Supplementary Material (ESI) for Organic and Biomolecular Chemistry This journal is (C) The Royal Society of Chemistry 2006 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_cambridge 0177 #============================================================================== # 1. SUBMISSION DETAILS _publ_contact_author # Name and address of author for correspondence ; Kunz, Horst Institut of Organic Chemistry University of Mainz Duesbergweg 10-14 55099 Mainz, Germany ; _publ_contact_author_phone '+49 6131 3922334' _publ_contact_author_fax '+49 6131 3924786' _publ_contact_author_email hokunz@uni-mainz.de _publ_section_title ; Stereoselective Syntheses of Piperidinones and their Modification by Organometallic Coupling Reactions ; loop_ _publ_author_name _publ_author_address 'Kranke, Birgit' ; Institut of Organic Chemistry University of Mainz Duesbergweg 10-14 55099 Mainz, Germay ; 'Kunz, Horst' ; Institut of Organic Chemistry University of Mainz Duesbergweg 10-14 55099 Mainz, Germay ; _publ_contact_author_name 'Prof. Horst Kunz' data_10 _database_code_depnum_ccdc_archive 'CCDC 624381' #data_bk172 _audit_creation_method SHELXL-97 _chemical_name_systematic ; (2R,5R,6S)-N-(2',3',4'-Tri-O-pivaloyl-a-d-arabinopyranosyl)-5,6-diallyl- 2-isopropyl-piperidin-4-one ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C34 H55 N O8' _chemical_formula_weight 605.79 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 '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' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 9.576(2) _cell_length_b 20.504(5) _cell_length_c 10.143(3) _cell_angle_alpha 90.00 _cell_angle_beta 112.421(11) _cell_angle_gamma 90.00 _cell_volume 1840.9(8) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 65 _cell_measurement_theta_max 72 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.64 _exptl_crystal_size_mid 0.58 _exptl_crystal_size_min 0.38 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.093 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 660 _exptl_absorpt_coefficient_mu 0.619 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.6928 _exptl_absorpt_correction_T_max 0.7970 _exptl_absorpt_process_details 'Corinc (Dr\"ager, 1971)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CAD4 Enraf Nonius' _diffrn_measurement_device '\k-geometry diffractometer' _diffrn_measurement_method \w/2\q _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 3 _diffrn_reflns_number 6668 _diffrn_reflns_av_R_equivalents 0.0243 _diffrn_reflns_av_sigmaI/netI 0.0200 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 4.31 _diffrn_reflns_theta_max 73.69 _reflns_number_total 