cell_measurement_reflns_used    8365
_cell_measurement_temperature    104(5)
_cell_measurement_theta_max      73.9700
_cell_measurement_theta_min      3.0580
_cell_volume                     2105.24(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      104(5)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.957
_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    -46.00   4.00   0.50    0.50    --    0.00 -77.00  60.00  100
  2  \w    -31.00  27.00   0.50    0.50    --    0.00 -82.00-180.00  116
  3  \w    -29.00  31.00   0.50    0.50    --    0.00 -82.00 120.00  120
  4  \w    -33.00  29.00   0.50    0.50    --    0.00 -82.00   0.00  124
  5  \w    -26.00   6.00   0.50    0.50    --    0.00 -77.00 -90.00   64
  6  \w     45.00  70.00   0.50    0.50    --   95.80 -77.00-150.00   50
  7  \w     17.00  43.00   0.50    0.50    --   95.80 -77.00-150.00   52
  8  \w     24.00  50.00   0.50    0.50    --   95.80 -82.00  30.00   52
  9  \w     76.00 116.00   0.50    0.50    --   95.80 -82.00-180.00   80
 10  \w    116.00 184.00   0.50    0.50    --   95.80  15.00 -30.00  136
 11  \w     52.00 127.00   0.50    0.50    --   95.80 -82.00 -90.00  150
 12  \w      6.00 127.00   0.50    0.50    --   95.80 -82.00  60.00  242
 13  \w     83.00 140.00   0.50    0.50    --   95.80  61.00   0.00  114
 14  \w      9.00  53.00   0.50    0.50    --   95.80 -82.00 120.00   88
 15  \w     11.00 112.00   0.50    0.50    --   95.80 -30.00 120.00  202
 16  \w      6.00 114.00   0.50    0.50    --   95.80 -61.00 -90.00  216
 17  \w     72.00 101.00   0.50    0.50    --   95.80  15.00 -30.00   58
 18  \w     84.00 122.00   0.50    0.50    --   95.80 -82.00 120.00   76
 19  \w     91.00 168.00   0.50    0.50    --   95.80  82.00   0.00  154
 20  \w      7.00 107.00   0.50    0.50    --   95.80 -61.00  60.00  200
 21  \w     76.00 101.00   0.50    0.50    --   95.80 -82.00  30.00   50
 22  \w     81.00 106.00   0.50    0.50    --   95.80 -82.00 -30.00   50
 23  \w     74.00 110.00   0.50    0.50    --   95.80 -30.00-150.00   72
 24  \w    116.00 141.00   0.50    0.50    --   95.80  82.00  60.00   50
 25  \w      8.00  47.00   0.50    0.50    --   95.80 -30.00-150.00   78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0824901000
_diffrn_orient_matrix_UB_12      0.0127832000
_diffrn_orient_matrix_UB_13      -0.0694225000
_diffrn_orient_matrix_UB_21      -0.1154541000
_diffrn_orient_matrix_UB_22      -0.0239730000
_diffrn_orient_matrix_UB_23      -0.0806632000
_diffrn_orient_matrix_UB_31      0.0272061000
_diffrn_orient_matrix_UB_32      0.1235162000
_diffrn_orient_matrix_UB_33      0.0035367000
_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  0.0580
_diffrn_reflns_av_unetI/netI     0.0752
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            21345
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.312
_diffrn_reflns_theta_min         3.054
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.240
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93053
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       block
_exptl_crystal_F_000             948
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.439
_refine_diff_density_min         -0.485
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     602
_refine_ls_number_reflns         8209
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0894
_refine_ls_R_factor_gt           0.0544
_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^)+(0.0552P)^2^+1.5573P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1326
_refine_ls_wR_factor_ref         0.1417
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6517
_reflns_number_total             8209
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob02014f2.cif
_cod_data_source_block           326
_cod_depositor_comments          'Adding full bibliography for 7160339.cif.'
_cod_database_code               7160339
_shelx_shelxl_version_number     2018/3
_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, All O(H) groups, All O(H,H) groups
2.a Free rotating group:
 O7(H7A,H7B)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C43(H43A,H43B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N3(H3), C2(H2A), C3(H3A), C4(H4), C5(H5), C9(H9), C11(H11), C12(H12),
 C13(H13), C14(H14), C19(H19), C20(H20), C22(H22), C23(H23), N4(H4A), N6(H6),
 C27(H27), C28(H28), C29(H29), C30(H30), C38(H38), C39(H39), C40(H40), C42(H42),
  C45(H45), C46(H46), C47(H47), C49(H49), C50(H50)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C51(H51A,H51B,H51C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2B)
;
_shelx_res_checksum              88555
_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 1.238
_oxdiff_exptl_absorpt_empirical_full_min 0.762