# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Phil Andrews' 'Steven Bull' 'Benjamin Fraser' 'Paul Jensen' 'Magdaline Minopoulos' _publ_contact_author_name 'Phil Andrews' _publ_contact_author_address ; School of Chemistry Monash University Wellington Road Clayton Melbourne Victoria 3800 AUSTRALIA ; _publ_contact_author_email PHIL.ANDREWS@SCI.MONASH.EDU.AU _publ_requested_journal 'Chemical Communications' _publ_section_title ; A New Diastereoselective Aza-Allyl - Michael Addition - Ring Closure Reaction Sequence and its Application in the Construction of Six Contiguous Stereogenic Centres ; data_pca06pj1 _database_code_depnum_ccdc_archive 'CCDC 648199' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C37 H47 N O4' _chemical_formula_sum 'C37 H47 N O4' _chemical_formula_weight 569.76 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 0.0000 '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 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21 ' _symmetry_space_group_name_Hall 'P 2ac 2ab ' _symmetry_int_tables_number 19 _chemical_absolute_configuration syn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 5.8650(2) _cell_length_b 19.1247(7) _cell_length_c 29.4680(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3305.3(2) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 5421 _cell_measurement_theta_min 2.7649 _cell_measurement_theta_max 26.8456 _exptl_crystal_description needle _exptl_crystal_colour colorless _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.145 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1232 _exptl_absorpt_coefficient_mu 0.073 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.844 _exptl_absorpt_correction_T_max 0.998 _exptl_absorpt_process_details ; SADABS Ver. 2.10 (Bruker-AXS, 2004) ; _diffrn_crystal_treatment ; attached with Exxon Paratone N, to a short length of fibre supported on a thin piece of copper wire inserted in a copper mounting pin. The crystal was quenched in a cold nitrogen gas stream from an Oxford Cryosystems Cryostream. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker-Nonius FR591 Kappa APEX II' _diffrn_measurement_method '\w and \f' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 20518 _diffrn_reflns_av_R_equivalents 0.0377 _diffrn_reflns_av_sigmaI/netI 0.0331 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -36 _diffrn_reflns_limit_l_max 38 _diffrn_reflns_theta_min 2.96 _diffrn_reflns_theta_max 27.47 _reflns_number_total 4289 _reflns_number_gt 3515 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'APEX2 Ver. 2.1-RC13 (Bruker-AXS, 