6285 _reflns_number_gt 5766 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Enraf Nonius Software V5' _computing_cell_refinement 'Enraf Nonius Software V5' _computing_data_reduction 'Corinc (Dr\"ager, 1971)' _computing_structure_solution 'SIR-92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.1151P)^2^+0.2078P] 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 constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0025(7) _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 0.1(2) _refine_ls_number_reflns 6285 _refine_ls_number_parameters 398 _refine_ls_number_restraints 13 _refine_ls_R_factor_all 0.0604 _refine_ls_R_factor_gt 0.0562 _refine_ls_wR_factor_ref 0.1696 _refine_ls_wR_factor_obs 0.1633 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.033 _refine_ls_shift/su_max 0.001 _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 0.18596(19) 0.24103(8) 0.16635(18) 0.0621(4) Uani 1 1 d . . . C2 C 0.1260(2) 0.29822(11) 0.0793(2) 0.0513(5) Uani 1 1 d . . . H2 H 0.1779 0.3019 0.0130 0.062 Uiso 1 1 calc R . . C3 C -0.0425(2) 0.28880(12) -0.0110(2) 0.0499(4) Uani 1 1 d . . . H3 H -0.1016 0.2897 0.0494 0.060 Uiso 1 1 calc R . . C4 C -0.0678(2) 0.22526(12) -0.0931(2) 0.0548(5) Uani 1 1 d . . . H4 H -0.0238 0.2285 -0.1657 0.066 Uiso 1 1 calc R . . C5 C 0.0027(3) 0.16833(12) 0.0043(3) 0.0618(6) Uani 1 1 d . . . H5 H -0.0098 0.1279 -0.0505 0.074 Uiso 1 1 calc R . . C6 C 0.1688(3) 0.18332(14) 0.0858(3) 0.0694(6) Uani 1 1 d . . . H6A H 0.2161 0.1473 0.1490 0.083 Uiso 1 1 calc R . . H6B H 0.2187 0.1883 0.0193 0.083 Uiso 1 1 calc R . . N7 N 0.1601(2) 0.35580(9) 0.16465(19) 0.0537(4) Uani 1 1 d . . . C8 C 0.0840(3) 0.36201(14) 0.2674(3) 0.0631(6) Uani 1 1 d . . . H8 H -0.0216 0.3490 0.2173 0.076 Uiso 1 1 calc R . . C9 C 0.0840(3) 0.43305(16) 0.3131(3) 0.0765(8) Uani 1 1 d . . . H9 H 0.0496 0.4336 0.3925 0.092 Uiso 1 1 calc R . . C10 C 0.2435(4) 0.45855(17) 0.3687(4) 0.0864(9) Uani 1 1 d . . . C11 C 0.3305(3) 0.44535(16) 0.2753(4) 0.0770(7) Uani 1 1 d . . . H11A H 0.4354 0.4573 0.3265 0.092 Uiso 1 1 calc R . . H11B H 0.2906 0.4726 0.1909 0.092 Uiso 1 1 calc R . . C12 C 0.3226(3) 0.37383(12) 0.2294(3) 0.0571(5) Uani 1 1 d . . . H12 H 0.3687 0.3477 0.3162 0.069 Uiso 1 1 calc R . . C13 C 0.1499(4) 0.31912(17) 0.4019(3) 0.0798(8) Uani 1 1 d . . . H13A H 0.1698 0.2760 0.3736 0.096 Uiso 1 1 calc R . . H13B H 0.2458 0.3375 0.4638 0.096 Uiso 1 1 calc R . . C14 C 0.0520(5) 0.3123(2) 0.4842(5) 0.1022(11) Uani 1 1 d . . . H14 H -0.0473 0.2998 0.4324 0.123 Uiso 1 1 calc R . . C15 C 0.0866(8) 0.3212(4) 0.6149(6) 0.158(3) Uani 1 1 d . . . H15A H 0.1843 0.3337 0.6723 0.190 Uiso 1 1 calc R . . H15B H 0.0145 0.3153 0.6547 0.190 Uiso 1 1 calc R . . C16 C -0.0228(4) 0.47531(19) 0.1960(4) 0.0904(10) Uani 1 1 d . . . H16A H 0.0150 0.4794 0.1202 0.108 Uiso 1 1 calc R . . H16B H -0.1208 0.4542 0.1565 0.108 Uiso 1 1 calc R . . C17 C -0.0409(6) 0.5410(2) 0.2470(5) 0.1065(12) Uani 1 1 d . . . H17 H 0.0460 0.5650 0.2954 0.128 Uiso 1 1 calc R . . C18 C -0.1713(7) 0.5675(3) 0.2283(7) 0.1376(19) Uani 1 1 d . . . H18A H -0.2603 0.5447 0.1802 0.165 Uiso 1 1 calc R . . H18B H -0.1752 0.6091 0.2630 0.165 Uiso 1 1 calc R . . O19 O 0.2991(4) 0.48707(19) 0.4812(4) 0.1336(13) Uani 1 1 d . . . C20 C 0.4123(3) 0.36088(15) 0.1350(3) 0.0678(6) Uani 1 1 d . . . H20 H 0.3977 0.3148 0.1071 0.081 Uiso 1 1 calc R . . C21 C 0.3572(5) 0.4010(2) -0.0017(4) 0.0967(11) Uani 1 1 d . . . H21A H 0.4163 0.3905 -0.0568 0.145 Uiso 1 1 calc R . . H21B H 0.3676 0.4465 0.0217 0.145 Uiso 1 1 calc R . . H21C H 0.2529 0.3911 -0.0561 0.145 Uiso 1 1 calc R . . C22 C 0.5818(3) 0.3709(2) 0.2207(4) 0.0958(11) Uani 1 1 d . . . H22A H 0.6133 0.3444 0.3051 0.144 Uiso 1 1 calc R . . H22B H 0.6008 0.4159 0.2471 0.144 Uiso 1 1 calc R . . H22C H 0.6374 0.3585 0.1634 0.144 Uiso 1 1 calc R . . O23 O -0.08703(18) 0.34100(8) -0.11274(16) 0.0560(4) Uani 1 1 d . . . C24 C -0.2066(3) 0.37795(14) -0.1197(3) 0.0642(6) Uani 1 1 d . . . O25 O -0.2758(3) 0.36871(14) -0.0468(3) 0.0982(8) Uani 1 1 d . . . C26 C -0.2415(4) 0.43059(16) -0.2350(3) 0.0797(8) Uani 1 1 d . . . C27 C -0.3156(7) 0.3976(3) -0.3788(4) 0.1348(19) Uani 1 1 d . . . H27A H -0.2475 0.3660 -0.3910 0.202 Uiso 1 1 calc R . . H27B H -0.3396 0.4297 -0.4531 0.202 Uiso 1 1 calc R . . H27C H -0.4065 0.3762 -0.3835 0.202 Uiso 1 1 calc R . . C28 C -0.3452(8) 0.4806(3) -0.2118(7) 0.156(3) Uani 1 1 d . . . H28A H -0.3675 0.5138 -0.2837 0.234 Uiso 1 1 calc R . . H28B H -0.2969 0.4999 -0.1193 0.234 Uiso 1 1 calc R . . H28C H -0.4373 0.4599 -0.2178 0.234 Uiso 1 1 calc R . . C29 C -0.0961(6) 0.4621(3) -0.2321(6) 0.1269(17) Uani 1 1 d . . . H29A H -0.0323 0.4293 -0.2473 0.190 Uiso 1 1 calc R . . H29B H -0.0446 0.4824 -0.1411 0.190 Uiso 1 1 calc R . . H29C H -0.1200 0.4943 -0.3060 0.190 Uiso 1 1 calc R . . O30 O -0.22851(18) 0.21605(10) -0.16198(19) 0.0650(4) Uani 1 1 d . . . C31 C -0.2832(3) 0.19446(17) -0.2952(3) 0.0719(7) Uani 1 1 d . . . O32 O -0.2041(3) 0.1829(3) -0.3562(3) 0.170(2) Uani 1 1 d . . . C33 C -0.4533(3) 0.18357(16) -0.3556(3) 0.0730(7) Uani 1 1 d . . . C34 C -0.5139(5) 0.1997(3) -0.5127(4) 0.1273(17) Uani 1 1 d . . . H34A H -0.4630 0.1736 -0.5592 0.191 Uiso 1 1 calc R . . H34B H -0.4969 0.2451 -0.5250 0.191 Uiso 1 1 calc R . . H34C H -0.6203 0.1908 -0.5538 0.191 Uiso 1 1 calc