Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2003 data_global _audit_update_record 18-Apr-2003 # #============================================================================== #2 Person making the deposition # _publ_contact_letter ; Please consider this CIF submission as deposition of the crystallographic material of the x-ray determination of the structure reported into an article which is being to be submitted for publication on the 'Chemical Communication' of the Royal Society of Chemistry. Suitable crystals of compound were obtained by crystallization from a methanol solution of the compound. Please, send us the identifier number (depository number CCDC) of this cif material which might be referenced into the article for the supp.mat. available by the Cambridge Crystallographic Data Center. Note that this cif file has been already checked by Encif and "checkcif utility" at the IUCr web server which has given the following acceptable Alert C (except the alert A about the absence of esd on the Flack parameter that has automatically been fixed to 0 for the twin treatment): - difference between the calculated and given Tmin and Tmax (however their ratio is equal then it is only a re-scaling factor) - some short hydrogen contacts in the C21 methyl (it is due to its rotational disorder giving two staggered H position) Note that I am the depositing author of the Structure data as crystallographer Best regards prof. Francesco NICOLO Dip. Ch.Inorg.Ch.Anal.Ch.Fisica Universita - Facolta di Scienze MM.FF.NN. via Salita Sperone 31, Vill. S. Agata I-98166 Messina ME Italy tel. ++39-090-6765730 fax. ++39-090-393756 cell. 339-6969493 E-mail fnicolo@unime.it or nicolo@chem.unime.it ; _journal_coden_Cambridge 182 _publ_contact_author_name 'Grassi, Giovanni' _publ_contact_author_email ggrassi@isengard.unime.it _publ_contact_author_fax 39(090)393897 _publ_contact_author_phone 39(090)6765513 _publ_contact_author_address ; Dip. di Chimica Organica e Biologica Universita degli Studi di Messina Via Salita Sperone 31 I-98166 Vill. S. Agata - Messina Italy ; _publ_requested_journal 'Chem. Comm.' _publ_section_title ; Regio and Diastereoselective Lactonisation of Enolisable 1,3-Dicarbonyles by Reaction with Mesoionic 1,3-Oxazolium-5-olates. ; loop_ _publ_author_name 'Giovanni Grassi' 'Giuseppe Bruno' 'Francessco Nicolo' _publ_section_experimental ; The suitable single crystal was obtained by recrystallization from methanol. Diffraction data of both compounds have been collected, at room temperature, with the Siemens automated four-circle single-crystal diffractometer P4. Reflection intensities were corrected for Lorentz polarization effects. Standard deviations \s(I) were estimated from counting statistics. Absorption correction was applied by fitting a pseudo-ellipsoid to the azimuthal scan data (0-360\% range by a 10\% step) of 8 high \c reflections (Kopfmann & Huber, 1968). The structures was solved by a combination of standard Direct Methods and