# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_cambridge 0177 _publ_contact_autor ; Martin Nieger Laboratory of Inorganic Chemistry Department of Chemistry Universitity of Helsinki P.O. Box 55 FIN-00014 University of Helsinki Finland ; _publ_contact_author_phone '++358 9 191 50223' _publ_contact_author_fax '++358 9 191 50198' _publ_contact_author_email martin.nieger@helsinki.fi _publ_requested_coeditor_name ? _publ_contact_letter ; enclosed you will find the necessary data for our publication in Org. Biomol. Chem. ; #============================================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; Synthetic Studies towards Marmycins A and B. Development of the vinylogous Aldol - aza-Michael Domino Reaction ; loop_ _publ_author_name _publ_author_address E.Bourcet ; Institut f\"ur Oorganische Chemie Universit\"at Karlsruhe (TH) Fritz-Haber-Weg 6 D-76131 Karlsruhe Germany ; M.C.Brohmer ; Institut f\"ur Oorganische Chemie Universit\"at Karlsruhe (TH) Fritz-Haber-Weg 6 D-76131 Karlsruhe Germany ; M.Nieger ; Laboratory of Inorganic Chemistry Department of Chemistry Universitity of Helsinki P.O. Box 55 FIN-00014 University of Helsinki Finland ; S.Brase ; Institut f\"ur Oorganische Chemie Universit\"at Karlsruhe (TH) Fritz-Haber-Weg 6 D-76131 Karlsruhe Germany ; _publ_contact_author_name 'Martin Nieger' #============================================================================== data_sb198_hy_compound_10a _database_code_depnum_ccdc_archive 'CCDC 808006' #TrackingRef 'obc-2011.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; rac-(2S,4S,6S)-2-methyl-2,3,4,6-tetrahydro-1H-2,6-methanobenzo[c]- [1,5]oxazocin-4-ol ; _chemical_name_common ; rac-(2S,4S,6S)-2-methyl-2,3,4,6-tetrahydro-1H-2,6- methanobenzo(c)-(1,5)oxazocin-4-ol ; _chemical_melting_point ? _chemical_formula_moiety 'C12 H15 N O2' _chemical_formula_sum 'C12 H15 N O2' _chemical_formula_weight 205.25 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/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 10.838(1) _cell_length_b 7.683(1) _cell_length_c 12.432(1) _cell_angle_alpha 90.00 _cell_angle_beta 97.66(1) _cell_angle_gamma 90.00 _cell_volume 1025.95(18) _cell_formula_units_Z 4 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used 128 _cell_measurement_theta_min 2.5 _cell_measurement_theta_max 25.0 _exptl_crystal_description plates _exptl_crystal_colour colourless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.329 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 440 _exptl_absorpt_coefficient_mu 0.090 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; dx = 35 mm, 30 sec./deg., 2 deg., 3 sets, 209 frames, 4166 refl. postref. ; _diffrn_ambient_temperature 123(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker-Nonius KappaCCD' _diffrn_measurement_method 'rotation in phi and omega, 2 deg.' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11513 _diffrn_reflns_av_R_equivalents 0.0254 _diffrn_reflns_av_sigmaI/netI 0.0214 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.12 _diffrn_reflns_theta_max 27.48 _reflns_number_total 2334 _reflns_number_gt 1961 _reflns_threshold_expression >2sigma(I) _computing_data_collection Collect _computing_cell_refinement EVALCCD _computing_data_reduction EVALCCD _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics XP _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^)+(0.0424P)^2^+0.4563P] 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 2334 _refine_ls_number_parameters 143 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0503 _refine_ls_R_factor_gt 0.0394 _refine_ls_wR_factor_ref 0.0977 _refine_ls_wR_factor_gt 0.0916 _refine_ls_goodness_of_fit_ref 1.036 _refine_ls_restrained_S_all 1.036 _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 N1 N 0.72613(10) 0.32913(14) 0.32244(9) 0.0211(2) Uani 1 1 d D . . H1 H 0.7043(14) 0.2400(19) 0.3573(12) 0.025 Uiso 1 1 d D . . C2 C 0.66125(11) 0.49328(16) 0.33577(9) 0.0182(3) Uani 1 1 d . . . C21 C 0.65712(13) 0.52043(18) 0.45670(10) 0.0245(3) Uani 1 1 d . . . H21A H 0.6168 0.4202 0.4861 0.037 Uiso 1 1 calc R . . H21B H 0.6098 0.6263 0.4675 0.037 Uiso 1 1 calc R . . H21C H 0.7421 0.5323 0.4943 0.037 Uiso 1 1 calc R . . C3 C 0.52819(11) 0.48948(16) 0.27406(9) 0.0171(2) Uani 1 1 d . . . H3A H 0.4822 0.3904 0.3006 0.021 Uiso 1 1 calc R . . H3B H 0.4844 0.5979 0.2895 0.021 Uiso 1 1 calc R . . C4 C 0.52738(11) 0.47226(16) 0.15266(9) 0.0161(2) Uani 1 1 d . . . H4 H 0.5536 0.3522 0.1345 0.019 Uiso 1 1 calc R . . O4 O 0.40722(8) 0.50576(12) 0.10106(7) 0.0193(2) Uani 1 1 d D . . H4O H 0.4004(15) 0.469(2) 0.0367(11) 0.029 Uiso 1 1 d D . . O5 O 0.60788(7) 0.59965(11) 0.11206(6) 0.0173(2) Uani 1 1 d . . . C6 C 0.73553(11) 0.59769(16) 0.16824(10) 0.0185(3) Uani 1 1 d . . . H6 H 0.7840 0.6910 0.1366 0.022 Uiso 1 1 calc R . . C6A C 0.80032(11) 0.42608(17) 0.15766(10) 0.0190(3) Uani 1 1 d . . . C7 C 0.87207(12) 0.39351(19) 0.07461(11) 0.0248(3) Uani 1 1 d . . . H7 H 0.8784 0.4804 0.0212 0.030 Uiso 1 1 calc R . . C8 C 0.93420(12) 0.2373(2) 0.06844(11) 0.0299(3) Uani 1 1 d . . . H8 H 0.9823 0.2166 0.0112 0.036 Uiso 1 1 calc R . . C9 C 0.92531(12) 0.11110(19) 0.14694(12) 0.0288(3) Uani 1 1 d . . . H9 H 0.9679 0.0036 0.1432 0.035 Uiso 1 1 calc R . . C10 C 0.85545(12) 0.13945(18) 0.23054(11) 0.0245(3) Uani 1 1 d . . . H10 H 0.8501 0.0516 0.2835 0.029 Uiso 1 1 calc R . . C10A C 0.79222(11) 0.29819(17) 0.23740(10) 0.0193(3) Uani 1 1 d . . . C11 C 0.73282(11) 0.63794(16) 0.28753(10) 0.0192(3) Uani 1 1 d . . . H11A H 0.6915 0.7513 0.2954 0.023 Uiso 1 1 calc R . . H11B H 0.8188 0.6446 0.3260 0.023 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 N1 0.0267(6) 0.0185(5) 0.0187(5) 0.0027(4) 0.0049(4) 0.0052(4) C2 0.0200(6) 0.0189(6) 0.0151(6) -0.0014(4) 0.0001(4) 0.0026(5) C21 0.0258(7) 0.0295(7) 0.0173(6) -0.0030(5) -0.0006(5) 0.0058(5) C3 0.0178(6) 0.0181(6) 0.0157(6) -0.0007(4) 0.0030(4) -0.0006(5) C4 0.0151(5) 0.0165(6) 0.0164(6) 0.0000(4) 0.0009(4) -0.0013(4) O4 0.0167(4) 0.0248(5) 0.0157(4) -0.0022(3) -0.0007(3) 0.0003(3) O5 0.0159(4) 0.0191(4) 0.0165(4) 0.0028(3) 0.0001(3) -0.0024(3) C6 0.0151(6) 0.0204(6) 0.0192(6) 0.0010(5) -0.0003(4) -0.0020(4) C6A 0.0139(5) 0.0233(6) 0.0192(6) -0.0034(5) -0.0006(4) -0.0014(5) C7 0.0165(6) 0.0353(8) 0.0225(7) -0.0041(5) 0.0029(5) -0.0035(5) C8 0.0164(6) 0.0437(9) 0.0300(7) -0.0144(6) 0.0047(5) 0.0001(6) C9 0.0179(6) 0.0294(8) 0.0375(8) -0.0138(6) -0.0024(5) 0.0052(5) C10 0.0205(6) 0.0230(7) 0.0281(7) -0.0042(5) -0.0034(5) 0.0037(5) C10A 0.0156(6) 0.0219(6) 0.0192(6) -0.0048(5) -0.0020(4) 0.0010(5) C11 0.0173(6) 0.0187(6) 0.0203(6) -0.0027(5) -0.0018(5) 0.0001(5) _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 N1 C10A 1.3744(16) . ? N1 C2 1.4641(15) . ? N1 H1 0.860(13) . ? C2 C11 1.5233(17) . ? C2 C21 1.5244(17) . ? C2 C3 1.5408(16) . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? C3 C4 1.5140(16) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 O4 1.3968(14) . ? C4 O5 1.4461(14) . ? C4 H4 1.0000 . ? O4 H4O 0.842(13) . ? O5 C6 1.4644(14) . ? C6 C6A 1.5078(17) . ? C6 C11 1.5190(17) . ? C6 H6 1.0000 . ? C6A C7 1.3954(17) . ? C6A C10A 1.4068(18) . ? C7 C8 1.383(2) . ? C7 H7 0.9500 . ? C8 C9 1.388(2) . ? C8 H8 0.9500 . ? C9 C10 1.382(2) . ? C9 H9 0.9500 . ? C10 C10A 1.4071(17) . ? C10 H10 0.9500 . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? 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 C10A N1 C2 122.92(11) . . ? C10A N1 H1 117.1(10) . . ? C2 N1 H1 117.4(10) . . ? N1 C2 C11 107.85(10) . . ? N1 C2 C21 107.89(10) . . ? C11 C2 C21 111.83(10) . . ? N1 C2 C3 111.04(10) . . ? C11 C2 C3 108.04(10) . . ? C21 C2 C3 110.19(10) . . ? C2 C21 H21A 109.5 . . ? C2 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C2 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C4 C3 C2 112.25(10) . . ? C4 C3 H3A 109.2 . . ? C2 C3 H3A 109.2 . . ? C4 C3 H3B 109.2 . . ? C2 C3 H3B 109.2 . . ? H3A C3 H3B 107.9 . . ? O4 C4 O5 106.49(9) . . ? O4 C4 C3 108.84(9) . . ? O5 C4 C3 111.42(9) . . ? O4 C4 H4 110.0 . . ? O5 C4 H4 110.0 . . ? C3 C4 H4 110.0 . . ? C4 O4 H4O 109.5(11) . . ? C4 O5 C6 113.71(8) . . ? O5 C6 C6A 112.88(10) . . ? O5 C6 C11 108.88(9) . . ? C6A C6 C11 109.45(10) . . ? O5 C6 H6 108.5 . . ? C6A C6 H6 108.5 . . ? C11 C6 H6 108.5 . . ? C7 C6A C10A 119.31(12) . . ? C7 C6A C6 122.22(12) . . ? C10A C6A C6 118.41(11) . . ? C8 C7 C6A 121.33(13) . . ? C8 C7 H7 119.3 . . ? C6A C7 H7 119.3 . . ? C7 C8 C9 119.15(12) . . ? C7 C8 H8 120.4 . . ? C9 C8 H8 120.4 . . ? C10 C9 C8 120.99(13) . . ? C10 C9 H9 119.5 . . ? C8 C9 H9 119.5 . . ? C9 C10 C10A 120.14(13) . . ? C9 C10 H10 119.9 . . ? C10A C10 H10 119.9 . . ? N1 C10A C6A 120.61(11) . . ? N1 C10A C10 120.29(12) . . ? C6A C10A C10 119.08(12) . . ? C6 C11 C2 108.24(10) . . ? C6 C11 H11A 110.1 . . ? C2 C11 H11A 110.1 . . ? C6 C11 H11B 110.1 . . ? C2 C11 H11B 110.1 . . ? H11A C11 H11B 108.4 . . ? 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 C10A N1 C2 C11 -30.56(15) . . . . ? C10A N1 C2 C21 -151.52(11) . . . . ? C10A N1 C2 C3 87.64(14) . . . . ? N1 C2 C3 C4 -63.53(13) . . . . ? C11 C2 C3 C4 54.55(13) . . . . ? C21 C2 C3 C4 176.99(10) . . . . ? C2 C3 C4 O4 -167.85(9) . . . . ? C2 C3 C4 O5 -50.72(13) . . . . ? O4 C4 O5 C6 172.55(9) . . . . ? C3 C4 O5 C6 54.00(12) . . . . ? C4 O5 C6 C6A 61.06(12) . . . . ? C4 O5 C6 C11 -60.69(12) . . . . ? O5 C6 C6A C7 91.90(13) . . . . ? C11 C6 C6A C7 -146.67(12) . . . . ? O5 C6 C6A C10A -91.03(13) . . . . ? C11 C6 C6A C10A 30.40(14) . . . . ? C10A C6A C7 C8 0.74(18) . . . . ? C6 C6A C7 C8 177.79(11) . . . . ? C6A C7 C8 C9 -0.35(19) . . . . ? C7 C8 C9 C10 0.1(2) . . . . ? C8 C9 C10 C10A -0.2(2) . . . . ? C2 N1 C10A C6A -0.06(18) . . . . ? C2 N1 C10A C10 178.28(11) . . . . ? C7 C6A C10A N1 177.52(11) . . . . ? C6 C6A C10A N1 0.36(17) . . . . ? C7 C6A C10A C10 -0.84(17) . . . . ? C6 C6A C10A C10 -178.01(11) . . . . ? C9 C10 C10A N1 -177.79(12) . . . . ? C9 C10 C10A C6A 0.59(18) . . . . ? O5 C6 C11 C2 63.27(12) . . . . ? C6A C6 C11 C2 -60.55(12) . . . . ? N1 C2 C11 C6 59.87(12) . . . . ? C21 C2 C11 C6 178.33(10) . . . . ? C3 C2 C11 C6 -60.24(12) . . . . ? 