R . . C35 C -0.5323(4) 0.2245(3) -0.2805(6) 0.1280(18) Uani 1 1 d . . . H35A H -0.6391 0.2166 -0.3227 0.192 Uiso 1 1 calc R . . H35B H -0.5128 0.2699 -0.2900 0.192 Uiso 1 1 calc R . . H35C H -0.4950 0.2130 -0.1813 0.192 Uiso 1 1 calc R . . C36 C -0.4772(6) 0.1129(3) -0.3317(8) 0.144(2) Uani 1 1 d . . . H36A H -0.4254 0.0863 -0.3765 0.216 Uiso 1 1 calc R . . H36B H -0.5833 0.1031 -0.3722 0.216 Uiso 1 1 calc R . . H36C H -0.4383 0.1040 -0.2312 0.216 Uiso 1 1 calc R . . O37 O -0.0674(2) 0.16301(9) 0.1074(2) 0.0686(5) Uani 1 1 d . . . C38 C -0.1688(4) 0.11616(14) 0.0919(3) 0.0775(7) Uani 1 1 d . A . O39 O -0.1964(4) 0.07495(13) 0.0017(3) 0.1116(9) Uani 1 1 d . . . C40 C -0.2388(6) 0.1222(2) 0.2023(5) 0.1064(13) Uani 1 1 d . . . C41 C -0.3029(9) 0.1907(3) 0.1918(8) 0.156(2) Uani 1 1 d . A . H41A H -0.3822 0.1966 0.0998 0.234 Uiso 1 1 calc R . . H41B H -0.2244 0.2220 0.2043 0.234 Uiso 1 1 calc R . . H41C H -0.3427 0.1967 0.2647 0.234 Uiso 1 1 calc R . . C42 C -0.1125(10) 0.1163(4) 0.3499(6) 0.174(3) Uani 1 1 d . A . H42A H -0.1544 0.1203 0.4217 0.261 Uiso 1 1 calc R . . H42B H -0.0398 0.1503 0.3621 0.261 Uiso 1 1 calc R . . H42C H -0.0641 0.0747 0.3584 0.261 Uiso 1 1 calc R . . C43 C -0.317(2) 0.0601(7) 0.2035(15) 0.141(5) Uani 0.50 1 d PU A 1 H43A H -0.3629 0.0627 0.2727 0.212 Uiso 0.50 1 calc PR A 1 H43B H -0.2454 0.0250 0.2279 0.212 Uiso 0.50 1 calc PR A 1 H43C H -0.3937 0.0524 0.1108 0.212 Uiso 0.50 1 calc PR A 1 C43A C -0.4020(18) 0.0867(9) 0.140(2) 0.160(6) Uani 0.50 1 d PU A 2 H43D H -0.4487 0.0899 0.2082 0.240 Uiso 0.50 1 calc PR A 2 H43E H -0.3891 0.0416 0.1216 0.240 Uiso 0.50 1 calc PR A 2 H43F H -0.4649 0.1076 0.0527 0.240 Uiso 0.50 1 calc PR A 2 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 0.0603(8) 0.0564(9) 0.0605(9) 0.0020(7) 0.0127(7) 0.0136(7) C2 0.0495(10) 0.0552(12) 0.0483(10) 0.0016(9) 0.0178(8) 0.0066(9) C3 0.0496(10) 0.0562(11) 0.0467(10) 0.0035(9) 0.0216(8) 0.0045(8) C4 0.0503(10) 0.0628(13) 0.0531(11) -0.0034(10) 0.0217(9) -0.0009(9) C5 0.0692(14) 0.0517(12) 0.0649(13) -0.0061(10) 0.0261(11) 0.0031(10) C6 0.0662(14) 0.0582(14) 0.0761(16) -0.0012(12) 0.0186(12) 0.0148(11) N7 0.0504(9) 0.0567(11) 0.0523(9) -0.0035(8) 0.0175(7) 0.0062(8) C8 0.0595(12) 0.0716(16) 0.0584(12) -0.0064(11) 0.0227(10) 0.0113(11) C9 0.0785(16) 0.0793(18) 0.0698(15) -0.0143(14) 0.0262(13) 0.0188(14) C10 0.0802(18) 0.079(2) 0.0815(18) -0.0236(15) 0.0098(15) 0.0142(14) C11 0.0667(15) 0.0685(17) 0.0832(18) -0.0125(14) 0.0144(13) -0.0059(12) C12 0.0522(11) 0.0587(13) 0.0554(11) 0.0021(10) 0.0149(9) 0.0027(9) C13 0.0881(19) 0.094(2) 0.0664(15) 0.0027(14) 0.0392(14) 0.0200(16) C14 0.101(3) 