Fourier synthesis, and refined by using full-matrix least-squares technique on all F^2^ data. All non hydrogen atoms were refined anisotropically. H atoms were located in idealized positions and allowed to ride on their parent C atoms with isotropic displacement parameters related to the refined values of their corresponding parent atoms. The usual rotational disorder of the C21 terminal methyl has been handled by splitting it into two staggered positions with equal site occupancy (0.5). An empirical extinction parameter was included in the last refinement cycles of the model. The Flack parameter has not converged for both the enantiomers and the absolute configuration was not determined. The crystal has been treated as a racemic twin. ; _publ_section_references ; Bruker (1999). XSCANS release 2.31 . Bruker AXS Inc., Madison, Wisconsin, USA. Altomare, A., Cascarano, O., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst., 27, 435-436. Cremer, D. & Pople, J.A. (1975). J. Amer. Chem. Soc. 97, 1354-1358. Kopfmann, G. & Huber, R. (1968). Acta Cryst. A24, 348-351. Nardelli, M. (1995). PARST95 (release locally modified). J. Appl. Cryst., 28, 659. Sheldrick, G.M. (1997). SHELXL-97. Program for the Refinement of Crystal Structures. University of Gottingen, Germany. Siemens (1996). XPW graphic utility in SHELXTL release 5.0.5. Siemens Industrial Automation, Inc. Analytical Instrumentation, Madison, Wisconsin, USA. ; #============================================================================== #============================================================================== #============================================================================== data_risi33 _database_code_CSD 209308 _audit_creation_date 17-APR-2003 _audit_creation_method SHELXL-97 _chemical_name_systematic ; N-Methyl-N-(3,7,7-trimethyl-2,5-dioxo-4-phenyl-3,4,5,6,7,8-hexahydro-2H -chromen-3-yl)-benzamide ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C26 H27 N O4' _chemical_formula_sum 'C26 H27 N O4' _chemical_formula_weight 417.49 _chemical_compound_source 'chemical synthesys' _chemical_absolute_configuration unk 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 'P 21' _symmetry_space_group_name_Hall 'P 2yb' _symmetry_Int_Tables_number 4 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 10.3788(9) _cell_length_b 6.4952(7) _cell_length_c 16.451(2) _cell_angle_alpha 90.00 _cell_angle_beta 92.587(8) _cell_angle_gamma 90.00 _cell_volume 1107.9(2) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 46 _cell_measurement_theta_min 14.320 _cell_measurement_theta_max 34.959 _exptl_crystal_preparation 're-crystallized from methanol solution' _exptl_crystal_description prism _exptl_crystal_colour colourles _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.46 _exptl_crystal_size_min 0.24 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.251 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 444 _exptl_absorpt_coefficient_mu 0.084 