Origin of the Thiopyrone CTP-431 "Unexpectedly" Isolated from the Marine Sponge Cacospongia mycofijiensis.
Przeslak, Adam D.; Inman, Martyn; Lewis, William; Moody, Christopher J.; The Journal of organic chemistry 83 (2018) 10595–10601; doi:10.1021/acs.joc.8b01258

data_4035032
_publ_section_title
;
 Origin of the Thiopyrone CTP-431 &quot;Unexpectedly&quot; Isolated from
 the Marine Sponge Cacospongia mycofijiensis.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10595
_journal_page_last               10601
_journal_paper_doi               10.1021/acs.joc.8b01258
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H21 N O3 S'
_chemical_formula_sum            'C18 H21 N O3 S'
_chemical_formula_weight         331.42
_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   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-04-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.974(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.0528(3)
_cell_length_b                   10.4267(4)
_cell_length_c                   20.0816(6)
_cell_measurement_reflns_used    7526
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.2350
_cell_measurement_theta_min      4.2520
_cell_volume                     1683.86(10)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details
;
  1 omega  -51.00  -11.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   45.0000  -60.0000 20

  2 omega  -30.00    8.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9304  -38.0000 -150.0000 19

  3 omega   52.00  110.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9304   38.0000  -60.0000 29

  4 omega   18.00  110.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9304   38.0000   30.0000 46

  5 omega   18.00   56.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9304   38.0000 -150.0000 19

  6 omega   14.00  104.00   2.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9304   57.0000 -120.0000 45

  7 omega   42.00   90.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -45.0000   90.0000 24

  8 omega   47.00  105.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -94.0000  -90.0000 29

  9 omega   27.00  107.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -94.0000    0.0000 40

 10 omega   41.00   97.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -45.0000 -120.0000 28

 11 omega   46.00  108.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -94.0000   60.0000 31

 12 omega   32.00   84.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -30.0000 -180.0000 26

 13 omega   94.00  120.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295 -125.0000 -180.0000 13

 14 omega   54.00   80.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -30.0000  -60.0000 13

 15 omega   59.00  105.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -94.0000  120.0000 23

 16 omega   92.00  120.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295   31.0000   90.0000 14

 17 omega   39.00   89.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -30.0000  120.0000 25

 18 omega  114.00  154.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295   30.0000   30.0000 20

 19 omega   33.00   81.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -30.0000  -30.0000 24

 20 omega   51.00  101.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295  -94.0000 -150.0000 25

 21 omega   21.00  167.00   2.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      102.8295    0.0000 -150.0000 73
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1479007000
_diffrn_orient_matrix_UB_12      -0.0782131000
_diffrn_orient_matrix_UB_13      0.0299662000
_diffrn_orient_matrix_UB_21      -0.1137126000
_diffrn_orient_matrix_UB_22      -0.1178040000
_diffrn_orient_matrix_UB_23      0.0058571000
_diffrn_orient_matrix_UB_31      0.0427843000
_diffrn_orient_matrix_UB_32      -0.0429628000
_diffrn_orient_matrix_UB_33      -0.0705365000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_wavelength_determination fundamental
_diffrn_reflns_av_R_equivalents  0.0273
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            12280
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.586
_diffrn_reflns_theta_min         4.409
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.826
_exptl_absorpt_correction_T_max  0.676
_exptl_absorpt_correction_T_min  0.421
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Numerical absorption correction based on gaussian integration over 			a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_recrystallization_method
'The material was recrystallised from toluene by slow evaporation'
_exptl_crystal_size_max          0.7274
_exptl_crystal_size_mid          0.4316
_exptl_crystal_size_min          0.2521
_refine_diff_density_max         0.206
_refine_diff_density_min         -0.326
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 2517 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.024(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     464
_refine_ls_number_reflns         6594
_refine_ls_number_restraints     76
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0392
_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^)+(0.0622P)^2^+0.2103P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1049
_refine_ls_wR_factor_ref         0.1074
_reflns_Friedel_coverage         0.853
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                6114
_reflns_number_total             6594
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01258_si_002.cif
_cod_data_source_block           adpcmd
_cod_original_cell_volume        1683.85(10)
_cod_database_code               4035032
_nottingham_internal_coll_name   ADPCMD
_nottingham_internal_coll_number 12984
_nottingham_internal_coll_client ADP/CJM
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'omega scans'
_nottingham_internal_coll_frame_time '2.0000, 2.5000'
_nottingham_internal_coll_frame_width 2.0000
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_date   07/11/2013
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_date 14/03/2014
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 30/4/2018
_nottingham_internal_validation_user pczwl
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C18 H21 N O3 S'
_chemical_oxdiff_usercomment
'ADPCMD #12984 IN FOMBLIN FILM ON MICROMOUNT FOR ADP/CJM'
_shelx_estimated_absorpt_t_max   0.656
_shelx_estimated_absorpt_t_min   0.350
_reflns_odcompleteness_completeness 99.87
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C43A-C42A \\sim C43-C42
 with sigma of 0.02
 C42A-C41 \\sim C42-C41
 with sigma of 0.02
 C43-C44 \\sim C43A-C44
 with sigma of 0.02
 C12A-C11 \\sim C12-C11
 with sigma of 0.02
 C13A-C12A \\sim C13-C12
 with sigma of 0.02
 C14-C13 \\sim C14-C13A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S1 \\sim S1A \\sim C2 \\sim C5 \\sim O6 \\sim O6A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 S1, S1A, C2, C5, O6, O6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43D)=
 Sof(H43C)=Sof(H44C)=Sof(H44D)=1-FVAR(1)
 Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H44A)=Sof(H44B)=FVAR(1)
 Sof(S1A)=Sof(H5BC)=Sof(H5BD)=Sof(O6A)=1-FVAR(2)
 Sof(S1)=Sof(H5AA)=Sof(H5AB)=Sof(O6)=FVAR(2)
 Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C13A)=Sof(H13D)=
 Sof(H13C)=Sof(H14C)=Sof(H14D)=1-FVAR(3)
 Sof(H11B)=Sof(H11A)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13B)=Sof(H13A)=
 Sof(H14A)=Sof(H14B)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C4(H4), C34(H34)
6.b Secondary CH2 refined with riding coordinates:
 C5(H5AA,H5AB), C5(H5BC,H5BD), C11(H11B,H11A), C11(H11C,H11D), C12(H12A,H12B),
 C12A(H12C,H12D), C13(H13B,H13A), C13A(H13D,H13C), C14(H14A,H14B), C14(H14C,
 H14D), C15(H15A,H15B), C35(H35B,H35A), C41(H41A,H41B), C41(H41C,H41D),
 C42(H42A,H42B), C42A(H42C,H42D), C43(H43A,H43B), C43A(H43D,H43C), C44(H44A,
 H44B), C44(H44C,H44D), C45(H45A,H45B)
6.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C17(H17), C18(H18), C20(H20), C21(H21), C40(H40), C47(H47),
 C48(H48), C50(H50), C51(H51)
6.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C53(H53A,H53B,H53C)
;
_shelx_res_checksum              92320
_shelx_hkl_checksum              67585
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'
_olex2_date_sample_data_collection 2013-11-07
_olex2_date_sample_submission    2013-11-05
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perflourotether oil'
_olex2_submission_original_sample_id ADP592a
_olex2_submission_special_instructions 'No special instructions were received'