0.122(3) 0.096(2) 0.006(2) 0.050(2) 0.005(2) C15 0.179(5) 0.226(7) 0.106(3) 0.053(4) 0.095(4) 0.082(5) C16 0.090(2) 0.095(2) 0.0807(19) -0.0035(17) 0.0272(16) 0.0309(18) C17 0.120(3) 0.079(2) 0.118(3) 0.005(2) 0.042(2) 0.027(2) C18 0.149(4) 0.115(3) 0.174(5) 0.015(3) 0.089(4) 0.056(3) O19 0.1035(18) 0.158(3) 0.118(2) -0.081(2) 0.0179(16) -0.0047(18) C20 0.0551(12) 0.0805(17) 0.0678(14) -0.0018(12) 0.0235(11) -0.0063(11) C21 0.105(2) 0.114(3) 0.0755(18) 0.0156(18) 0.0392(18) -0.015(2) C22 0.0583(15) 0.138(3) 0.093(2) -0.016(2) 0.0303(15) -0.0147(18) O23 0.0537(8) 0.0621(9) 0.0527(8) 0.0086(7) 0.0209(6) 0.0105(7) C24 0.0594(12) 0.0701(15) 0.0591(12) 0.0001(11) 0.0180(10) 0.0168(11) O25 0.0869(14) 0.1226(19) 0.1035(16) 0.0251(14) 0.0568(13) 0.0446(14) C26 0.0863(18) 0.0752(18) 0.0650(15) 0.0101(13) 0.0147(13) 0.0231(15) C27 0.167(5) 0.120(3) 0.072(2) 0.014(2) -0.006(2) 0.027(3) C28 0.191(6) 0.139(4) 0.151(4) 0.053(4) 0.079(4) 0.104(4) C29 0.127(3) 0.111(3) 0.129(3) 0.052(3) 0.034(3) 0.004(3) O30 0.0513(8) 0.0809(12) 0.0631(9) -0.0106(8) 0.0223(7) -0.0054(8) C31 0.0623(13) 0.092(2) 0.0585(13) -0.0106(13) 0.0200(11) 0.0009(13) O32 0.0761(15) 0.348(7) 0.0869(17) -0.094(3) 0.0310(13) -0.025(2) C33 0.0595(13) 0.0748(17) 0.0739(16) -0.0024(13) 0.0134(12) -0.0001(12) C34 0.097(2) 0.180(5) 0.079(2) 0.003(3) 0.0041(19) 0.026(3) C35 0.0642(17) 0.176(5) 0.135(4) -0.047(4) 0.028(2) 0.004(2) C36 0.106(3) 0.103(3) 0.206(6) 0.017(4) 0.039(4) -0.015(3) O37 0.0886(13) 0.0567(10) 0.0646(10) -0.0034(8) 0.0339(9) -0.0086(8) C38 0.107(2) 0.0524(14) 0.0782(17) 0.0000(13) 0.0411(16) -0.0111(14) O39 0.162(3) 0.0807(15) 0.1101(18) -0.0304(14) 0.0721(18) -0.0451(17) C40 0.161(4) 0.084(2) 0.101(2) -0.0146(19) 0.080(3) -0.041(2) C41 0.200(6) 0.137(5) 0.195(6) 0.011(4) 0.146(5) 0.022(4) C42 0.273(8) 0.177(6) 0.091(3) 0.020(4) 0.090(4) 0.043(6) C43 0.191(13) 0.139(10) 0.132(8) -0.012(7) 0.105(9) -0.068(9) C43A 0.151(10) 0.149(11) 0.213(14) -0.045(10) 0.106(10) -0.075(9) _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 C6 1.411(3) . ? O1 C2 1.448(3) . ? C2 N7 1.427(3) . ? C2 C3 1.533(3) . ? C3 O23 1.434(3) . ? C3 C4 1.515(3) . ? C4 O30 1.440(3) . ? C4 C5 1.512(4) . ? C5 O37 1.446(3) . ? C5 C6 1.518(4) . ? N7 C12 1.486(3) . ? N7 C8 1.488(3) . ? C8 C9 1.528(4) . ? C8 C13 1.541(4) . ? C9 C10 1.505(5) . ? C9 C16 1.510(5) . ? C10 O19 1.210(4) . ? C10 C11 1.506(5) . ? C11 C12 1.532(4) . ? C12 C20 1.533(3) . ? C13 C14 1.481(5) . ? C14 C15 1.252(7) . ? C16 C17 1.476(5) . ? C17 C18 1.308(6) . ? C20 C21 1.523(4) . ? C20 C22 1.535(4) . ? O23 C24 1.352(3) . ? C24 O25 1.181(3) . ? C24 C26 1.531(4) . ? C26 C28 1.506(6) . ? C26 C27 1.517(5) . ? C26 C29 1.525(6) . ? O30 C31 1.325(3) . ? C31 O32 1.171(4) . ? C31 C33 1.522(4) . ? C33 C36 1.502(6) . ? C33 C34 1.510(5) . ? C33 C35 1.515(5) . ? O37 C38 1.332(3) . ? C38 O39 1.198(4) . ? C38 C40 1.514(5) . ? C40 C43 1.480(13) . ? C40 C41 1.519(8) . ? C40 C42 1.529(9) . ? C40 C43A 1.618(14) . ? 