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_correction_T_min 0.24474 _exptl_absorpt_correction_T_max 0.26619 _exptl_absorpt_process_details ; \y scan method among Kopfmann & Huber, 1968 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Siemens P4 diffractometer' _diffrn_measurement_method '2\q/\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 197 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 1 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l 1 -2 -7 -1 -2 7 5 -3 8 _diffrn_reflns_number 3734 _diffrn_reflns_av_R_equivalents 0.0132 _diffrn_reflns_av_sigmaI/netI 0.0285 _diffrn_reflns_limit_h_min -1 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.27 _diffrn_reflns_theta_max 27.50 _reflns_number_total 2771 _reflns_number_gt 2114 _reflns_threshold_expression >2\s(I) _computing_data_collection 'XSCANS (Bruker,1999)' _computing_cell_refinement 'XSCANS ' _computing_data_reduction 'XSCANS ' _computing_structure_solution 'SIR97 (Altomare, 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPW (Siemens, 1996)' _computing_publication_material 'PARST97 (Nardelli, 1995) and SHELXL-97' _refine_special_details ; Absolute configuration has not been determined and the crystal model has been treated as a racemic twin. The methyl C21 shows a significant rotational disorder and two staggered positions have been used for its hydrogen atoms. 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^)+(0.0402P)^2^+0.1511P] 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 0.035(3) _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 0.00 _refine_ls_number_reflns 2771 _refine_ls_number_parameters 282 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0638 _refine_ls_R_factor_gt 0.0409 _refine_ls_wR_factor_ref 0.0961 _refine_ls_wR_factor_gt 0.0842 _refine_ls_goodness_of_fit_ref 1.048 _refine_ls_restrained_S_all 1.048 _refine_ls_shift/su_max 0.006 _refine_ls_shift/su_mean 0.001 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 0.64718(17) -0.2815(3) 0.74213(11) 0.0490(5) Uani 1 1 d . . . C2 C 0.5286(3) -0.1912(5) 0.71866(14) 0.0412(6) Uani 1 1 d . . . C3 C 0.5373(2) 0.0374(4) 0.69991(15) 0.0386(6) Uani 1 1 d . . . C4 C 0.5881(2) 0.1339(4) 0.78249(14) 0.0371(6) Uani 1 1 d . . . H4 H 0.6071 0.2792 0.7723 0.045 Uiso 1 1 calc R . . C5 C 0.7138(2) 0.0300(4) 0.80705(15) 0.0368(6) Uani 1 1 d . . . C6 C 0.8095(3) 0.1324(5) 0.86092(16) 0.0433(6) Uani 1 1 d . . . C7 C 0.9281(3) 0.0123(6) 0.88699(18) 0.0586(8) Uani 1 1 d . . . H7A H 0.9099 -0.0673 0.9350 0.070 Uiso 1 1 calc R . . H7B H 0.9968 0.1082 0.9019 0.070 Uiso 1 1 calc R . . C8 C 0.9751(3) -0.1334(5) 0.82183(18) 0.0537(8) Uani 1 1 d . . . C9 C 0.8636(3) -0.2727(5) 0.79455(18) 0.0506(7) Uani 1 1 d . . . H9A H 0.8843 -0.3399 0.7441 0.061 Uiso 1 1 calc R . . H9B H 0.8535 -0.3790 0.8352 0.061 Uiso 1 1 calc R . . C10 C 0.7393(2) -0.1609(4) 0.78184(15) 0.0397(6) Uani 1 1 d . . . O11 O 0.43378(18) -0.2919(3) 0.72371(11) 0.0552(6) Uani 1 1 d . . . N12 N 0.63473(19) 0.0693(3) 0.63717(12) 0.0384(5) Uani 1 1 d . . . C13 C 0.6416(2) -0.0756(5) 0.57796(16) 0.0406(6) Uani 1 1 d . . . O14 O 0.57421(18) -0.2305(4) 0.57814(11) 0.0551(5) Uani 1 1 d . . . C15 C 0.7399(2) -0.0547(4) 0.51434(14) 0.0382(6) Uani 1 1 d . . . C16 C 0.8438(3) -0.1868(6) 0.51871(18) 0.0607(8) Uani 1 1 d . . . H16 H 0.8553 -0.2750 0.5630 0.073 Uiso 1 1 calc R . . C17 C 0.9312(3) -0.1892(7) 0.4577(2) 0.0726(10) Uani 1 1 d . . . H17 H 1.0020 -0.2769 0.4615 0.087 Uiso 1 1 calc R . . C18 C 0.9134(3) -0.0626(6) 0.39190(19) 0.0598(8) Uani 1 1 d . . . H18 H 0.9721 -0.0642 0.3508 0.072 Uiso 1 1 calc R . . C19 C 0.8094(3) 0.0666(6) 0.38627(16) 0.0566(8) Uani 1 1 d . . . H19 H 0.7972 0.1519 0.3412 0.068 Uiso 1 1 calc R . . C20 C 0.7223(2) 0.0708(5) 0.44730(16) 0.0508(7) Uani 1 1 d . . . H20 H 0.6516 0.1588 0.4431 0.061 Uiso 1 1 calc R . . C21 C 0.6954(3) 0.2716(5) 0.63191(18) 0.0545(7) Uani 1 1 d . . . H21A H 0.7033 0.3321 0.6851 0.082 Uiso 0.50 1 calc PR . . H21B H 0.6433 0.3588 0.5966 0.082 Uiso 0.50 1 calc PR . . H21C H 0.7795 0.2569 0.6105 0.082 Uiso 0.50 1 calc PR . . H21D H 0.7140 0.2997 0.5764 0.082 Uiso 0.50 1 d PR . . H21E H 0.6379 0.3748 0.6510 0.082 Uiso 0.50 1 d PR . . H21F H 0.7742 0.2733 0.6649 0.082 Uiso 0.50 1 d PR . . C22 C 0.4070(2) 0.1210(6) 0.66978(16) 0.0523(8) Uani 1 1 d . . . H22A H 0.4146 0.2653 0.6583 0.079 Uiso 1 1 calc R . . H22B H 0.3454 0.1010 0.7109 0.079 Uiso 1 1 calc R . . H22C H 0.3787 0.0495 0.6211 0.079 Uiso 1 1 calc R . . C23 C 0.4890(2) 0.1260(4) 0.84872(14) 0.0379(6) Uani 1 1 d . . . C24 C 0.4084(3) 0.2926(5) 0.85960(16) 0.0495(7) Uani 1 1 d . . . H24 H 0.4138 0.4074 0.8261 0.059 Uiso 1 1 calc R . . C25 C 0.3195(3) 0.2893(6) 0.92007(17) 0.0585(8) Uani 1 1 d . . . H25 H 0.2656 0.4017 0.9270 0.070 Uiso 1 1 calc R . . C26 C 0.3110(3) 0.1195(6) 0.96988(17) 0.0576(8) Uani 1 1 d . . . H26 H 0.2506 0.1168 1.0100 0.069 Uiso 1 1 calc R . . C27 C 0.3909(3) -0.0444(6) 0.96038(16) 0.0533(8) Uani 1 1 d . . . H27 H 0.3859 -0.1578 0.9946 0.064 Uiso 1 1 calc R . . C28 C 0.4801(3) -0.0424(5) 0.89958(15) 0.0460(7) Uani 1 1 d . . . H28 H 0.5339 -0.1551 0.8932 0.055 Uiso 1 1 calc R . . O29 O 0.7918(2) 0.3069(4) 0.88561(13) 0.0615(6) Uani 1 1 d . . . C30 C 1.0869(3) -0.2668(8) 0.8553(2) 0.0894(13) Uani 1 1 d . . . H30A H 1.1578 -0.1800 0.8726 0.134 Uiso 1 1 calc R . . H30B H 1.1137 -0.3584 0.8135 0.134 Uiso 1 1 calc R . . H30C H 1.0592 -0.3455 0.9007 0.134 Uiso 1 1 calc R . . C31 C 1.0205(3) -0.0061(7) 0.7502(2) 0.0796(11) Uani 1 1 d . . . H31A H 1.0907 0.0810 0.7684 0.119 Uiso 1 1 calc R . . H31B H 0.9505 0.0774 0.7288 0.119 Uiso 1 1 calc R . . H31C H 1.0486 -0.0967 0.7084 0.119 Uiso 1 1 calc R . . 