Supplementary Material (ESI) for Perkin Transactions This journal is © The Royal Society of Chemistry 2002 data_ah9705 _database_code_CSD 178859 _journal_coden_Cambridge 207 _publ_requested_journal 'Perkin Transactions 1' loop_ _publ_author_name 'Holmes, Andrew' 'Adams, Joseph P.' 'Davies, John E.' 'Davison, Edwin C.' 'Forbes, Ian T.' 'Fox, Martin E.' 'Press, Neil J.' 'Raithby, Paul R.' 'Roughley, Stephen D.' 'Smith, Catherine' 'Thompson, Mervyn J.' 'Williams, Geoffrey M.' _publ_contact_author_name 'Prof Andrew Holmes' _publ_contact_author_address ; Chemistry University of Cambridge Lensfield Road Cambridge Cambs CB2 1EW UNITED KINGDOM ; _publ_contact_author_email 'ABH1@CAM.AC.UK' _publ_section_title ; Nitrone Dipolar Cycloaddition Routes to Piperidines and Indolizidines. Part 9. Formal Synthesis of (-)-Pinidine and Total Synthesis of (-)-Histrionicotoxin, (+)-Histrionicotoxin and (-)-Histrionicotoxin 235A ; _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C12 H18 N2 O2' _chemical_formula_sum 'C12 H18 N2 O2' _chemical_formula_weight 222.28 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 6.949(2) _cell_length_b 14.011(4) _cell_length_c 12.055(3) _cell_angle_alpha 90.00 _cell_angle_beta 93.60(2) _cell_angle_gamma 90.00 _cell_volume 1171.4(6) _cell_formula_units_Z 4 _cell_measurement_temperature 294(2) _cell_measurement_reflns_used 19 _cell_measurement_theta_min 10 _cell_measurement_theta_max 17.5 _exptl_crystal_description block _exptl_crystal_colour white _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.260 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 480 _exptl_absorpt_coefficient_mu 0.087 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 294(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Rigaku R-AXIS IIc' _diffrn_measurement_method '/f scans' _diffrn_standards_number 0 _diffrn_reflns_number 6718 _diffrn_reflns_av_R_equivalents 0.0653 _diffrn_reflns_av_sigmaI/netI 0.0682 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 3.69 _diffrn_reflns_theta_max 25.25 _diffrn_measured_fraction_theta_max 0.951 _diffrn_reflns_theta_full 25.25 _diffrn_measured_fraction_theta_full 0.951 _reflns_number_total 3371 _reflns_number_gt 3088 _reflns_threshold_expression >2\s(I) _computing_data_collection 'R-Axis PROCESS (MSC, 1995)' _computing_cell_refinement 'R-Axis PROCESS (MSC, 1995)' _computing_data_reduction 'R-Axis PROCESS (MSC, 1995)' _computing_structure_solution 'SIR-92 (Altomare et al., 