Condensation of Macrocyclic Polyketides Produced by Penicillium sp. DRF2 with Mercaptopyruvate Represents a New Fungal Detoxification Pathway.
de Castro, Marcos V.; Ióca, Laura P; Williams, David E.; Costa, Bruna Z.; Mizuno, Carolina M.; Santos, Mario F. C.; de Jesus, Karen; Ferreira, Éverton L F; Seleghim, Mirna H. R.; Sette, Lara D.; Pereira Filho, Edenir R.; Ferreira, Antonio G.; Gonçalves, Natália S; Santos, Raquel A.; Patrick, Brian O.; Andersen, Raymond J.; Berlinck, Roberto G. S.; Journal of natural products 79 (2016) 1668–1678; doi:10.1021/acs.jnatprod.6b00295

data_1543601
_publ_section_title
;
 Condensation of Macrocyclic Polyketides Produced by Penicillium sp. DRF2
 with Mercaptopyruvate Represents a New Fungal Detoxification Pathway.
;
_journal_issue                   6
_journal_name_full               'Journal of natural products'
_journal_page_first              1668
_journal_page_last               1678
_journal_paper_doi               10.1021/acs.jnatprod.6b00295
_journal_volume                  79
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H28 O8 S'
_chemical_formula_sum            'C22 H28 O8 S'
_chemical_formula_weight         452.50
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_symmetry_space_group_name_Hall  'P 4cw'
_symmetry_space_group_name_H-M   'P 43'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.019(3)
_cell_length_b                   10.019(3)
_cell_length_c                   42.875(12)
_cell_measurement_reflns_used    3432
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.44
_cell_measurement_theta_min      2.24
_cell_volume                     4304(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'Bruker-Nonius Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0984
_diffrn_reflns_av_unetI/netI     0.1039
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            25385
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.198
_diffrn_reflns_theta_max         24.198
_diffrn_reflns_theta_min         0.950
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.197
_exptl_absorpt_correction_T_max  0.994
_exptl_absorpt_correction_T_min  0.747
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1289 before and 0.0945 after correction.
The Ratio of minimum to maximum transmission is 0.7012.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_description       plate
_exptl_crystal_F_000             1920
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.573
_refine_diff_density_min         -0.598
_refine_diff_density_rms         0.140
_refine_ls_abs_structure_details
;
 Flack x determined using 2354 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     570
_refine_ls_number_reflns         6912
_refine_ls_number_restraints     859
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1165
_refine_ls_R_factor_gt           0.1115
_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^)+(0.1530P)^2^+37.0040P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3003
_refine_ls_wR_factor_ref         0.3038
_reflns_Friedel_coverage         0.970
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                6318
_reflns_number_total             6912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np6b00295_si_004.cif
_cod_data_source_block           ra106
_cod_original_cell_volume        4304(3)
_cod_database_code               1543601
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.703(6) 0.297(6)
2. 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
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.005 and
sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C10A(H10A), C11A(H11A), C15A(H15A), C10B(H10B), C11B(H11B), C15B(H15B)
5.b Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C12A(H12A,H12B), C13A(H13A,H13B), C14A(H14A,H14B), C17A(H17A,
 H17B), C2B(H2BA,H2BB), C12B(H12C,H12D), C13B(H13C,H13D), C14B(H14C,H14D),
 C17B(H17C,H17D)
5.c Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C6A(H6AA), C4B(H4B), C6B(H6BA)
5.d Idealised Me refined as rotating group:
 C16A(H16A,H16B,H16C), C20A(H20A,H20B,H20C), C21A(H21A,H21B,H21C), C22A(H22A,
 H22B,H22C), C16B(H16D,H16E,H16F), C20B(H20D,H20E,H20F), C21B(H21D,H21E,H21F),
 C22B(H22D,H22E,H22F)
5.e Idealised tetrahedral OH refined as rotating group:
 O6A(H6A), O6B(H6B)
;
_shelx_res_checksum              3318
_shelx_hkl_checksum              59941
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'