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 0.0541(11) 0.0307(10) 0.0606(11) -0.0004(9) -0.0132(9) -0.0024(9) C2 0.0450(15) 0.0420(16) 0.0364(12) 0.0002(12) -0.0012(11) -0.0046(14) C3 0.0376(13) 0.0405(15) 0.0379(12) 0.0033(12) 0.0047(10) 0.0012(13) C4 0.0402(13) 0.0318(13) 0.0398(12) 0.0032(12) 0.0059(10) 0.0007(12) C5 0.0368(12) 0.0349(14) 0.0391(12) 0.0004(11) 0.0053(10) -0.0025(12) C6 0.0453(14) 0.0420(16) 0.0432(14) -0.0085(13) 0.0077(11) -0.0095(14) C7 0.0488(15) 0.068(2) 0.0584(17) -0.0116(17) -0.0097(13) -0.0041(17) C8 0.0394(14) 0.062(2) 0.0598(16) -0.0059(16) -0.0031(13) 0.0060(15) C9 0.0529(15) 0.0447(16) 0.0536(15) -0.0020(14) -0.0036(13) 0.0096(15) C10 0.0424(14) 0.0358(15) 0.0405(13) 0.0008(12) -0.0038(11) -0.0020(12) O11 0.0545(11) 0.0594(13) 0.0513(11) 0.0092(10) -0.0024(9) -0.0233(12) N12 0.0421(11) 0.0353(12) 0.0383(10) 0.0020(10) 0.0090(9) -0.0035(10) C13 0.0398(14) 0.0376(14) 0.0442(14) -0.0001(12) -0.0001(11) -0.0007(13) O14 0.0561(11) 0.0519(13) 0.0582(11) -0.0108(10) 0.0117(9) -0.0170(11) C15 0.0358(12) 0.0382(14) 0.0405(13) -0.0056(12) 0.0010(10) -0.0015(12) C16 0.0590(17) 0.063(2) 0.0607(17) 0.0160(17) 0.0128(14) 0.0164(18) C17 0.0587(18) 0.074(2) 0.088(2) 0.009(2) 0.0238(17) 0.024(2) C18 0.0535(17) 0.072(2) 0.0557(17) -0.0100(18) 0.0201(14) -0.0042(19) C19 0.0508(15) 0.076(2) 0.0424(14) 0.0138(16) -0.0005(12) -0.0092(18) C20 0.0387(13) 0.062(2) 0.0513(15) 0.0111(15) 0.0003(12) 0.0044(15) C21 0.0722(18) 0.0364(16) 0.0568(16) -0.0012(14) 0.0242(14) -0.0098(16) C22 0.0455(14) 0.068(2) 0.0439(14) 0.0044(15) 0.0006(12) 0.0106(16) C23 0.0389(13) 0.0417(15) 0.0329(11) 0.0022(12) 0.0000(10) 0.0021(13) C24 0.0555(16) 0.0477(16) 0.0458(14) 0.0064(14) 0.0074(12) 0.0107(16) C25 0.0512(16) 0.071(2) 0.0544(16) 0.0011(18) 0.0130(13) 0.0153(18) C26 0.0455(16) 0.084(2) 0.0445(15) 0.0036(17) 0.0105(12) -0.0018(18) C27 0.0512(16) 0.065(2) 0.0437(15) 0.0165(15) 0.0035(12) -0.0093(17) C28 0.0457(14) 0.0491(17) 0.0431(13) 0.0072(13) 0.0006(12) 0.0035(14) O29 0.0661(13) 0.0504(13) 0.0684(12) -0.0205(12) 0.0055(10) -0.0098(12) C30 0.0588(19) 0.103(3) 0.104(3) -0.016(3) -0.0224(19) 0.024(2) C31 0.0607(19) 0.083(3) 0.097(3) -0.003(2) 0.0282(18) -0.001(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 C10 1.378(3) . ? O1 C2 1.402(3) . ? C2 O11 1.188(3) . ? C2 C3 1.520(4) . ? C3 N12 1.491(3) . ? C3 C22 1.520(4) . ? C3 C4 1.566(3) . ? C4 C5 1.507(3) . ? C4 C23 1.533(3) . ? C4 H4 0.9800 . ? C5 C10 1.338(4) . ? C5 C6 1.462(4) . ? C6 O29 1.221(4) . ? C6 C7 1.503(4) . ? C7 C8 1.527(4) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 C9 1.521(4) . ? C8 C31 1.531(5) . ? C8 C30 1.530(4) . ? C9 C10 1.487(4) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? N12 C13 1.358(3) . ? N12 C21 1.462(4) . ? C13 O14 1.225(3) . ? C13 C15 1.501(4) . ? C15 C20 1.377(4) . ? C15 C16 1.377(4) . ? C16 C17 1.383(4) . ? C16 H16 0.9300 . ? C17 C18 1.365(5) . ? C17 H17 0.9300 . ? C18 C19 1.367(4) . ? C18 H18 0.9300 . ? C19 C20 1.381(4) . ? C19 H19 0.9300 . ? C20 H20 0.9300 . ? C21 H21A 0.9600 . ? C21 H21B 0.9600 . ? C21 H21C 0.9600 . ? C21 H21D 0.9599 . ? C21 H21E 0.9602 . ? C21 H21F 0.9605 . ? C22 H22A 0.9600 . ? C22 H22B 0.9600 . ? C22 H22C 0.9600 . ? C23 C28 1.383(4) . ? C23 C24 1.385(4) . ? C24 C25 1.387(4) . ? C24 H24 0.9300 . ? C25 C26 1.380(5) . ? C25 H25 0.9300 . ? C26 C27 1.363(5) . ? C26 H26 0.9300 . ? C27 C28 1.393(4) . ? C27 H27 0.9300 . ? C28 H28 0.9300 . ? C30 H30A 0.9600 . ? C30 H30B 0.9600 . ? C30 H30C 0.9600 . ? C31 H31A 0.9600 . ? C31 H31B 0.9600 . ? C31 H31C 0.9600 . ? 