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XP (Sheldrick, 1996)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0634P)^2^+0.2085P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.35(2) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -2(2) _refine_ls_number_reflns 3371 _refine_ls_number_parameters 296 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0719 _refine_ls_R_factor_gt 0.0647 _refine_ls_wR_factor_ref 0.1552 _refine_ls_wR_factor_gt 0.1493 _refine_ls_goodness_of_fit_ref 1.273 _refine_ls_restrained_S_all 1.273 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.201 _refine_diff_density_min -0.216 _refine_diff_density_rms 0.054 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1 O 0.1245(4) 0.2104(2) 0.0749(2) 0.0416(7) Uani 1 1 d . . . O14 O 0.5986(5) 0.0808(2) 0.1242(3) 0.0542(8) Uani 1 1 d D . . H14 H 0.594(7) 0.099(4) 0.1889(17) 0.065 Uiso 1 1 d D . . N11 N 0.2830(4) 0.1936(2) 0.0016(2) 0.0347(7) Uani 1 1 d . . . N16 N -0.2080(7) 0.2995(4) -0.2667(4) 0.0703(12) Uani 1 1 d . . . C2 C -0.0438(5) 0.2478(3) 0.0105(3) 0.0411(10) Uani 1 1 d . . . H2 H -0.1639 0.2207 0.0354 0.049 Uiso 1 1 calc R . . C3 C -0.0426(6) 0.3551(3) 0.0184(4) 0.0475(10) Uani 1 1 d . . . H3A H -0.0762 0.3744 0.0920 0.057 Uiso 1 1 calc R . . H3B H -0.1383 0.3813 -0.0352 0.057 Uiso 1 1 calc R . . C4 C 0.1545(7) 0.3942(3) -0.0040(4) 0.0518(11) Uani 1 1 d . . . H4A H 0.2400 0.3862 0.0621 0.062 Uiso 1 1 calc R . . H4B H 0.1435 0.4620 -0.0193 0.062 Uiso 1 1 calc R . . C5 C 0.2424(6) 0.3451(3) -0.1014(4) 0.0486(11) Uani 1 1 d . . . H5A H 0.3799 0.3578 -0.0974 0.058 Uiso 1 1 calc R . . H5B H 0.1875 0.3729 -0.1700 0.058 Uiso 1 1 calc R . . C6 C 0.2110(5) 0.2364(3) -0.1060(3) 0.0368(9) Uani 1 1 d . . . C7 C 0.3118(6) 0.1950(4) -0.2053(4) 0.0517(11) Uani 1 1 d . . . H7A H 0.2392 0.2132 -0.2733 0.062 Uiso 1 1 calc R . . H7B H 0.4391 0.2233 -0.2068 0.062 Uiso 1 1 calc R . . C8 C 0.3328(7) 0.0867(4) -0.2030(4) 0.0565(12) Uani 1 1 d . . . H8A H 0.2068 0.0571 -0.2137 0.068 Uiso 1 1 calc R . . H8B H 0.4104 0.0662 -0.2627 0.068 Uiso 1 1 calc R . . C9 C 0.4274(6) 0.0568(3) -0.0931(4) 0.0499(11) Uani 1 1 d . . . H9A H 0.5549 0.0849 -0.0839 0.060 Uiso 1 1 calc R . . H9B H 0.4416 -0.0121 -0.0915 0.060 Uiso 1 1 calc R . . C10 C 0.3070(5) 0.0885(3) 0.0022(3) 0.0381(9) Uani 1 1 d . . . H10 H 0.1792 0.0591 -0.0080 0.046 Uiso 1 1 calc R . . C12 C -0.0059(5) 0.2153(3) -0.1070(3) 0.0379(9) Uani 1 1 d . . . H12 H -0.0268 0.1463 -0.1133 0.045 Uiso 1 1 calc R . . C13 C 0.3979(6) 0.0580(3) 0.1134(4) 0.0450(10) Uani 1 1 d . . . H13A H 0.3327 0.0895 0.1721 0.054 Uiso 1 1 calc R . . H13B H 0.3817 -0.0103 0.1220 0.054 Uiso 1 1 calc R . . C15 C -0.1214(6) 0.2639(3) -0.1956(4) 0.0497(11) Uani 1 1 d . . . O17 O 0.4604(4) 0.1368(2) 0.3833(2) 0.0449(7) Uani 1 1 d . . . O30 O 0.5686(4) 0.2983(2) 0.1493(2) 0.0502(8) Uani 1 1 d D . . H30 H 0.469(4) 0.274(4) 0.122(4) 0.060 Uiso 1 1 d D . . N27 N 0.6469(4) 0.1675(2) 0.3442(3) 0.0353(8) Uani 1 1 d . . . N32 N 0.8495(7) 0.0300(4) 0.6970(4) 0.0745(13) Uani 1 1 d . . . C18 C 0.4907(6) 0.0888(4) 0.4899(3) 0.0484(11) Uani 1 1 d . . . H18 H 0.3908 0.1065 0.5400 0.058 Uiso 1 1 calc R . . C19 C 0.4941(9) -0.0165(4) 0.4717(5) 0.0707(17) Uani 1 1 d . . . H19A H 0.3657 -0.0387 0.4484 0.085 Uiso 1 1 calc R . . H19B H 0.5347 -0.0484 0.5406 0.085 Uiso 1 1 calc R . . C20 C 0.6322(10) -0.0405(4) 0.3832(5) 0.0764(18) Uani 1 1 d . . . H20A H 0.6650 -0.1077 0.3888 0.092 Uiso 1 1 calc R . . H20B H 0.5677 -0.0299 0.3106 0.092 Uiso 1 1 calc R . . C21 C 0.8146(8) 0.0172(4) 0.3923(4) 0.0630(14) Uani 1 1 d . . . H21A H 0.8733 0.0144 0.3214 0.076 Uiso 1 1 calc R . . H21B H 0.9032 -0.0127 0.4472 0.076 Uiso 1 1 calc R . . C22 C 0.7920(6) 0.1224(3) 0.4242(3) 0.0412(9) Uani 1 1 d . . . C23 C 0.9871(6) 0.1727(4) 0.4261(5) 0.0647(14) Uani 1 1 d . . . H23A H 1.0507 0.1552 0.3597 0.078 Uiso 1 1 calc R . . H23B H 1.0666 0.1501 0.4897 0.078 Uiso 1 1 calc R . . C24 C 0.9738(8) 0.2817(5) 0.4320(5) 0.0739(16) Uani 1 1 d . . . H24A H 0.9255 0.3009 0.5023 0.089 Uiso 1 1 calc R . . H24B H 1.1004 0.3097 0.4262 0.089 Uiso 1 1 calc R . . C25 C 0.8382(7) 0.3155(4) 0.3368(4) 0.0615(14) Uani 1 1 d . . . H25A H 0.8875 0.2961 0.2667 0.074 Uiso 1 1 calc R . . H25B H 0.8306 0.3846 0.3377 0.074 Uiso 1 1 calc R . . C26 C 0.6381(6) 0.2733(3) 0.3470(3) 0.0425(10) Uani 1 1 d . . . H26 H 0.5921 0.2928 0.4188 0.051 Uiso 1 1 calc R . . C28 C 0.6887(6) 0.1270(3) 0.5327(3) 0.0415(10) Uani 1 1 d . . . H28 H 0.6765 0.1938 0.5557 0.050 Uiso 1 1 calc R . . C29 C 0.4942(7) 0.3082(3) 0.2556(3) 0.0455(10) Uani 1 1 d . . . H29B H 0.3757 0.2719 0.2578 0.055 Uiso 1 1 calc R . . H29A H 0.4642 0.3748 0.2683 0.055 Uiso 1 1 calc R . . C31 C 0.7790(6) 0.0715(4) 0.6243(4) 0.0509(11) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 O1 0.0472(15) 0.0423(17) 0.0359(13) 0.0011(12) 0.0068(11) 0.0066(13) O14 0.0525(18) 0.061(2) 0.0472(17) -0.0114(16) -0.0119(15) 0.0134(15) N11 0.0347(16) 0.0327(19) 0.0366(16) -0.0022(13) 