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 C6 O1 C2 113.22(18) . . ? N7 C2 O1 110.72(17) . . ? N7 C2 C3 114.33(17) . . ? O1 C2 C3 110.14(18) . . ? O23 C3 C4 107.74(17) . . ? O23 C3 C2 106.97(17) . . ? C4 C3 C2 110.34(17) . . ? O30 C4 C5 110.1(2) . . ? O30 C4 C3 107.27(18) . . ? C5 C4 C3 111.53(19) . . ? O37 C5 C4 108.43(19) . . ? O37 C5 C6 107.4(2) . . ? C4 C5 C6 108.3(2) . . ? O1 C6 C5 110.6(2) . . ? C2 N7 C12 115.66(17) . . ? C2 N7 C8 115.87(19) . . ? C12 N7 C8 112.27(17) . . ? N7 C8 C9 110.5(2) . . ? N7 C8 C13 115.3(2) . . ? C9 C8 C13 108.8(2) . . ? C10 C9 C16 112.4(3) . . ? C10 C9 C8 109.1(2) . . ? C16 C9 C8 112.8(2) . . ? O19 C10 C9 122.7(3) . . ? O19 C10 C11 122.0(3) . . ? C9 C10 C11 115.3(2) . . ? C10 C11 C12 112.9(3) . . ? N7 C12 C11 107.11(19) . . ? N7 C12 C20 114.97(19) . . ? C11 C12 C20 112.4(2) . . ? C14 C13 C8 114.8(3) . . ? C15 C14 C13 128.0(5) . . ? C17 C16 C9 112.5(3) . . ? C18 C17 C16 124.1(5) . . ? C21 C20 C12 113.1(3) . . ? C21 C20 C22 111.6(3) . . ? C12 C20 C22 110.3(2) . . ? C24 O23 C3 117.97(18) . . ? O25 C24 O23 122.9(2) . . ? O25 C24 C26 125.4(2) . . ? O23 C24 C26 111.6(2) . . ? C28 C26 C27 111.1(4) . . ? C28 C26 C29 111.1(5) . . ? C27 C26 C29 107.2(4) . . ? C28 C26 C24 109.0(3) . . ? C27 C26 C24 107.8(3) . . ? C29 C26 C24 110.6(3) . . ? C31 O30 C4 118.17(18) . . ? O32 C31 O30 121.6(3) . . ? O32 C31 C33 124.5(3) . . ? O30 C31 C33 113.9(2) . . ? C36 C33 C34 111.1(4) . . ? C36 C33 C35 108.6(4) . . ? C34 C33 C35 110.1(4) . . ? C36 C33 C31 106.4(3) . . ? C34 C33 C31 108.3(3) . . ? C35 C33 C31 112.3(3) . . ? C38 O37 C5 119.2(2) . . ? O39 C38 O37 122.5(3) . . ? O39 C38 C40 126.2(3) . . ? O37 C38 C40 111.2(3) . . ? C43 C40 C38 107.7(6) . . ? C43 C40 C41 127.1(8) . . ? C38 C40 C41 107.8(3) . . ? C43 C40 C42 97.9(8) . . ? C38 C40 C42 108.0(4) . . ? C41 C40 C42 106.8(5) . . ? C43 C40 C43A 36.8(8) . . ? C38 C40 C43A 107.9(7) . . ? C41 C40 C43A 94.8(8) . . ? C42 C40 C43A 129.3(9) . . ? 