2006)' _computing_cell_refinement 'SAINT Ver. 6.45A (Bruker-AXS, 2004)' _computing_data_reduction 'SAINT Ver. 6.45A' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; X-Seed (Barbour, 2001), SHELXTL Ver. 6.14 (Bruker-AXS, 2003) ; _computing_publication_material 'modiCIFer-12162005 (Guzei, 2005)' _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^)+(0.0363P)^2^+0.4924P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4289 _refine_ls_number_parameters 393 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0525 _refine_ls_R_factor_gt 0.0363 _refine_ls_wR_factor_ref 0.0820 _refine_ls_wR_factor_gt 0.0752 _refine_ls_goodness_of_fit_ref 1.028 _refine_ls_restrained_S_all 1.028 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 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 0.4973(2) -0.07522(6) 0.04051(4) 0.0247(3) Uani 1 1 d . . . O2 O 0.2009(2) -0.03534(7) 0.08291(5) 0.0283(3) Uani 1 1 d . . . O3 O 1.0597(2) 0.16044(7) 0.16347(5) 0.0329(3) Uani 1 1 d . . . O4 O 0.6825(2) 0.18491(6) 0.15723(5) 0.0254(3) Uani 1 1 d . . . N1 N 0.5350(3) 0.05856(8) 0.22034(5) 0.0244(3) Uani 1 1 d . . . H1 H 0.447(4) 0.0802(11) 0.1997(7) 0.029 Uiso 1 1 d . . . C1 C 0.2384(4) -0.04203(12) -0.02104(8) 0.0452(6) Uani 1 1 d . . . H1A H 0.1152 -0.0250 -0.0015 0.068 Uiso 1 1 calc R . . H1B H 0.1745 -0.0582 -0.0499 0.068 Uiso 1 1 calc R . . H1C H 0.3467 -0.0040 -0.0268 0.068 Uiso 1 1 calc R . . C2 C 0.5479(4) -0.13188(13) -0.02812(8) 0.0445(6) Uani 1 1 d . . . H2A H 0.6601 -0.0953 -0.0347 0.067 Uiso 1 1 calc R . . H2B H 0.4807 -0.1486 -0.0566 0.067 Uiso 1 1 calc R . . H2C H 0.6231 -0.1708 -0.0125 0.067 Uiso 1 1 calc R . . C3 C 0.1998(5) -0.15898(12) 0.01860(8) 0.0451(6) Uani 1 1 d . . . H3A H 0.2847 -0.1929 0.0369 0.068 Uiso 1 1 calc R . . H3B H 0.1320 -0.1827 -0.0076 0.068 Uiso 1 1 calc R . . H3C H 0.0787 -0.1380 0.0371 0.068 Uiso 1 1 calc R . . C4 C 0.3605(4) -0.10211(10) 0.00222(7) 0.0300(5) Uani 1 1 d . . . C5 C 0.4031(3) -0.04526(9) 0.07709(6) 0.0216(4) Uani 1 1 d . . . C6 C 0.5860(3) -0.02647(9) 0.11121(6) 0.0207(4) Uani 1 1 d . . . H6 H 0.7359 -0.0426 0.0989 0.025 Uiso 1 1 calc R . . C7 C 0.5998(3) 0.05358(9) 0.11838(6) 0.0203(4) Uani 1 1 d . . . H7 H 0.453(4) 0.0691(10) 0.1317(6) 0.024 Uiso 1 1 d . . . C8 C 0.6282(3) 0.09186(9) 0.07339(6) 0.0219(4) Uani 1 1 d . . . C9 C 0.4523(4) 0.13338(10) 0.05639(7) 0.0291(4) Uani 1 1 d . . . H9 H 0.3166 0.1390 0.0736 0.035 Uiso 1 1 calc R . . C10 C 0.4727(4) 0.16655(11) 0.01468(7) 0.0352(5) Uani 1 1 d . . . H10 H 0.3512 0.1946 0.0036 0.042 Uiso 1 1 calc R . . C11 C 0.6688(4) 0.15896(11) -0.01074(7) 0.0357(5) Uani 1 1 d . . . H11 H 0.6824 0.1816 -0.0393 0.043 Uiso 1 1 calc R . . C12 C 0.8458(4) 0.11812(11) 0.00563(7) 0.0332(5) Uani 1 1 d . . . H12 H 0.9813 0.1130 -0.0117 0.040 Uiso 1 1 calc R . . C13 C 0.8258(3) 0.08459(10) 0.04740(7) 0.0278(4) Uani 1 1 d . . . H13 H 0.9477 0.0565 0.0583 0.033 Uiso 1 1 calc R . . C14 C 0.7962(3) 0.06615(9) 0.15228(6) 0.0212(4) Uani 1 1 d . . . H14 H 0.9328 0.0417 0.1396 0.025 Uiso 1 1 calc R . . C15 C 0.8636(3) 0.14221(10) 0.15825(6) 0.0235(4) Uani 1 1 d . . . C16 C 0.7110(3) 0.26204(10) 0.15638(8) 0.0295(4) Uani 1 1 d . . . C17 C 0.4657(4) 0.28701(11) 0.15124(9) 0.0423(6) Uani 1 1 d . . . H17A H 0.4030 0.2696 0.1226 0.063 Uiso 1 1 calc R . . H17B H 0.4621 0.3382 0.1513 0.063 Uiso 1 1 calc R . . H17C H 0.3741 0.2693 0.1766 0.063 Uiso 1 1 calc R . . C18 C 0.8133(4) 0.28753(11) 0.20075(8) 0.0415(6) Uani 1 1 d . . . H18A H 0.7194 0.2712 0.2261 0.062 Uiso 1 1 calc R . . H18B H 0.8181 0.3388 0.2008 0.062 Uiso 1 1 calc R . . H18C H 0.9683 0.2691 0.2039 0.062 Uiso 1 1 calc R . . C19 C 0.8507(4) 0.28246(12) 0.11481(8) 0.0398(5) Uani 1 1 d . . . H19A H 1.0067 0.2648 0.1181 0.060 Uiso 1 1 calc R . . H19B H 0.8540 0.3335 0.1120 0.060 Uiso 1 1 calc R . . H19C H 0.7813 0.2622 0.0876 0.060 Uiso 1 1 calc R . . C20 C 0.7427(3) 0.03047(9) 0.19855(6) 0.0237(4) Uani 1 1 d . . . H20 H 0.8740 0.0396 0.2194 0.028 Uiso 1 1 calc R . . C21 C 0.5745(3) 0.10658(10) 0.25867(6) 0.0239(4) Uani 1 1 d . . . H21 H 0.7137 0.1351 0.2522 0.029 Uiso 1 1 calc R . . C22 C 0.3697(4) 0.15554(11) 0.26241(7) 0.0320(5) Uani 1 1 d . . . H22A H 0.3604 0.1847 0.2351 0.048 Uiso 1 1 calc R . . H22B H 0.3873 0.1855 0.2892 0.048 Uiso 1 1 calc R . . H22C H 0.2299 0.1278 0.2653 0.048 Uiso 1 1 calc R . . C23 C 0.6133(3) 0.06524(10) 0.30209(6) 0.0255(4) Uani 1 1 d . . . C24 C 0.4429(4) 0.02221(10) 0.31963(7) 0.0314(5) Uani 1 1 d . . . H24 H 0.3023 0.0178 0.3039 0.038 Uiso 1 1 calc R . . C25 C 0.4758(4) -0.01425(11) 0.35970(7) 0.0387(5) Uani 1 1 d . . . H25 H 0.3567 -0.0426 0.3715 0.046 Uiso 1 1 calc R . . C26 C 0.6825(5) -0.00959(12) 0.38270(8) 0.0453(6) Uani 1 1 d . . . H26 H 0.7057 -0.0350 0.4100 0.054 Uiso 1 1 calc R . . C27 C 0.8532(4) 0.03219(13) 0.36543(8) 0.0436(6) Uani 1 1 d . . . H27 H 0.9949 0.0356 0.3809 0.052 Uiso 1 1 calc R . . C28 C 0.8186(4) 0.06942(11) 0.32537(7) 0.0319(5) Uani 1 1 d . . . H28 H 0.9374 0.0981 0.3138 0.038 Uiso 1 1 calc R . . C29 C 0.7277(3) -0.04911(9) 0.19099(6) 0.0255(4) Uani 1 1 d . . . H29 H 0.8766 -0.0646 0.1779 0.031 Uiso 1 1 calc R . . C30 C 0.6934(4) -0.08871(10) 0.23559(7) 0.0369(5) Uani 1 1 d . . . H30A H 0.5422 -0.0780 0.2479 0.055 Uiso 