Isolation, Structure Elucidation, and Absolute Configuration of Highly Oxygenated Germacranolides from Carpesium cernuum.
Liu, Qing-Xin; Yang, Yong-Xun; Zhang, Jian-Ping; Chen, Li-Ping; Shen, Yun-Heng; Li, Hui-Liang; Zhang, Wei-Dong; Journal of natural products 79 (2016) 2479–2486; doi:10.1021/acs.jnatprod.6b00315

data_1544486
_publ_section_title
;
 Isolation, Structure Elucidation, and Absolute Configuration of Highly
 Oxygenated Germacranolides from Carpesium cernuum.
;
_journal_issue                   10
_journal_name_full               'Journal of natural products'
_journal_page_first              2479
_journal_page_last               2486
_journal_paper_doi               10.1021/acs.jnatprod.6b00315
_journal_volume                  79
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C24 H34 O9'
_chemical_formula_sum            'C24 H34 O9'
_chemical_formula_weight         466.51
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-08-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.8736(3)
_cell_length_b                   18.0856(6)
_cell_length_c                   27.7795(9)
_cell_measurement_reflns_used    6333
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      65.98
_cell_measurement_theta_min      2.92
_cell_volume                     4960.6(3)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1054
_diffrn_reflns_av_unetI/netI     0.0892
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            30960
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.607
_diffrn_reflns_theta_min         2.915
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.793
_exptl_absorpt_correction_T_max  0.7532
_exptl_absorpt_correction_T_min  0.4036
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1489 before and 0.0862 after correction.
The Ratio of minimum to maximum transmission is 0.5358.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       block
_exptl_crystal_F_000             2000
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 1509 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.42(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     611
_refine_ls_number_reflns         8790
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.1267
_refine_ls_R_factor_gt           0.0721
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1147P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1846
_refine_ls_wR_factor_ref         0.2190
_reflns_Friedel_coverage         0.726
_reflns_Friedel_fraction_full    0.924
_reflns_Friedel_fraction_max     0.897
_reflns_number_gt                5132
_reflns_number_total             8790
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np6b00315_si_005.cif
_cod_data_source_block           cu_dm15639_0m
_cod_database_code               1544486
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.826
_shelx_estimated_absorpt_t_min   0.797
_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. Restrained distances
 H2A-H2AB
 2 with sigma of 0.01
3.a Ternary CH refined with riding coordinates:
 C5(H5), C6(H6), C7(H7B), C8(H8), C9(H9), C10(H10), C2"(H2"), C2"A(H2"A),
 C5A(H5A), C6A(H6A), C7A(H7AA), C8A(H8A), C9A(H9A), C10A(H10A)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2B,H2C), C1A(H1AA,H1AB), C2A(H2AA,H2AB)
3.c Aromatic/amide H refined with riding coordinates:
 C3'(H3'), C3'A(H3'A)
3.d X=CH2 refined with riding coordinates:
 C13(H13C,H13D), C13A(H13A,H13B)
3.e Idealised Me refined as rotating group:
 C14(H14D,H14E,H14F), C15(H15D,H15E,H15F), C3"(H3"D,H3"E,H3"F), C4"(H4"D,H4"E,
 H4"F), C4'(H4'D,H4'E,H4'F), C5'(H5'D,H5'E,H5'F), C3"A(H3"A,H3"B,H3"C),
 C4"A(H4"A,H4"B,H4"C), C4'A(H4'A,H4'B,H4'C), C5'A(H5'A,H5'B,H5'C), C14A(H14A,
 H14B,H14C), C15A(H15A,H15B,H15C)
3.f Idealised tetrahedral OH refined as rotating group:
 O2(H2), O7(H7), O2A(H2A), O7A(H7A)
;
_shelx_res_checksum              16799
_shelx_hkl_checksum              82217
_olex2_submission_special_instructions 'No special instructions were received'