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 C6 O1 C2 N7 -174.0(2) . . . . ? C6 O1 C2 C3 58.5(2) . . . . ? N7 C2 C3 O23 65.3(2) . . . . ? O1 C2 C3 O23 -169.31(16) . . . . ? N7 C2 C3 C4 -177.80(18) . . . . ? O1 C2 C3 C4 -52.4(2) . . . . ? O23 C3 C4 O30 -70.0(2) . . . . ? C2 C3 C4 O30 173.55(17) . . . . ? O23 C3 C4 C5 169.36(18) . . . . ? C2 C3 C4 C5 52.9(2) . . . . ? O30 C4 C5 O37 -58.0(2) . . . . ? C3 C4 C5 O37 61.0(2) . . . . ? O30 C4 C5 C6 -174.23(19) . . . . ? C3 C4 C5 C6 -55.3(3) . . . . ? C2 O1 C6 C5 -62.6(3) . . . . ? O37 C5 C6 O1 -57.7(3) . . . . ? C4 C5 C6 O1 59.2(3) . . . . ? O1 C2 N7 C12 67.2(2) . . . . ? C3 C2 N7 C12 -167.66(17) . . . . ? O1 C2 N7 C8 -67.2(2) . . . . ? C3 C2 N7 C8 57.9(2) . . . . ? C2 N7 C8 C9 -160.3(2) . . . . ? C12 N7 C8 C9 63.8(3) . . . . ? C2 N7 C8 C13 75.8(3) . . . . ? C12 N7 C8 C13 -60.1(3) . . . . ? N7 C8 C9 C10 -54.0(3) . . . . ? C13 C8 C9 C10 73.5(3) . . . . ? N7 C8 C9 C16 71.7(3) . . . . ? C13 C8 C9 C16 -160.8(3) . . . . ? C16 C9 C10 O19 103.4(4) . . . . ? C8 C9 C10 O19 -130.7(4) . . . . ? C16 C9 C10 C11 -77.3(3) . . . . ? C8 C9 C10 C11 48.5(4) . . . . ? O19 C10 C11 C12 129.4(4) . . . . ? C9 C10 C11 C12 -49.8(4) . . . . ? C2 N7 C12 C11 162.8(2) . . . . ? C8 N7 C12 C11 -61.2(3) . . . . ? C2 N7 C12 C20 37.1(3) . . . . ? C8 N7 C12 C20 173.1(2) . . . . ? C10 C11 C12 N7 53.1(3) . . . . ? C10 C11 C12 C20 -179.7(2) . . . . ? N7 C8 C13 C14 -164.9(3) . . . . ? C9 C8 C13 C14 70.3(4) . . . . ? C8 C13 C14 C15 -128.9(6) . . . . ? C10 C9 C16 C17 -65.3(4) . . . . ? C8 C9 C16 C17 170.8(3) . . . . ? C9 C16 C17 C18 -127.0(5) . . . . ? N7 C12 C20 C21 63.3(3) . . . . ? C11 C12 C20 C21 -59.6(3) . . . . ? N7 C12 C20 C22 -171.0(3) . . . . ? C11 C12 C20 C22 66.1(3) . . . . ? C4 C3 O23 C24 115.0(2) . . . . ? C2 C3 O23 C24 -126.4(2) . . . . ? C3 O23 C24 O25 -0.6(4) . . . . ? C3 O23 C24 C26 -179.0(2) . . . . ? O25 C24 C26 C28 16.8(6) . . . . ? O23 C24 C26 C28 -164.9(4) . . . . ? O25 C24 C26 C27 -103.8(4) . . . . ? O23 C24 C26 C27 74.5(4) . . . . ? O25 C24 C26 C29 139.3(4) . . . . ? O23 C24 C26 C29 -42.4(4) . . . . ? C5 C4 O30 C31 -100.4(3) . . . . ? C3 C4 O30 C31 138.0(2) . . . . ? C4 O30 C31 O32 0.1(5) . . . . ? C4 O30 C31 C33 177.4(2) . . . . ? O32 C31 C33 C36 82.7(6) . . . . ? O30 C31 C33 C36 -94.5(4) . . . . ? O32 C31 C33 C34 -36.9(6) . . . . ? O30 C31 C33 C34 145.9(4) . . . . ? O32 C31 C33 C35 -158.7(5) . . . . ? O30 C31 C33 C35 24.1(5) . . . . ? C4 C5 O37 C38 104.1(3) . . . . ? C6 C5 O37 C38 -139.1(3) . . . . ? C5 O37 C38 O39 5.7(5) . . . . ? C5 O37 C38 C40 -175.1(3) . . . . ? O39 C38 C40 C43 14.1(10) . . . . ? O37 C38 C40 C43 -165.1(8) . . . . ? O39 C38 C40 C41 -126.0(5) . . . . ? O37 C38 C40 C41 54.8(5) . . . . ? O39 C38 C40 C42 118.9(5) . . . . ? O37 C38 C40 C42 -60.3(5) . . . . ? O39 C38 C40 C43A -24.7(9) . . . . ? O37 C38 C40 C43A 156.1(8) . . . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 73.69 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.305 _refine_diff_density_min -0.238 _refine_diff_density_rms 0.039