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 C10 O1 C2 118.3(2) . . ? O11 C2 O1 118.0(3) . . ? O11 C2 C3 127.5(3) . . ? O1 C2 C3 113.9(2) . . ? N12 C3 C22 110.2(2) . . ? N12 C3 C2 108.9(2) . . ? C22 C3 C2 110.8(2) . . ? N12 C3 C4 109.43(19) . . ? C22 C3 C4 113.6(2) . . ? C2 C3 C4 103.6(2) . . ? C5 C4 C23 113.3(2) . . ? C5 C4 C3 107.9(2) . . ? C23 C4 C3 113.12(19) . . ? C5 C4 H4 107.4 . . ? C23 C4 H4 107.4 . . ? C3 C4 H4 107.4 . . ? C10 C5 C6 118.1(2) . . ? C10 C5 C4 120.9(2) . . ? C6 C5 C4 121.0(2) . . ? O29 C6 C5 121.1(3) . . ? O29 C6 C7 121.4(3) . . ? C5 C6 C7 117.5(2) . . ? C6 C7 C8 113.9(2) . . ? C6 C7 H7A 108.8 . . ? C8 C7 H7A 108.8 . . ? C6 C7 H7B 108.8 . . ? C8 C7 H7B 108.8 . . ? H7A C7 H7B 107.7 . . ? C9 C8 C7 108.2(2) . . ? C9 C8 C31 110.5(3) . . ? C7 C8 C31 108.9(3) . . ? C9 C8 C30 108.9(3) . . ? C7 C8 C30 111.1(3) . . ? C31 C8 C30 109.2(3) . . ? C10 C9 C8 113.3(3) . . ? C10 C9 H9A 108.9 . . ? C8 C9 H9A 108.9 . . ? C10 C9 H9B 108.9 . . ? C8 C9 H9B 108.9 . . ? H9A C9 H9B 107.7 . . ? C5 C10 O1 122.1(2) . . ? C5 C10 C9 126.3(3) . . ? O1 C10 C9 111.6(2) . . ? C13 N12 C21 122.9(2) . . ? C13 N12 C3 117.3(2) . . ? C21 N12 C3 118.2(2) . . ? O14 C13 N12 121.2(2) . . ? O14 C13 C15 118.8(2) . . ? N12 C13 C15 119.8(2) . . ? C20 C15 C16 119.1(2) . . ? C20 C15 C13 122.9(2) . . ? C16 C15 C13 117.6(2) . . ? C15 C16 C17 120.4(3) . . ? C15 C16 H16 119.8 . . ? C17 C16 H16 119.8 . . ? C18 C17 C16 119.9(3) . . ? C18 C17 H17 120.0 . . ? C16 C17 H17 120.0 . . ? C17 C18 C19 120.1(3) . . ? C17 C18 H18 119.9 . . ? C19 C18 H18 119.9 . . ? C18 C19 C20 120.2(3) . . ? C18 C19 H19 119.9 . . ? C20 C19 H19 119.9 . . ? C15 C20 C19 120.2(3) . . ? C15 C20 H20 119.9 . . ? C19 C20 H20 119.9 . . ? N12 C21 H21A 109.5 . . ? N12 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? N12 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N12 C21 H21D 109.4 . . ? H21A C21 H21D 141.1 . . ? H21B C21 H21D 56.2 . . ? H21C C21 H21D 56.3 . . ? N12 C21 H21E 109.4 . . ? H21A C21 H21E 56.3 . . ? H21B C21 H21E 56.2 . . ? H21C C21 H21E 141.1 . . ? H21D C21 H21E 109.5 . . ? N12 C21 H21F 109.6 . . ? H21A C21 H21F 56.3 . . ? H21B C21 H21F 141.0 . . ? H21C C21 H21F 56.2 . . ? H21D C21 H21F 109.4 . . ? H21E C21 H21F 109.5 . . ? C3 C22 H22A 109.5 . . ? C3 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C3 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? C28 C23 C24 118.8(2) . . ? C28 C23 C4 121.5(2) . . ? C24 C23 C4 119.7(2) . . ? C23 C24 C25 120.4(3) . . ? C23 C24 H24 119.8 . . ? C25 C24 H24 119.8 . . ? C26 C25 C24 120.1(3) . . ? C26 C25 H25 120.0 . . ? C24 C25 H25 120.0 . . ? C27 C26 C25 120.0(3) . . ? C27 C26 H26 120.0 . . ? C25 C26 H26 120.0 . . ? C26 C27 C28 120.2(3) . . ? C26 C27 H27 119.9 . . ? C28 C27 H27 119.9 . . ? C23 C28 C27 120.4(3) . . ? C23 C28 H28 119.8 . . ? C27 C28 H28 119.8 . . ? C8 C30 H30A 109.5 . . ? C8 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? C8 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? C8 C31 H31A 109.5 . . ? C8 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? C8 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? 