1 1 calc R . . H30B H 0.8107 -0.0744 0.2574 0.055 Uiso 1 1 calc R . . H30C H 0.7055 -0.1391 0.2300 0.055 Uiso 1 1 calc R . . C31 C 0.5408(3) -0.06622(9) 0.15602(6) 0.0222(4) Uani 1 1 d . . . H31 H 0.3922 -0.0493 0.1685 0.027 Uiso 1 1 calc R . . C32 C 0.5166(3) -0.14419(9) 0.14612(6) 0.0240(4) Uani 1 1 d . . . C33 C 0.3171(4) -0.17999(10) 0.15656(8) 0.0340(5) Uani 1 1 d . . . H33 H 0.1977 -0.1564 0.1721 0.041 Uiso 1 1 calc R . . C34 C 0.2896(4) -0.24979(11) 0.14466(8) 0.0430(6) Uani 1 1 d . . . H34 H 0.1518 -0.2734 0.1519 0.052 Uiso 1 1 calc R . . C35 C 0.4613(5) -0.28494(11) 0.12240(8) 0.0411(6) Uani 1 1 d . . . H35 H 0.4420 -0.3325 0.1140 0.049 Uiso 1 1 calc R . . C36 C 0.6616(5) -0.25036(11) 0.11242(7) 0.0391(5) Uani 1 1 d . . . H36 H 0.7812 -0.2746 0.0974 0.047 Uiso 1 1 calc R . . C37 C 0.6904(4) -0.18063(10) 0.12410(7) 0.0323(5) Uani 1 1 d . . . H37 H 0.8294 -0.1576 0.1171 0.039 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 0.0271(7) 0.0281(7) 0.0188(7) -0.0047(5) -0.0022(6) -0.0001(6) O2 0.0233(7) 0.0331(8) 0.0286(8) -0.0012(6) -0.0041(6) 0.0032(6) O3 0.0207(7) 0.0356(8) 0.0424(9) -0.0031(7) -0.0035(6) -0.0036(6) O4 0.0213(6) 0.0217(6) 0.0331(7) -0.0033(6) 0.0009(6) -0.0021(5) N1 0.0257(8) 0.0291(9) 0.0183(8) -0.0040(7) -0.0017(7) 0.0007(7) C1 0.0537(15) 0.0542(15) 0.0277(12) -0.0001(10) -0.0115(11) 0.0080(12) C2 0.0458(13) 0.0557(15) 0.0319(12) -0.0204(11) -0.0045(11) -0.0008(12) C3 0.0504(14) 0.0428(13) 0.0420(14) -0.0101(10) -0.0062(12) -0.0153(12) C4 0.0352(10) 0.0328(11) 0.0219(10) -0.0077(8) -0.0060(9) -0.0034(9) C5 0.0254(10) 0.0187(9) 0.0206(10) 0.0029(7) -0.0027(8) 0.0015(7) C6 0.0207(9) 0.0220(9) 0.0193(10) -0.0027(7) -0.0012(8) 0.0021(7) C7 0.0196(9) 0.0210(9) 0.0202(10) -0.0013(7) -0.0006(8) 0.0028(7) C8 0.0248(9) 0.0184(9) 0.0227(10) -0.0024(7) -0.0037(8) -0.0016(7) C9 0.0277(10) 0.0273(10) 0.0322(11) 0.0008(8) -0.0031(9) 0.0030(8) C10 0.0379(11) 0.0307(11) 0.0372(12) 0.0079(9) -0.0102(10) 0.0039(9) C11 0.0454(13) 0.0346(11) 0.0272(11) 0.0089(9) -0.0051(10) -0.0078(10) C12 0.0325(11) 0.0402(12) 0.0269(11) 0.0044(9) 0.0028(10) -0.0018(9) C13 0.0261(9) 0.0309(11) 0.0264(10) 0.0034(8) -0.0023(9) 0.0044(8) C14 0.0200(8) 0.0241(9) 0.0193(9) -0.0029(7) -0.0011(8) 0.0028(8) C15 0.0228(9) 0.0297(10) 0.0179(9) -0.0024(8) -0.0004(8) 0.0000(8) C16 0.0250(9) 0.0206(9) 0.0430(12) 0.0006(8) 0.0026(10) -0.0034(8) C17 0.0276(10) 0.0259(11) 0.0734(17) 0.0039(11) 0.0070(12) 0.0013(9) C18 0.0422(12) 0.0309(11) 0.0515(15) -0.0118(10) 0.0021(12) -0.0065(10) C19 0.0335(11) 0.0375(12) 0.0483(14) 0.0118(11) 0.0032(11) -0.0041(10) C20 0.0234(9) 