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_1543602
_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         'C19 H22 O8 S, 0.5(C H4 O), 2.49(H2 O)'
_chemical_formula_sum            'C19.5 H28.98 O10.99 S'
_chemical_formula_weight         471.33
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-11-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.7952(7)
_cell_length_b                   17.2819(11)
_cell_length_c                   23.5916(13)
_cell_measurement_reflns_used    5755
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.29
_cell_measurement_theta_min      2.22
_cell_volume                     4401.3(5)
_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 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'Bruker-Nonius Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w 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  0.0501
_diffrn_reflns_av_unetI/netI     0.0679
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            30204
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.404
_diffrn_reflns_theta_max         25.404
_diffrn_reflns_theta_min         1.461
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.206
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.924
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0887 before and 0.0465 after correction.
The Ratio of minimum to maximum transmission is 0.9431.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_description       block
_exptl_crystal_F_000             1999
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.287
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 2362 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     662
_refine_ls_number_reflns         8055
_refine_ls_number_restraints     1066
_refine_ls_restrained_S_all      0.962
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0414
_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^)+(0.0533P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0944
_refine_ls_wR_factor_ref         0.1055
_reflns_Friedel_coverage         0.791
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                6376
_reflns_number_total             8055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np6b00295_si_003.cif
_cod_data_source_block           ra100
_cod_depositor_comments
;

2019-08-18
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C39 H57.97 O21.98 S2'
_cod_original_formula_weight         942.66
_cod_original_formula_moiety         '2(C19 H22 O8 S), C H4 O, 4.98(H2 O)'
_cod_original_formula_units_Z            4
_cod_database_code               1543602
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.931
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O20A-C40A = O20-C40
 1.45 with sigma of 0.02
 O17A-C39A
 1.45 with sigma of 0.02
 O20-C40 \\sim O20A-C40A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(O13) = Uanis(O13A)
Uanis(C34) = Uanis(C34A)
Uanis(C35) = Uanis(C35A)
Uanis(C33A) = Uanis(C33)
Uanis(C20A) = Uanis(C20)
Uanis(O9A) = Uanis(O9)
Uanis(C40) = Uanis(C40A)
Uanis(O20) = Uanis(O20A)
Uanis(O17) = Uanis(O17A)
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. Others
 Sof(O9)=Sof(O13)=Sof(C20)=Sof(H21C)=Sof(H21D)=Sof(H32C)=Sof(H32D)=Sof(C33)=
 Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=1-
 FVAR(1)
 Sof(O13A)=Sof(H21A)=Sof(H21B)=Sof(H32A)=Sof(H32B)=Sof(O9A)=Sof(C20A)=
 Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35D)=
 Sof(H35E)=Sof(H35F)=FVAR(1)
 Sof(O20A)=Sof(H20A)=Sof(C40A)=Sof(H40D)=Sof(H40E)=Sof(H40F)=0.75*(1-FVAR(3))
 Sof(O20)=Sof(H20)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=0.75*FVAR(3)
 Fixed Sof: O17(0.75) H17D(0.75) H17E(0.75) O17A(0.25) H17C(0.25) C39A(0.25)
 H39A(0.25) H39B(0.25) H39C(0.25) O19(0.9) H19A(0.9) H19B(0.9) O21A(0.5)
 H21E(0.5) H21F(0.5) O23(0.33333) H23A(0.33333) H23B(0.33333) O21(0.5)
 H21G(0.5) H21H(0.5)
6.a Free rotating group:
 O17(H17D,H17E), O19(H19A,H19B), O21A(H21E,H21F), O18(H18A,H18B), O22(H22A,
 H22B), O23(H23A,H23B), O21(H21G,H21H)
6.b Ternary CH refined with riding coordinates:
 C10(H10A), C11(H11A), C15(H15), C29(H29), C30(H30), C34(H34), C34A(H34A)
6.c Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C17(H17A,H17B),
 C21(H21A,H21B), C21(H21C,H21D), C31(H31A,H31B), C32(H32A,H32B), C32(H32C,H32D),
  C33(H33A,H33B), C36(H36A,H36B), C33A(H33C,H33D)
6.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6A), C23(H23), C25(H25)
6.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C35(H35A,H35B,H35C), C35A(H35D,H35E,H35F), C40(H40A,H40B,
 H40C), C39A(H39A,H39B,H39C), C40A(H40D,H40E,H40F)
6.f Idealised tetrahedral OH refined as rotating group:
 O2(H2), O3(H3), O6(H6), O8(H8), O10(H10), O11(H11), O14(H14), O16(H16),
 O20(H20), O17A(H17C), O20A(H20A)
;
_shelx_res_checksum              22948
_shelx_hkl_checksum              33265
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'