Discovery of an Unexpected 1,4-Oxazepine-Linked <i>seco</i>-Fluostatin Heterodimer by Inactivation of the Oxidoreductase-Encoding Gene <i>flsP</i>.
Huang, Chunshuai; Yang, Chunfang; Zhang, Wenjun; Zhang, Liping; Zhu, Yiguang; Zhang, Changsheng; Journal of natural products 84 (2021) 2336–2344; doi:10.1021/acs.jnatprod.1c00461

data_1564534
_publ_section_title
;
 Discovery of an Unexpected 1,4-Oxazepine-Linked <i>seco</i>-Fluostatin
 Heterodimer by Inactivation of the Oxidoreductase-Encoding Gene
 <i>flsP</i>.
;
_journal_issue                   8
_journal_name_full               'Journal of natural products'
_journal_page_first              2336
_journal_page_last               2344
_journal_paper_doi               10.1021/acs.jnatprod.1c00461
_journal_volume                  84
_journal_year                    2021
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C19 H15 Cl O6, H2 O'
_chemical_formula_sum            'C19 H17 Cl O7'
_chemical_formula_weight         392.77
_chemical_name_systematic
(1R,2S,3R)-3-chloro-2,6,7-trihydroxy-1-methoxy-3-methyl-2,3-dihydro-1H-benzo[a]fluorene-4,11-dione
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2021-07-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.1790(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.86876(5)
_cell_length_b                   11.85008(7)
_cell_length_c                   21.07510(10)
_cell_measurement_reflns_used    24402
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.9830
_cell_measurement_theta_min      4.2230
_cell_volume                     1697.967(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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   -116.00 -18.00   1.00    1.00    --  -41.89 -37.00 120.00   98
  2  \w   -116.00 -18.00   1.00    1.00    --  -41.89 -37.00 150.00   98
  3  \w    -74.00  34.00   1.00    1.00    --  -41.89  77.00 120.00  108
  4  \w    -33.00  66.00   1.00    1.00    --   41.89 -37.00-150.00   99
  5  \w     23.00  98.00   1.00    1.00    --   41.89-125.00   0.00   75
  6  \w     18.00 116.00   1.00    1.00    --   41.89  37.00  60.00   98
  7  \w     29.00 103.00   1.00    1.00    --   41.89-134.00 131.00   74
  8  \w     32.00 140.00   1.00    2.00    --  107.79 -77.00 -30.00  108
  9  \w     32.00 136.00   1.00    2.00    --  107.79 -30.00 120.00  104
 10  \w     80.00 178.00   1.00    2.00    --  107.79  30.00  30.00   98
 11  \w     32.00 136.00   1.00    2.00    --  107.79 -30.00  30.00  104
 12  \w     35.00 134.00   1.00    2.00    --  107.79 -45.00-150.00   99
 13  \w     25.00 109.00   1.00    2.00    --  107.79 -94.00 -30.00   84
 14  \w     35.00 122.00   1.00    2.00    --  107.79-125.00-180.00   87
 15  \w     80.00 178.00   1.00    2.00    --  107.79  30.00  90.00   98
 16  \w     94.00 178.00   1.00    2.00    --  107.79 125.00  60.00   84
 17  \w     55.00 178.00   1.00    2.00    --  107.79  15.00 -60.00  123
 18  \w    101.00 178.00   1.00    2.00    --  107.79  96.00 -51.00   77
 19  \w     25.00 109.00   1.00    2.00    --  107.79 -94.00-150.00   84
 20  \w   -118.00  -9.00   1.00    1.00    --  -41.89 -77.00  90.00  109
 21  \w   -115.00 -14.00   1.00    1.00    --  -41.89 -57.00   0.00  101
 22  \w   -118.00  -9.00   1.00    1.00    --  -41.89 -77.00 -60.00  109
 23  \w    -66.00  33.00   1.00    1.00    --  -41.89  37.00  60.00   99
 24  \w      9.00 118.00   1.00    1.00    --   41.89  77.00-150.00  109
 25  \w     75.00 178.00   1.00    2.00    --  107.79  77.00 120.00  103
 26  \w     79.00 178.00   1.00    2.00    --  107.79  61.00 -90.00   99
 27  \w     82.00 178.00   1.00    2.00    --  107.79  45.00-180.00   96
 28  \w     79.00 178.00   1.00    2.00    --  107.79  61.00  30.00   99
 29  \w     75.00 178.00   1.00    2.00    --  107.79  77.00  90.00  103
 30  \w     75.00 178.00   1.00    2.00    --  107.79  77.00-180.00  103
 31  \w     75.00 162.00   1.00    2.00    --  107.79  77.00 -30.00   87
 32  \w     75.00 178.00   1.00    2.00    --  107.79  77.00 -60.00  103
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0525637000
_diffrn_orient_matrix_UB_12      0.0327824000
_diffrn_orient_matrix_UB_13      -0.0710994000
_diffrn_orient_matrix_UB_21      -0.0655808000
_diffrn_orient_matrix_UB_22      0.1174949000
_diffrn_orient_matrix_UB_23      0.0199463000
_diffrn_orient_matrix_UB_31      0.2105000000
_diffrn_orient_matrix_UB_32      0.0448663000
_diffrn_orient_matrix_UB_33      -0.0002368000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_av_unetI/netI     0.0221
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            32152
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.042
_diffrn_reflns_theta_min         4.239
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.376
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25380
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.536
_exptl_crystal_description       needle
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.250
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 3096 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     500
_refine_ls_number_reflns         6802
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0280
_refine_ls_R_factor_gt           0.0278
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0462P)^2^+0.3486P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0750
_refine_ls_wR_factor_ref         0.0752
_reflns_Friedel_coverage         0.883
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.971
_reflns_number_gt                6735
_reflns_number_total             6802
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np1c00461_si_002.cif
_cod_data_source_block           1611013
_cod_original_cell_volume        1697.968(18)
_cod_database_code               1564534
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     Y20-6
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups, All O(H,H) groups
2.a Riding coordinates:
 O25(H25A,H25B)
2.b Free rotating group:
 O26(H26A,H26B)
2.c Ternary CH refined with riding coordinates:
 C1(H1), C1'(H1'), C3(H2A), C2'(H2')
2.d Aromatic/amide H refined with riding coordinates:
 C5'(H5'), C5(H5), C10(H10), C10'(H10'), C8'(H8'), C9(H8), C9'(H9'), C14(H9)
2.e Idealised Me refined as rotating group:
 C13(H13D,H13E,H13F), C12'(H12A,H12B,H12C), C12(H12D,H12E,H12F), C13'(H13A,
 H13B,H13C)
2.f Idealised tetrahedral OH refined as rotating group:
 O19(H19), O20(H20), O2(H2), O15(H15), O6(H6), O7(H7)
;
_shelx_res_checksum              72452
_shelx_hkl_checksum              78869
_olex2_submission_original_sample_id Y20-6
_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 2.735
_oxdiff_exptl_absorpt_empirical_full_min 0.553