0.0282(10) 0.0196(9) -0.0018(8) -0.0044(8) 0.0020(7) C21 0.0267(10) 0.0255(10) 0.0194(9) -0.0020(8) 0.0026(8) -0.0022(8) C22 0.0397(11) 0.0313(11) 0.0251(11) -0.0017(9) 0.0002(9) 0.0061(9) C23 0.0309(10) 0.0265(10) 0.0193(9) -0.0062(8) 0.0032(8) 0.0049(8) C24 0.0363(11) 0.0285(10) 0.0293(11) -0.0022(8) 0.0058(10) 0.0030(9) C25 0.0513(14) 0.0310(12) 0.0337(12) 0.0042(9) 0.0158(11) 0.0079(10) C26 0.0616(16) 0.0478(14) 0.0264(12) 0.0089(10) 0.0082(12) 0.0250(13) C27 0.0422(13) 0.0602(16) 0.0285(12) -0.0007(11) -0.0043(11) 0.0178(12) C28 0.0312(10) 0.0398(12) 0.0248(10) -0.0041(9) 0.0026(9) 0.0056(10) C29 0.0305(10) 0.0263(10) 0.0196(9) -0.0007(7) -0.0044(8) 0.0053(8) C30 0.0584(14) 0.0288(11) 0.0235(11) 0.0017(8) -0.0089(11) 0.0033(11) C31 0.0248(8) 0.0220(9) 0.0198(9) -0.0006(7) 0.0003(8) 0.0035(8) C32 0.0315(10) 0.0216(9) 0.0189(9) 0.0017(7) -0.0052(8) 0.0028(8) C33 0.0339(11) 0.0271(11) 0.0410(12) 0.0054(9) 0.0003(11) 0.0046(9) C34 0.0465(13) 0.0270(11) 0.0556(15) 0.0096(10) -0.0110(13) -0.0051(10) C35 0.0668(16) 0.0213(10) 0.0354(12) 0.0008(9) -0.0137(13) 0.0006(11) C36 0.0569(15) 0.0296(11) 0.0309(12) -0.0051(9) 0.0036(12) 0.0106(11) C37 0.0406(11) 0.0276(10) 0.0286(11) -0.0019(8) 0.0020(10) 0.0049(10) _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 C5 1.340(2) . ? O1 C4 1.477(2) . ? O2 C5 1.213(2) . ? O3 C15 1.212(2) . ? O4 C15 1.340(2) . ? O4 C16 1.485(2) . ? N1 C21 1.474(2) . ? N1 C20 1.478(2) . ? N1 H1 0.90(2) . ? C1 C4 1.518(3) . ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C1 H1C 0.9800 . ? C2 C4 1.527(3) . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 0.9800 . ? C3 C4 1.518(3) . ? C3 H3A 0.9800 . ? C3 H3B 0.9800 . ? C3 H3C 0.9800 . ? C5 C6 1.514(3) . ? C6 C31 1.547(2) . ? C6 C7 1.548(2) . ? C6 H6 1.0000 . ? C7 C8 1.524(3) . ? C7 C14 1.544(2) . ? C7 H7 0.99(2) . ? C8 C9 1.395(3) . ? C8 C13 1.396(3) . ? C9 C10 1.388(3) . ? C9 H9 0.9500 . ? C10 C11 1.380(3) . ? C10 H10 0.9500 . ? C11 C12 1.386(3) . ? C11 H11 0.9500 . ? C12 C13 1.393(3) . ? C12 H12 0.9500 . ? C13 H13 0.9500 . ? C14 C15 1.518(3) . ? C14 C20 1.557(3) . ? C14 H14 1.0000 . ? C16 C18 1.519(3) . ? C16 C17 1.523(3) . ? C16 C19 1.525(3) . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? C18 H18C 0.9800 . ? C19 H19A 0.9800 . ? C19 H19B 0.9800 . ? C19 H19C 0.9800 . ? C20 C29 1.541(3) . ? C20 H20 1.0000 . ? C21 C23 1.521(3) . ? C21 C22 1.527(3) . ? C21 H21 1.0000 . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 0.9800 . ? C23 C28 1.388(3) . ? C23 C24 1.394(3) . ? C24 C25 1.385(3) . ? C24 H24 0.9500 . ? C25 C26 1.391(4) . ? C25 H25 0.9500 . ? C26 C27 1.379(4) . ? C26 H26 0.9500 . ? C27 C28 1.393(3) . ? C27 H27 0.9500 . ? C28 H28 0.9500 . ? C29 C30 1.530(3) . ? C29 C31 1.540(3) . ? C29 H29 1.0000 . ? C30 H30A 0.9800 . ? C30 H30B 0.9800 . ? C30 H30C 0.9800 . ? C31 C32 1.526(2) . ? C31 H31 1.0000 . ? C32 C33 1.390(3) . ? C32 C37 1.395(3) . ? C33 C34 1.390(3) . ? C33 H33 0.9500 . ? C34 C35 1.377(3) . ? C34 H34 0.9500 . ? C35 C36 1.380(3) . ? C35 H35 0.9500 . ? C36 C37 1.388(3) . ? C36 H36 0.9500 . ? C37 H37 0.9500 . ? 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 C5 O1 C4 122.64(15) . . ? C15 O4 C16 121.10(15) . . ? C21 N1 C20 115.44(15) . . ? C21 N1 H1 108.8(13) . . ? C20 N1 H1 110.3(13) . . ? C4 C1 H1A 109.5 . . ? C4 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C4 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? C4 C2 H2A 109.5 . . ? C4 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? C4 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? C4 C3 H3A 109.5 . . ? C4 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? C4 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? O1 C4 C1 109.74(16) . . ? O1 C4 C3 110.12(16) . . ? C1 C4 C3 113.13(19) . . ? O1 C4 C2 100.73(16) . . ? C1 C4 C2 110.9(2) . . ? C3 C4 C2 111.46(18) . . ? O2 C5 O1 125.73(18) . . ? O2 C5 C6 124.18(18) . . ? O1 C5 C6 110.09(15) . . ? C5 C6 C31 109.20(15) . . ? C5 C6 C7 111.25(14) . . ? C31 C6 C7 112.24(14) . . ? C5 C6 H6 108.0 . . ? C31 C6 H6 108.0 . . ? C7 C6 H6 108.0 . . ? C8 C7 C14 114.00(14) . . ? C8 C7 C6 111.23(14) . . ? C14 C7 C6 106.33(14) . . ? C8 C7 H7 107.2(11) . . ? C14 C7 H7 110.1(11) . . ? C6 C7 H7 107.8(11) . . ? C9 C8 C13 118.28(17) . . ? C9 C8 C7 120.33(17) . . ? C13 C8 C7 121.35(16) . . ? C10 C9 C8 120.9(2) . . ? C10 C9 H9 119.5 . . ? C8 C9 H9 119.5 . . ? C11 C10 C9 120.3(2) . . ? C11 C10 H10 119.9 . . ? C9 C10 H10 119.9 . . ? C10 C11 C12 119.65(19) . . ? C10 C11 H11 120.2 . . ? C12 C11 H11 120.2 . . ? C11 C12 C13 120.3(2) . . ? C11 C12 H12 119.9 . . ? C13 C12 H12 119.9 . . ? C12 C13 C8 120.60(18) . . ? C12 C13 H13 119.7 . . ? C8 C13 H13 119.7 . . ? C15 C14 C7 114.74(15) . . ? C15 C14 C20 111.79(14) . . ? C7 C14 C20 110.38(14) . . ? C15 C14 H14 106.5 . . ? C7 C14 H14 106.5 . . ? C20 C14 H14 106.5 . . ? O3 C15 O4 125.43(17) . . ? O3 C15 C14 122.53(17) . . ? O4 C15 C14 112.03(15) . . ? O4 C16 C18 110.42(16) . . ? O4 C16 C17 101.93(15) . . ? C18 C16 C17 110.98(19) . . ? O4 C16 C19 109.18(16) . . ? C18 C16 C19 113.40(17) . . ? C17 C16 C19 110.33(19) . . ? C16 C17 H17A 109.5 . . ? C16 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C16 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C16 