Asperginols A and B, Diterpene Pyrones, from an <i>Aspergillus</i> sp. and the Structure Revision of Previously Reported Analogues.
Al-Khdhairawi, Amjad Ayad Qatran; Low, Yun-Yee; Manshoor, Nurhuda; Arya, Aditya; Jelecki, Maciej; Alshawsh, Mohammed Abdullah; Kamran, Sareh; Suliman, Rasha Saad; Low, Anis; Shivanagere Nagojappa, Narendra Babu; Weber, Jean-Frédéric F; Journal of natural products 83 (2020) 3564–3570; doi:10.1021/acs.jnatprod.0c00618

data_1559923
_publ_section_title
;
 Asperginols A and B, Diterpene Pyrones, from an <i>Aspergillus</i> sp.
 and the Structure Revision of Previously Reported Analogues.
;
_journal_issue                   12
_journal_name_full               'Journal of natural products'
_journal_page_first              3564
_journal_page_last               3570
_journal_paper_doi               10.1021/acs.jnatprod.0c00618
_journal_volume                  83
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H40 O6'
_chemical_formula_sum            'C27 H40 O6'
_chemical_formula_weight         460.59
_chemical_melting_point          554.5(5)
_chemical_name_common            'Asperginol A'
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5284(2)
_cell_length_b                   13.0274(2)
_cell_length_c                   17.2404(2)
_cell_measurement_reflns_used    29018
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.1360
_cell_measurement_theta_min      4.2090
_cell_volume                     2589.25(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'X-SEED (Barbour, 2001)'
_computing_publication_material  'enCIFer (Allen et al., 2004)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4041
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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      2.00  33.00   1.00    1.00    --   38.00  88.00-132.17   31
  2  \w   -116.00 -17.00   1.00    1.00    --  -41.63 -37.00 -90.00   99
  3  \w   -114.00 -13.00   1.00    1.00    --  -41.63 -57.00   0.00  101
  4  \w   -114.00 -13.00   1.00    1.00    --  -41.63 -57.00 120.00  101
  5  \w   -115.00 -17.00   1.00    1.00    --  -41.63 -41.00-160.20   98
  6  \w    -96.00  -2.00   1.00    1.00    --  -41.63 125.00-150.00   94
  7  \w     23.00  98.00   1.00    1.00    --   41.63-125.00-180.00   75
  8  \w     23.00  98.00   1.00    1.00    --   41.63-125.00  90.00   75
  9  \w      6.00  33.00   1.00    1.00    --   42.00  88.00 107.99   27
 10  \w      6.00  33.00   1.00    1.00    --   42.00  88.00 -19.87   27
 11  \w     21.00  47.00   1.00    1.00    --   54.00  79.00  14.63   26
 12  \w     20.00  46.00   1.00    1.00    --   54.00  81.00 174.86   26
 13  \w     21.00  49.00   1.00    1.00    --   54.00  78.00  68.79   28
 14  \w     20.00  46.00   1.00    1.00    --   54.00  81.00 103.95   26
 15  \w     21.00  47.00   1.00    1.00    --   54.00  79.00-121.25   26
 16  \w     20.00  46.00   1.00    1.00    --   54.00  81.00 -57.19   26
 17  \w     33.00 142.00   1.00    1.00    --   66.00  77.00  83.67  109
 18  \w     33.00 142.00   1.00    1.00    --   66.00  77.00 -31.52  109
 19  \w     34.00 142.00   1.00    1.00    --   66.00  76.00-139.66  108
 20  \w     34.00 141.00   1.00    1.00    --   66.00  75.00 -83.32  107
 21  \w     37.00 146.00   1.00    1.00    --   70.00  77.00 123.51  109
 22  \w     38.00 145.00   1.00    1.00    --   70.00  75.00 167.95  107
 23  \w     37.00 146.00   1.00    1.00    --   70.00  77.00 109.12  109
 24  \w     42.00 150.00   1.00    1.00    --   74.00  76.00  40.81  108
 25  \w     42.00 149.00   1.00    1.00    --   74.00  75.00 -18.78  107
 26  \w     41.00 150.00   1.00    1.00    --   74.00  77.00   3.87  109
 27  \w     42.00 150.00   1.00    1.00    --   74.00  76.00-114.76  108
 28  \w     26.00 109.00   1.00    2.50    --  108.56 -94.00  90.00   83
 29  \w     76.00 178.00   1.00    2.50    --  108.56  77.00   0.00  102
 30  \w     79.00 178.00   1.00    2.50    --  108.56  61.00 150.00   99
 31  \w     76.00 178.00   1.00    2.50    --  108.56  77.00 -30.00  102
 32  \w     79.00 178.00   1.00    2.50    --  108.56  61.00   0.00   99
 33  \w     79.00 178.00   1.00    2.50    --  108.56  61.00  90.00   99
 34  \w     76.00 178.00   1.00    2.50    --  108.56  77.00  30.00  102
 35  \w     94.00 178.00   1.00    2.50    --  108.56 125.00 120.00   84
 36  \w     26.00 109.00   1.00    2.50    --  108.56 -94.00-180.00   83
 37  \w     76.00 178.00   1.00    2.50    --  108.56  77.00 -90.00  102
 38  \w     26.00 109.00   1.00    2.50    --  108.56 -94.00  60.00   83
 39  \w     76.00 178.00   1.00    2.50    --  108.56  77.00-180.00  102
 40  \w     76.00 178.00   1.00    2.50    --  108.56  77.00 150.00  102