0.0017(13) 0.0038(13) N16 0.073(3) 0.072(3) 0.062(3) 0.004(2) -0.021(2) 0.016(3) C2 0.033(2) 0.042(2) 0.049(2) 0.0057(18) 0.0082(19) 0.0000(16) C3 0.056(3) 0.040(3) 0.047(2) 0.001(2) 0.002(2) 0.012(2) C4 0.057(2) 0.028(2) 0.070(3) 0.003(2) -0.001(2) 0.001(2) C5 0.047(2) 0.037(2) 0.061(3) 0.017(2) 0.002(2) -0.0058(19) C6 0.0347(19) 0.039(2) 0.036(2) 0.0065(16) 0.0012(17) 0.0000(16) C7 0.049(2) 0.066(3) 0.041(2) 0.004(2) 0.0094(19) 0.007(2) C8 0.057(3) 0.072(3) 0.041(2) -0.012(2) 0.007(2) 0.017(2) C9 0.047(2) 0.048(3) 0.053(3) -0.016(2) -0.006(2) 0.0129(19) C10 0.037(2) 0.028(2) 0.048(2) -0.0015(17) -0.0066(18) 0.0014(15) C12 0.0346(18) 0.037(2) 0.042(2) 0.0010(18) -0.0033(16) -0.0022(17) C13 0.051(2) 0.035(2) 0.048(2) -0.0021(18) -0.005(2) 0.0003(18) C15 0.047(2) 0.050(3) 0.052(3) 0.000(2) -0.004(2) 0.003(2) O17 0.0346(14) 0.0526(19) 0.0465(16) 0.0135(13) -0.0063(12) -0.0085(13) O30 0.0545(18) 0.0542(19) 0.0411(16) 0.0019(15) -0.0043(13) -0.0083(15) N27 0.0332(16) 0.0348(19) 0.0384(17) 0.0017(14) 0.0050(14) 0.0000(13) N32 0.084(3) 0.076(3) 0.060(3) 0.011(2) -0.024(2) 0.002(3) C18 0.047(2) 0.062(3) 0.036(2) 0.012(2) -0.0016(18) -0.007(2) C19 0.087(4) 0.063(4) 0.058(3) 0.027(3) -0.025(3) -0.037(3) C20 0.126(5) 0.037(3) 0.062(3) 0.004(2) -0.027(3) -0.003(3) C21 0.087(4) 0.049(3) 0.052(3) -0.004(2) -0.003(3) 0.026(3) C22 0.038(2) 0.044(2) 0.042(2) -0.0017(18) -0.0003(17) 0.0048(17) C23 0.033(2) 0.091(4) 0.070(3) 0.006(3) -0.002(2) -0.003(2) C24 0.058(3) 0.089(4) 0.072(3) 0.006(3) -0.015(3) -0.032(3) C25 0.073(3) 0.047(3) 0.063(3) 0.003(2) -0.011(3) -0.029(2) C26 0.055(3) 0.037(3) 0.037(2) -0.0048(17) 0.0034(19) -0.0014(18) C28 0.041(2) 0.044(3) 0.039(2) -0.0002(18) -0.0033(17) 0.0022(18) C29 0.063(3) 0.035(2) 0.039(2) 0.0015(18) 0.0047(19) 0.009(2) C31 0.054(3) 0.055(3) 0.042(2) 0.001(2) -0.014(2) 0.003(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag O1 C2 1.459(5) . ? O1 N11 1.474(4) . ? O14 C13 1.428(5) . ? O14 H14 0.82(1) . ? N11 C10 1.481(5) . ? N11 C6 1.486(5) . ? N16 C15 1.132(6) . ? C2 C3 1.507(6) . ? C2 C12 1.527(6) . ? C2 H2 0.9800 . ? C3 C4 1.515(6) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 C5 1.522(7) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 C6 1.538(6) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 C12 1.536(5) . ? C6 C7 1.539(6) . ? C7 C8 1.524(7) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 C9 1.501(6) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C9 C10 1.530(6) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 C13 1.508(6) . ? C10 H10 0.9800 . ? C12 C15 1.463(6) . ? C12 H12 0.9800 . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? O17 C18 1.453(5) . ? O17 N27 1.471(4) . ? O30 C29 1.418(5) . ? O30 H30 0.82(1) . ? N27 C26 1.484(5) . ? N27 C22 1.492(5) . ? N32 C31 1.137(6) . ? C18 C19 1.492(8) . ? C18 C28 1.536(6) . ? C18 H18 0.9800 . ? C19 C20 1.516(9) . ? C19 H19A 0.9700 . ? C19 H19B 0.9700 . ? C20 C21 1.501(8) . ? C20 H20A 0.9700 . ? C20 H20B 0.9700 . ? C21 C22 1.534(6) . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C22 C23 1.527(6) . ? C22 C28 1.532(5) . ? C23 C24 1.531(9) . ? C23 H23A 0.9700 . ? C23 H23B 0.9700 . ? C24 C25 1.514(7) . ? C24 H24A 0.9700 . ? C24 H24B 0.9700 . ? C25 C26 1.523(6) . ? C25 H25A 0.9700 . ? C25 H25B 0.9700 . ? C26 C29 1.522(6) . ? C26 H26 0.9800 . ? C28 C31 1.460(6) . ? C28 H28 0.9800 . ? C29 H29B 0.9700 . ? C29 H29A 0.9700 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C2 O1 N11 110.1(2) . . ? C13 O14 H14 93(4) . . ? O1 N11 C10 104.1(3) . . ? O1 N11 C6 103.6(3) . . ? C10 N11 C6 115.9(3) . . ? O1 C2 C3 108.9(3) . . ? O1 C2 C12 102.0(3) . . ? C3 C2 C12 110.8(3) . . ? O1 C2 H2 111.6 . . ? C3 C2 H2 111.6 . . ? C12 C2 H2 111.6 . . ? C2 C3 C4 110.6(3) . . ? C2 C3 H3A 109.5 . . ? C4 C3 H3A 109.5 . . ? C2 C3 H3B 109.5 . . ? C4 C3 H3B 109.5 . . ? H3A C3 H3B 108.1 . . ? C3 C4 C5 112.7(4) . . ? C3 C4 H4A 109.1 . . ? C5 C4 H4A 109.1 . . ? C3 C4 H4B 109.1 . . ? C5 C4 H4B 109.1 . . ? H4A C4 H4B 107.8 . . ? C4 C5 C6 114.3(3) . . ? C4 C5 H5A 108.7 . . ? C6 C5 H5A 108.7 . . ? C4 C5 H5B 108.7 . . ? C6 C5 H5B 108.7 . . ? H5A C5 H5B 107.6 . . ? N11 C6 C12 101.9(3) . . ? N11 C6 C5 109.2(3) . . ? C12 C6 C5 109.1(3) . . ? N11 C6 C7 112.4(3) . . ? C12 C6 C7 114.5(3) . . ? C5 C6 C7 109.3(3) . . ? C8 C7 C6 114.2(4) . . ? C8 C7 H7A 108.7 . . ? C6 C7 H7A 108.7 . . ? C8 C7 H7B 108.7 . . ? C6 C7 H7B 108.7 . . ? H7A C7 H7B 107.6 . . ? C9 C8 C7 109.3(4) . . ? C9 C8 H8A 109.8 . . ? C7 C8 H8A 109.8 . . ? C9 C8 H8B 109.8 . . ? C7 C8 H8B 109.8 . . ? H8A C8 H8B 108.3 . . ? C8 C9 C10 110.6(3) . . ? C8 C9 H9A 109.5 . . ? C10 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? C10 C9 H9B 109.5 . . ? H9A C9 H9B 108.1 . . ? N11 C10 C13 109.1(3) . . ? N11 C10 C9 110.6(3) . . ? C13 C10 C9 111.5(3) . . ? N11 C10 H10 108.5 . . ? C13 C10 H10 108.5 . . ? C9 C10 H10 108.5 . . ? C15 C12 C2 114.8(3) . . ? C15 C12 C6 114.2(3) . . ? C2 C12 C6 99.3(3) . . ? C15 C12 H12 109.4 . . ? C2 C12 