C18 H18A 109.5 . . ? C16 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C16 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C16 C19 H19A 109.5 . . ? C16 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C16 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? N1 C20 C29 112.02(15) . . ? N1 C20 C14 112.78(15) . . ? C29 C20 C14 108.53(14) . . ? N1 C20 H20 107.8 . . ? C29 C20 H20 107.8 . . ? C14 C20 H20 107.8 . . ? N1 C21 C23 110.14(15) . . ? N1 C21 C22 108.27(15) . . ? C23 C21 C22 112.07(16) . . ? N1 C21 H21 108.8 . . ? C23 C21 H21 108.8 . . ? C22 C21 H21 108.8 . . ? C21 C22 H22A 109.5 . . ? C21 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C21 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? C28 C23 C24 118.20(19) . . ? C28 C23 C21 121.04(18) . . ? C24 C23 C21 120.76(18) . . ? C25 C24 C23 120.9(2) . . ? C25 C24 H24 119.5 . . ? C23 C24 H24 119.5 . . ? C24 C25 C26 120.3(2) . . ? C24 C25 H25 119.9 . . ? C26 C25 H25 119.9 . . ? C27 C26 C25 119.4(2) . . ? C27 C26 H26 120.3 . . ? C25 C26 H26 120.3 . . ? C26 C27 C28 120.2(2) . . ? C26 C27 H27 119.9 . . ? C28 C27 H27 119.9 . . ? C23 C28 C27 121.0(2) . . ? C23 C28 H28 119.5 . . ? C27 C28 H28 119.5 . . ? C30 C29 C31 112.09(17) . . ? C30 C29 C20 111.85(15) . . ? C31 C29 C20 110.33(14) . . ? C30 C29 H29 107.4 . . ? C31 C29 H29 107.4 . . ? C20 C29 H29 107.4 . . ? C29 C30 H30A 109.5 . . ? C29 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? C29 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? C32 C31 C29 113.69(15) . . ? C32 C31 C6 109.45(14) . . ? C29 C31 C6 110.18(14) . . ? C32 C31 H31 107.8 . . ? C29 C31 H31 107.8 . . ? C6 C31 H31 107.8 . . ? C33 C32 C37 118.17(18) . . ? C33 C32 C31 121.14(18) . . ? C37 C32 C31 120.61(18) . . ? C34 C33 C32 121.0(2) . . ? C34 C33 H33 119.5 . . ? C32 C33 H33 119.5 . . ? C35 C34 C33 120.3(2) . . ? C35 C34 H34 119.9 . . ? C33 C34 H34 119.9 . . ? C34 C35 C36 119.3(2) . . ? C34 C35 H35 120.3 . . ? C36 C35 H35 120.3 . . ? C35 C36 C37 120.8(2) . . ? C35 C36 H36 119.6 . . ? C37 C36 H36 119.6 . . ? C36 C37 C32 120.4(2) . . ? C36 C37 H37 119.8 . . ? C32 C37 H37 119.8 . . ? 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 C5 O1 C4 C1 64.8(2) . . . . ? C5 O1 C4 C3 -60.4(2) . . . . ? C5 O1 C4 C2 -178.14(17) . . . . ? C4 O1 C5 O2 -1.6(3) . . . . ? C4 O1 C5 C6 177.23(15) . . . . ? O2 C5 C6 C31 59.5(2) . . . . ? O1 C5 C6 C31 -119.33(16) . . . . ? O2 C5 C6 C7 -64.9(2) . . . . ? O1 C5 C6 C7 116.24(16) . . . . ? C5 C6 C7 C8 -53.42(19) . . . . ? C31 C6 C7 C8 -176.13(14) . . . . ? C5 C6 C7 C14 -178.07(15) . . . . ? C31 C6 C7 