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 C10 O1 C2 O11 -142.5(2) . . . . ? C10 O1 C2 C3 29.9(3) . . . . ? O11 C2 C3 N12 -133.6(3) . . . . ? O1 C2 C3 N12 54.9(3) . . . . ? O11 C2 C3 C22 -12.1(4) . . . . ? O1 C2 C3 C22 176.4(2) . . . . ? O11 C2 C3 C4 110.0(3) . . . . ? O1 C2 C3 C4 -61.5(2) . . . . ? N12 C3 C4 C5 -59.2(3) . . . . ? C22 C3 C4 C5 177.2(2) . . . . ? C2 C3 C4 C5 56.9(2) . . . . ? N12 C3 C4 C23 174.7(2) . . . . ? C22 C3 C4 C23 51.1(3) . . . . ? C2 C3 C4 C23 -69.2(3) . . . . ? C23 C4 C5 C10 99.9(3) . . . . ? C3 C4 C5 C10 -26.1(3) . . . . ? C23 C4 C5 C6 -78.3(3) . . . . ? C3 C4 C5 C6 155.7(2) . . . . ? C10 C5 C6 O29 179.7(3) . . . . ? C4 C5 C6 O29 -2.0(4) . . . . ? C10 C5 C6 C7 -2.4(4) . . . . ? C4 C5 C6 C7 175.9(2) . . . . ? O29 C6 C7 C8 -147.2(3) . . . . ? C5 C6 C7 C8 34.9(4) . . . . ? C6 C7 C8 C9 -54.5(3) . . . . ? C6 C7 C8 C31 65.7(3) . . . . ? C6 C7 C8 C30 -174.0(3) . . . . ? C7 C8 C9 C10 43.7(3) . . . . ? C31 C8 C9 C10 -75.5(3) . . . . ? C30 C8 C9 C10 164.6(3) . . . . ? C6 C5 C10 O1 169.3(2) . . . . ? C4 C5 C10 O1 -8.9(4) . . . . ? C6 C5 C10 C9 -8.3(4) . . . . ? C4 C5 C10 C9 173.5(2) . . . . ? C2 O1 C10 C5 8.2(3) . . . . ? C2 O1 C10 C9 -173.9(2) . . . . ? C8 C9 C10 C5 -14.2(4) . . . . ? C8 C9 C10 O1 168.0(2) . . . . ? C22 C3 N12 C13 -85.1(3) . . . . ? C2 C3 N12 C13 36.6(3) . . . . ? C4 C3 N12 C13 149.3(2) . . . . ? C22 C3 N12 C21 81.3(3) . . . . ? C2 C3 N12 C21 -156.9(2) . . . . ? C4 C3 N12 C21 -44.3(3) . . . . ? C21 N12 C13 O14 -168.8(3) . . . . ? C3 N12 C13 O14 -3.0(4) . . . . ? C21 N12 C13 C15 15.7(4) . . . . ? C3 N12 C13 C15 -178.5(2) . . . . ? O14 C13 C15 C20 103.5(3) . . . . ? N12 C13 C15 C20 -81.0(3) . . . . ? O14 C13 C15 C16 -68.1(3) . . . . ? N12 C13 C15 C16 107.4(3) . . . . ? C20 C15 C16 C17 1.8(5) . . . . ? C13 C15 C16 C17 173.7(3) . . . . ? C15 C16 C17 C18 -1.2(6) . . . . ? C16 C17 C18 C19 0.0(6) . . . . ? C17 C18 C19 C20 0.5(5) . . . . ? C16 C15 C20 C19 -1.3(4) . . . . ? C13 C15 C20 C19 -172.8(3) . . . . ? C18 C19 C20 C15 0.2(5) . . . . ? C5 C4 C23 C28 -35.0(3) . . . . ? C3 C4 C23 C28 88.1(3) . . . . ? C5 C4 C23 C24 143.4(3) . . . . ? C3 C4 C23 C24 -93.5(3) . . . . ? C28 C23 C24 C25 -0.5(4) . . . . ? C4 C23 C24 C25 -179.0(3) . . . . ? C23 C24 C25 C26 0.0(4) . . . . ? C24 C25 C26 C27 0.8(5) . . . . ? C25 C26 C27 C28 -1.0(5) . . . . ? C24 C23 C28 C27 0.3(4) . . . . ? C4 C23 C28 C27 178.7(2) . . . . ? C26 C27 C28 C23 0.4(4) . . . . ? 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 C20 H20 O14 0.93 2.46 3.346(3) 158.9 2_656 C9 H9B O29 0.97 2.30 3.218(4) 156.7 1_545 C24 H24 O11 0.93 2.59 3.522(4) 175.5 1_565 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.175 _refine_diff_density_min -0.176 _refine_diff_density_rms 0.033