 41  \w     76.00 178.00   1.00    2.50    --  108.56  77.00-150.00  102
 42  \w     26.00 109.00   1.00    2.50    --  108.56 -94.00-120.00   83
 43  \w     79.00 178.00   1.00    2.50    --  108.56  61.00 -30.00   99
 44  \w     76.00 178.00   1.00    2.50    --  108.56  77.00  60.00  102
 45  \w     79.00 178.00   1.00    2.50    --  108.56  61.00 120.00   99
 46  \w     76.00 178.00   1.00    2.50    --  108.56  77.00-120.00  102
 47  \w     79.00 178.00   1.00    2.50    --  108.56  61.00 -90.00   99
 48  \w     79.00 178.00   1.00    2.50    --  108.56  61.00  60.00   99
 49  \w     79.00 178.00   1.00    2.50    --  108.56  61.00-180.00   99
 50  \w     79.00 178.00   1.00    2.50    --  108.56  61.00 -60.00   99
 51  \w     76.00 178.00   1.00    2.50    --  108.56  77.00  90.00  102
 52  \w     35.00 122.00   1.00    2.50    --  108.56-125.00   0.00   87
 53  \w   -116.00 -17.00   1.00    1.00    --  -41.63 -37.00  90.00   99
 54  \w   -114.00 -14.00   1.00    1.00    --  -41.63 -56.00-125.00  100
 55  \w     23.00  98.00   1.00    1.00    --   41.63-125.00 -60.00   75
 56  \w     21.00  47.00   1.00    1.00    --   54.00  79.00-145.75   26
 57  \w     21.00  49.00   1.00    1.00    --   54.00  78.00 147.76   28
 58  \w     20.00  46.00   1.00    1.00    --   54.00  81.00 -31.55   26
 59  \w     20.00  46.00   1.00    1.00    --   54.00  81.00 -99.08   26
 60  \w     25.00 134.00   1.00    1.00    --   58.00  77.00 119.30  109
 61  \w     26.00 133.00   1.00    1.00    --   58.00  75.00 -36.73  107
 62  \w     30.00 138.00   1.00    1.00    --   62.00  76.00 169.11  108
 63  \w     33.00 142.00   1.00    1.00    --   66.00  77.00-164.48  109
 64  \w     33.00 142.00   1.00    1.00    --   66.00  77.00  60.67  109
 65  \w     33.00 142.00   1.00    1.00    --   66.00  77.00-120.42  109
 66  \w     33.00 142.00   1.00    1.00    --   66.00  77.00   9.47  109
 67  \w     34.00 141.00   1.00    1.00    --   66.00  75.00  40.49  107
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1210276000
_diffrn_orient_matrix_UB_12      0.0209623000
_diffrn_orient_matrix_UB_13      0.0345296000
_diffrn_orient_matrix_UB_21      0.0506782000
_diffrn_orient_matrix_UB_22      -0.0876822000
_diffrn_orient_matrix_UB_23      -0.0494640000
_diffrn_orient_matrix_UB_31      0.0253126000
_diffrn_orient_matrix_UB_32      0.0765286000
_diffrn_orient_matrix_UB_33      -0.0659276000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1075
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            92565
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.520
_diffrn_reflns_theta_min         4.254
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.661
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37226
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.182
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.128
_refine_diff_density_min         -0.159
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1957 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.07(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         5316
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0457
_refine_ls_R_factor_gt           0.0405
_refine_ls_shift/su_max          <0.001
_refine_ls_shift/su_mean         <0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0654P)^2^+0.2577P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1065
_refine_ls_wR_factor_ref         0.1118
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                4808
_reflns_number_total             5316
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np0c00618_si_001.cif
_cod_data_source_block           Asperginol_A
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '554-555 K' was changed to
'554.5(5)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               1559923
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C27 H40 O6'
_exptl_absorpt_special_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_reflns_odcompleteness_completeness 99.92
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C2(H2), C10(H10), C14(H14A), C4(H4A)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C9(H9A,H9B), C1(H1A,H1B), C13(H13A,H13B), C8(H8A,H8B), C5(H5A,
 H5B)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C18(H18A,H18B,H18C), C16(H16A,H16B,H16C), C7'(H7'A,H7'B,
 H7'C), C6'(H6'A,H6'B,H6'C), C17(H17A,H17B,H17C)
2.d Idealised tetrahedral OH refined as rotating group:
 O14(H14), O3'(H3')
;
_shelx_res_checksum              65673
_shelx_hkl_checksum              8582
_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 2.928
_oxdiff_exptl_absorpt_empirical_full_min 0.319