Absolute Configuration of Periplosides C and F and Isolation of Minor Spiro-orthoester Group-Containing Pregnane-type Steroidal Glycosides from Periploca sepium and Their T-Lymphocyte Proliferation Inhibitory Activities.
Wang, Luo-Yi; Qin, Jun-Jun; Chen, Zhen-Hua; Zhou, Yu; Tang, Wei; Zuo, Jian-Ping; Zhao, Wei-Min; Journal of natural products 80 (2017) 1102–1109; doi:10.1021/acs.jnatprod.7b00017

data_1545923
_publ_section_title
;
 Absolute Configuration of Periplosides C and F and Isolation of Minor
 Spiro-orthoester Group-Containing Pregnane-type Steroidal Glycosides from
 Periploca sepium and Their T-Lymphocyte Proliferation Inhibitory
 Activities.
;
_journal_issue                   4
_journal_name_full               'Journal of natural products'
_journal_page_first              1102
_journal_page_last               1109
_journal_paper_doi               10.1021/acs.jnatprod.7b00017
_journal_volume                  80
_journal_year                    2017
_chemical_absolute_configuration unk
_chemical_formula_moiety
'C37 H58 O10, H2 O'
_chemical_formula_sum            'C37 H60 O11'
_chemical_formula_weight         680.82
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-28
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.11.10 svn.r3248 for OlexSys, GUI svn.r5133)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.788(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.5069(16)
_cell_length_b                   23.641(3)
_cell_length_c                   25.417(3)
_cell_measurement_reflns_used    2872
_cell_measurement_temperature    296
_cell_measurement_theta_max      20.47
_cell_measurement_theta_min      2.30
_cell_volume                     7427.0(16)
_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  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.944
_diffrn_measured_fraction_theta_max 0.944
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0606
_diffrn_reflns_av_unetI/netI     0.1544
_diffrn_reflns_Laue_measured_fraction_full 0.944
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            27481
_diffrn_reflns_point_group_measured_fraction_full 0.853
_diffrn_reflns_point_group_measured_fraction_max 0.853
_diffrn_reflns_theta_full        24.499
_diffrn_reflns_theta_max         24.499
_diffrn_reflns_theta_min         0.811
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.088
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6086
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0654 before and 0.0546 after correction.
The Ratio of minimum to maximum transmission is 0.8163.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_description       needle
_exptl_crystal_F_000             2930
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.685
_refine_diff_density_min         -0.337
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 3541 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   1.9(8)
_refine_ls_extinction_coef       0.0020(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.977
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1781
_refine_ls_number_reflns         21112
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      0.978
_refine_ls_R_factor_all          0.1501
_refine_ls_R_factor_gt           0.0761
_refine_ls_shift/su_max          0.020
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0832P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1596
_refine_ls_wR_factor_ref         0.1886
_reflns_Friedel_coverage         0.760
_reflns_Friedel_fraction_full    0.757
_reflns_Friedel_fraction_max     0.757
_reflns_number_gt                12199
_reflns_number_total             21112
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np7b00017_si_003.cif
_cod_data_source_block           20120036_0m
_cod_depositor_comments
;

2019-07-31
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C148 H225 O44'
_cod_original_formula_weight         2708.27
_cod_original_formula_moiety
'C37 H55 O10, 2(C37 H57 O10), C37 H58 O10, 4(O)'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        7426.9(16)
_cod_database_code               1545923
_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
2. Restrained distances
 C149-C1A
 1.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C147) \\sim Ueq, Uanis(O45) \\sim Ueq, Uanis(O42) \\sim Ueq, Uanis(O46)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C77) \\sim Ueq, Uanis(C123) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: H14d(0.5) H14e(0.5) H14f(0.5) H14g(0.5) C149(0.5) O45(0.5)
 O42(0.5) C1A(0.5)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8a), C9(H9), C10(H10a), C14(H14), C15(H15),
 C23(H23), C25(H25), C32(H32), C38(H38), C39(H39), C43(H43), C44(H44), C45(H45),
  C48(H48), C49(H49), C51(H51), C54(H54), C68(H68), C70(H70), C74(H74),
 C75(H75), C79(H79), C80(H80), C81(H81), C84(H84), C85(H85), C87(H87), C91(H91),
  C106(H106), C107(H107), C112(H112), C114(H114), C115(H115), C118(H118),
 C119(H119), C124(H124), C125(H125), C130(H130), C131(H131), C138(H138),
 C139(H139)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1a,H1b), C3(H3a,H3b), C13(H13a,H13b), C19(H19a,H19b), C20(H20a,H20b),
 C21(H21a,H21b), C22(H22a,H22b), C27(H27a,H27b), C28(H28a,H28b), C29(H29a,H29b),
  C50(H50a,H50b), C52(H52a,H52b), C53(H53a,H53b), C57(H57a,H57b), C58(H58a,
 H58b), C60(H60a,H60b), C62(H62a,H62b), C63(H63a,H63b), C64(H64a,H64b),
 C65(H65a,H65b), C76(H76a,H76b), C86(H86a,H86b), C88(H88a,H88b), C89(H89a,H89b),
  C95(H95a,H95b), C96(H96a,H96b), C98(H98a,H98b), C100(H10b,H10c), C101(H10d,
 H10e), C102(H10f,H10g), C103(H10h,H10i), C110(H11a,H11b), C111(H11c,H11d),
 C113(H11e,H11f), C120(H12a,H12b), C134(H13f,H13g), C135(H13h,H13i), C136(H13j,
 H13k), C137(H13l,H13m), C142(H14q,H14r), C143(H14s,H14t), C147(H14d,H14e),
 C147(H14f,H14g)
5.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C33(H33), C40(H40), C56(H56), C59(H59), C92(H92), C97(H97),
 C121(H121), C123(H123), C129(H129)
5.d Tetrahedral OH refined with riding coordinates:
 O17(H17), O27(H27)
5.e Idealised Me refined as rotating group:
 C146(H14a,H14b,H14c), C18(H18a,H18b,H18c), C24(H24a,H24b,H24c), C26(H26a,H26b,
 H26c), C31(H31a,H31b,H31c), C34(H34a,H34b,H34c), C35(H35a,H35b,H35c), C55(H55a,
 H55b,H55c), C61(H61a,H61b,H61c), C66(H66a,H66b,H66c), C67(H67a,H67b,H67c),
 C69(H69a,H69b,H69c), C71(H71a,H71b,H71c), C90(H90a,H90b,H90c), C94(H94a,H94b,
 H94c), C99(H99a,H99b,H99c), C104(H10j,H10k,H10l), C105(H10m,H10n,H10o),
 C108(H10p,H10q,H10r), C109(H10s,H10t,H10u), C128(H12c,H12d,H12e), C133(H13c,
 H13d,H13e), C140(H14k,H14l,H14m), C141(H14n,H14o,H14p), C144(H14u,H14v,H14w),
 C145(H14x,H14y,H), C148(H14h,H14i,H14j)
5.f Idealised tetrahedral OH refined as rotating group:
 O8(H8), O10(H10), O21(H21), O30(H30a), O37(H37), O39(H39a)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'