H12 109.4 . . ? C6 C12 H12 109.4 . . ? O14 C13 C10 111.7(3) . . ? O14 C13 H13A 109.3 . . ? C10 C13 H13A 109.3 . . ? O14 C13 H13B 109.3 . . ? C10 C13 H13B 109.3 . . ? H13A C13 H13B 107.9 . . ? N16 C15 C12 177.7(5) . . ? C18 O17 N27 109.7(3) . . ? C29 O30 H30 93(4) . . ? O17 N27 C26 104.3(3) . . ? O17 N27 C22 104.0(3) . . ? C26 N27 C22 115.8(3) . . ? O17 C18 C19 109.3(4) . . ? O17 C18 C28 102.3(3) . . ? C19 C18 C28 111.8(4) . . ? O17 C18 H18 111.0 . . ? C19 C18 H18 111.0 . . ? C28 C18 H18 111.0 . . ? C18 C19 C20 109.9(4) . . ? C18 C19 H19A 109.7 . . ? C20 C19 H19A 109.7 . . ? C18 C19 H19B 109.7 . . ? C20 C19 H19B 109.7 . . ? H19A C19 H19B 108.2 . . ? C21 C20 C19 113.5(4) . . ? C21 C20 H20A 108.9 . . ? C19 C20 H20A 108.9 . . ? C21 C20 H20B 108.9 . . ? C19 C20 H20B 108.9 . . ? H20A C20 H20B 107.7 . . ? C20 C21 C22 115.9(4) . . ? C20 C21 H21A 108.3 . . ? C22 C21 H21A 108.3 . . ? C20 C21 H21B 108.3 . . ? C22 C21 H21B 108.3 . . ? H21A C21 H21B 107.4 . . ? N27 C22 C23 112.2(4) . . ? N27 C22 C28 101.5(3) . . ? C23 C22 C28 115.5(4) . . ? N27 C22 C21 108.7(3) . . ? C23 C22 C21 110.1(4) . . ? C28 C22 C21 108.4(4) . . ? C22 C23 C24 113.9(4) . . ? C22 C23 H23A 108.8 . . ? C24 C23 H23A 108.8 . . ? C22 C23 H23B 108.8 . . ? C24 C23 H23B 108.8 . . ? H23A C23 H23B 107.7 . . ? C25 C24 C23 108.2(4) . . ? C25 C24 H24A 110.1 . . ? C23 C24 H24A 110.1 . . ? C25 C24 H24B 110.1 . . ? C23 C24 H24B 110.1 . . ? H24A C24 H24B 108.4 . . ? C24 C25 C26 110.2(4) . . ? C24 C25 H25A 109.6 . . ? C26 C25 H25A 109.6 . . ? C24 C25 H25B 109.6 . . ? C26 C25 H25B 109.6 . . ? H25A C25 H25B 108.1 . . ? N27 C26 C29 109.3(3) . . ? N27 C26 C25 110.3(3) . . ? C29 C26 C25 112.2(4) . . ? N27 C26 H26 108.3 . . ? C29 C26 H26 108.3 . . ? C25 C26 H26 108.3 . . ? C31 C28 C22 114.9(4) . . ? C31 C28 C18 113.7(4) . . ? C22 C28 C18 99.0(3) . . ? C31 C28 H28 109.6 . . ? C22 C28 H28 109.6 . . ? C18 C28 H28 109.6 . . ? O30 C29 C26 111.2(3) . . ? O30 C29 H29B 109.4 . . ? C26 C29 H29B 109.4 . . ? O30 C29 H29A 109.4 . . ? C26 C29 H29A 109.4 . . ? H29B C29 H29A 108.0 . . ? N32 C31 C28 178.5(6) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C2 O1 N11 C10 -113.4(3) . . . . ? C2 O1 N11 C6 8.3(4) . . . . ? N11 O1 C2 C3 -95.5(4) . . . . ? N11 O1 C2 C12 21.7(4) . . . . ? O1 C2 C3 C4 48.0(4) . . . . ? C12 C2 C3 C4 -63.3(4) . . . . ? C2 C3 C4 C5 42.8(5) . . . . ? C3 C4 C5 C6 -40.7(5) . . . . ? O1 N11 C6 C12 -34.6(3) . . . . ? C10 N11 C6 C12 78.7(4) . . . . ? O1 N11 C6 C5 80.7(3) . . . . ? C10 