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_1545571
_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 ad
_chemical_formula_moiety         'C63 H101 O23'
_chemical_formula_sum            'C63 H101 O23'
_chemical_formula_weight         1226.43
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-12-02
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.11.10 svn.r3248 for OlexSys, GUI svn.r5133)
;
_cell_angle_alpha                109.544(2)
_cell_angle_beta                 94.088(2)
_cell_angle_gamma                113.055(2)
_cell_formula_units_Z            1
_cell_length_a                   11.5223(5)
_cell_length_b                   11.5593(5)
_cell_length_c                   14.8540(6)
_cell_measurement_reflns_used    9776
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      64.07
_cell_measurement_theta_min      3.25
_cell_volume                     1668.16(13)
_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)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      170
_diffrn_measured_fraction_theta_full 0.891
_diffrn_measured_fraction_theta_max 0.954
_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  0.0428
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 0.891
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            36648
_diffrn_reflns_point_group_measured_fraction_full 0.838
_diffrn_reflns_point_group_measured_fraction_max 0.898
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         64.728
_diffrn_reflns_theta_min         3.247
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.763
_exptl_absorpt_correction_T_max  0.7525
_exptl_absorpt_correction_T_min  0.6953
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0925 before and 0.0601 after correction.
The Ratio of minimum to maximum transmission is 0.9240.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear blackish black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.221
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             663
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.196
_refine_diff_density_min         -0.222
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 3841 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.10(8)
_refine_ls_extinction_coef       0.00062(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     805
_refine_ls_number_reflns         10137
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0363
_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^)+(0.0520P)^2^+0.1373P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0906
_refine_ls_wR_factor_ref         0.0942
_reflns_Friedel_coverage         0.881
_reflns_Friedel_fraction_full    0.785
_reflns_Friedel_fraction_max     0.841
_reflns_number_gt                9125
_reflns_number_total             10137
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np7b00017_si_002.cif
_cod_data_source_block           cu_2015583_0m
_cod_depositor_comments          'Adding full bibliography for 1545571.cif.'
_cod_database_code               1545571
_shelxl_version_number           2013-2
_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. Others
 Fixed Sof: C35A(0.5) C35B(0.5)
3.a Ternary CH refined with riding coordinates:
 C58(H58), C57(H57), C56(H56), C52(H52), C53(H53), C50(H50), C46(H46),
 C47(H47), C43(H43), C39(H39), C40(H40), C36(H36), C32(H32), C33(H33), C25(H25),
  C26(H26), C22(H22A), C20(H20A), C10(H10), C2(H2A), C59(H59), C63(H63),
 C31(H31), C14(H14), C9(H9), C24(H24), C38(H38), C45(H45), C60(H60)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C11(H11A,H11B), C1(H1A,H1B), C51(H51A,H51B), C30(H30A,H30B),
 C16(H16A,H16B), C15(H15A,H15B), C8(H8A,H8B), C4(H4A,H4B), C3(H3A,H3B),
 C23(H23A,H23B), C28(H28A,H28B), C37(H37A,H37B), C44(H44A,H44B)
3.c Aromatic/amide H refined with riding coordinates:
 C7(H7)
3.d Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C), C54(H54A,H54B,H54C), C34(H34A,H34B,H34C), C19(H19A,H19B,
 H19C), C18(H18A,H18B,H18C), C21(H21A,H21B,H21C), C27(H27A,H27B,H27C), C42(H42A,
 H42B,H42C), C41(H41A,H41B,H41C), C49(H49A,H49B,H49C), C48(H48A,H48B,H48C),
 C61(H61A,H61B,H61C), C55(H55A,H55B,H55C)
3.e Idealised tetrahedral OH refined as rotating group:
 O22(H22), O20(H20), O2(H2)
;
_shelx_res_checksum              25604
_shelx_hkl_checksum              97160
_olex2_submission_special_instructions 'No special instructions were received'