C14 59.22(18) . . . . ? C14 C7 C8 C9 -128.45(18) . . . . ? C6 C7 C8 C9 111.33(18) . . . . ? C14 C7 C8 C13 53.8(2) . . . . ? C6 C7 C8 C13 -66.4(2) . . . . ? C13 C8 C9 C10 0.1(3) . . . . ? C7 C8 C9 C10 -177.70(18) . . . . ? C8 C9 C10 C11 -0.1(3) . . . . ? C9 C10 C11 C12 -0.1(3) . . . . ? C10 C11 C12 C13 0.3(3) . . . . ? C11 C12 C13 C8 -0.3(3) . . . . ? C9 C8 C13 C12 0.0(3) . . . . ? C7 C8 C13 C12 177.84(18) . . . . ? C8 C7 C14 C15 47.7(2) . . . . ? C6 C7 C14 C15 170.62(15) . . . . ? C8 C7 C14 C20 175.08(14) . . . . ? C6 C7 C14 C20 -61.99(18) . . . . ? C16 O4 C15 O3 8.4(3) . . . . ? C16 O4 C15 C14 -171.94(15) . . . . ? C7 C14 C15 O3 -142.86(19) . . . . ? C20 C14 C15 O3 90.5(2) . . . . ? C7 C14 C15 O4 37.5(2) . . . . ? C20 C14 C15 O4 -89.18(18) . . . . ? C15 O4 C16 C18 -66.7(2) . . . . ? C15 O4 C16 C17 175.28(17) . . . . ? C15 O4 C16 C19 58.6(2) . . . . ? C21 N1 C20 C29 133.30(16) . . . . ? C21 N1 C20 C14 -103.91(18) . . . . ? C15 C14 C20 N1 67.49(19) . . . . ? C7 C14 C20 N1 -61.51(18) . . . . ? C15 C14 C20 C29 -167.79(15) . . . . ? C7 C14 C20 C29 63.21(18) . . . . ? C20 N1 C21 C23 -83.6(2) . . . . ? C20 N1 C21 C22 153.57(16) . . . . ? N1 C21 C23 C28 117.66(19) . . . . ? C22 C21 C23 C28 -121.74(19) . . . . ? N1 C21 C23 C24 -62.5(2) . . . . ? C22 C21 C23 C24 58.1(2) . . . . ? C28 C23 C24 C25 1.3(3) . . . . ? C21 C23 C24 C25 -178.51(17) . . . . ? C23 C24 C25 C26 -1.4(3) . . . . ? C24 C25 C26 C27 0.6(3) . . . . ? C25 C26 C27 C28 0.1(3) . . . . ? C24 C23 C28 C27 -0.6(3) . . . . ? C21 C23 C28 C27 179.24(18) . . . . ? C26 C27 C28 C23 -0.1(3) . . . . ? N1 C20 C29 C30 -59.2(2) . . . . ? C14 C20 C29 C30 175.65(17) . . . . ? N1 C20 C29 C31 66.32(19) . . . . ? C14 C20 C29 C31 -58.85(19) . . . . ? C30 C29 C31 C32 -55.3(2) . . . . ? C20 C29 C31 C32 179.31(15) . . . . ? C30 C29 C31 C6 -178.59(15) . . . . ? C20 C29 C31 C6 56.05(19) . . . . ? C5 C6 C31 C32 53.13(19) . . . . ? C7 C6 C31 C32 176.98(15) . . . . ? C5 C6 C31 C29 178.84(15) . . . . ? C7 C6 C31 C29 -57.31(18) . . . . ? C29 C31 C32 C33 116.4(2) . . . . ? C6 C31 C32 C33 -119.97(19) . . . . ? C29 C31 C32 C37 -67.0(2) . . . . ? C6 C31 C32 C37 56.6(2) . . . . ? C37 C32 C33 C34 -1.2(3) . . . . ? C31 C32 C33 C34 175.50(19) . . . . ? C32 C33 C34 C35 0.3(3) . . . . ? C33 C34 C35 C36 0.6(3) . . . . ? C34 C35 C36 C37 -0.7(3) . . . . ? C35 C36 C37 C32 -0.1(3) . . . . ? C33 C32 C37 C36 1.1(3) . . . . ? C31 C32 C37 C36 -175.63(18) . . . . ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 27.47 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 0.171 _refine_diff_density_min -0.192 _refine_diff_density_rms 0.034