N11 C6 C5 -165.9(3) . . . . ? O1 N11 C6 C7 -157.7(3) . . . . ? C10 N11 C6 C7 -44.4(4) . . . . ? C4 C5 C6 N11 -54.7(4) . . . . ? C4 C5 C6 C12 55.9(5) . . . . ? C4 C5 C6 C7 -178.1(4) . . . . ? N11 C6 C7 C8 44.6(5) . . . . ? C12 C6 C7 C8 -71.1(5) . . . . ? C5 C6 C7 C8 166.1(4) . . . . ? C6 C7 C8 C9 -52.8(5) . . . . ? C7 C8 C9 C10 59.5(5) . . . . ? O1 N11 C10 C13 -72.2(3) . . . . ? C6 N11 C10 C13 174.7(3) . . . . ? O1 N11 C10 C9 164.8(3) . . . . ? C6 N11 C10 C9 51.7(4) . . . . ? C8 C9 C10 N11 -59.2(5) . . . . ? C8 C9 C10 C13 179.2(4) . . . . ? O1 C2 C12 C15 -163.8(3) . . . . ? C3 C2 C12 C15 -48.0(5) . . . . ? O1 C2 C12 C6 -41.6(4) . . . . ? C3 C2 C12 C6 74.2(4) . . . . ? N11 C6 C12 C15 170.1(3) . . . . ? C5 C6 C12 C15 54.6(5) . . . . ? C7 C6 C12 C15 -68.3(5) . . . . ? N11 C6 C12 C2 47.4(4) . . . . ? C5 C6 C12 C2 -68.0(4) . . . . ? C7 C6 C12 C2 169.0(3) . . . . ? N11 C10 C13 O14 -74.5(4) . . . . ? C9 C10 C13 O14 47.9(5) . . . . ? C18 O17 N27 C26 -113.4(4) . . . . ? C18 O17 N27 C22 8.4(4) . . . . ? N27 O17 C18 C19 -97.0(4) . . . . ? N27 O17 C18 C28 21.6(4) . . . . ? O17 C18 C19 C20 50.2(5) . . . . ? C28 C18 C19 C20 -62.3(5) . . . . ? C18 C19 C20 C21 40.4(6) . . . . ? C19 C20 C21 C22 -38.9(6) . . . . ? O17 N27 C22 C23 -158.9(4) . . . . ? C26 N27 C22 C23 -45.1(5) . . . . ? O17 N27 C22 C28 -35.0(4) . . . . ? C26 N27 C22 C28 78.8(4) . . . . ? O17 N27 C22 C21 79.2(4) . . . . ? C26 N27 C22 C21 -167.0(4) . . . . ? C20 C21 C22 N27 -54.7(5) . . . . ? C20 C21 C22 C23 -177.9(4) . . . . ? C20 C21 C22 C28 54.9(5) . . . . ? N27 C22 C23 C24 46.2(6) . . . . ? C28 C22 C23 C24 -69.5(6) . . . . ? C21 C22 C23 C24 167.4(5) . . . . ? C22 C23 C24 C25 -54.6(6) . . . . ? C23 C24 C25 C26 60.9(6) . . . . ? O17 N27 C26 C29 -70.3(3) . . . . ? C22 N27 C26 C29 176.0(3) . . . . ? O17 N27 C26 C25 165.8(3) . . . . ? C22 N27 C26 C25 52.1(4) . . . . ? C24 C25 C26 N27 -60.0(5) . . . . ? C24 C25 C26 C29 177.8(4) . . . . ? N27 C22 C28 C31 168.8(4) . . . . ? C23 C22 C28 C31 -69.6(5) . . . . ? C21 C22 C28 C31 54.4(5) . . . . ? N27 C22 C28 C18 47.3(4) . . . . ? C23 C22 C28 C18 168.9(4) . . . . ? C21 C22 C28 C18 -67.1(4) . . . . ? O17 C18 C28 C31 -164.2(4) . . . . ? C19 C18 C28 C31 -47.4(5) . . . . ? O17 C18 C28 C22 -41.9(4) . . . . ? C19 C18 C28 C22 74.9(4) . . . . ? N27 C26 C29 O30 -73.1(4) . . . . ? C25 C26 C29 O30 49.6(5) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O30 H30 N11 0.822(10) 2.19(2) 2.970(4) 158(5) . O14 H14 N27 0.821(10) 2.119(18) 2.917(4) 164(5) .