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 N1 H1 O4 0.860(13) 2.266(14) 3.0875(15) 159.7(14) 2_645 O4 H4O O5 0.842(13) 1.914(14) 2.7544(12) 175.9(16) 3_665 _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.315 _refine_diff_density_min -0.229 _refine_diff_density_rms 0.042 #============================================================================== data_sb220_c_compound_10b _database_code_depnum_ccdc_archive 'CCDC 808007' #TrackingRef 'obc_2011.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; rac-(2S,4S,6S)-2,10-dimethyl-2,3,4,6-tetrahydro-1H-2,6-methanobenzo[c]- [1,5]oxazocin-4-ol ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C13 H17 N O2' _chemical_formula_sum 'C13 H17 N O2' _chemical_formula_weight 219.28 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 'P 21/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.5344(6) _cell_length_b 22.2980(13) _cell_length_c 7.2117(7) _cell_angle_alpha 90.00 _cell_angle_beta 114.172(7) _cell_angle_gamma 90.00 _cell_volume 1105.35(15) _cell_formula_units_Z 4 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used 137 _cell_measurement_theta_min 2.5 _cell_measurement_theta_max 25.0 _exptl_crystal_description plates _exptl_crystal_colour colourless _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.318 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 472 _exptl_absorpt_coefficient_mu 0.089 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; dx = 50 mm, 60 sec./deg., 1 deg., 8 sets, 921 frames, 12553 refl. postref. ; _diffrn_ambient_temperature 123(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker-Nonius KappaCCD' _diffrn_measurement_method 'rotation in phi and omega, 1 deg.' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 19255 _diffrn_reflns_av_R_equivalents 0.0469 _diffrn_reflns_av_sigmaI/netI 0.0228 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 2.96 _diffrn_reflns_theta_max 27.47 _reflns_number_total 2532 _reflns_number_gt 2324 _reflns_threshold_expression >2sigma(I) _computing_data_collection Collect _computing_cell_refinement EVALCCD _computing_data_reduction EVALCCD _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics XP _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^)+(0.0459P)^2^+0.4601P] 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 2532 _refine_ls_number_parameters 153 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0438 _refine_ls_R_factor_gt 0.0403 _refine_ls_wR_factor_ref 0.1033 _refine_ls_wR_factor_gt 0.1004 _refine_ls_goodness_of_fit_ref 1.078 _refine_ls_restrained_S_all 1.078 _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 N1 N 0.56508(14) 0.61454(4) 0.62465(14) 0.0173(2) Uani 1 1 d D . . H1N H 0.4431(18) 0.6054(6) 0.561(2) 0.021 Uiso 1 1 d D . . C2 C 0.67203(16) 0.57781(5) 0.80575(15) 0.0162(2) Uani 1 1 d . . . C21 C 0.55770(18) 0.57749(5) 0.93771(17) 0.0214(2) Uani 1 1 d . . . H21A H 0.4299 0.5592 0.8622 0.032 Uiso 1 1 calc R . . H21B H 0.5407 0.6188 0.9743 0.032 Uiso 1 1 calc R . . H21C H 0.6289 0.5543 1.0615 0.032 Uiso 1 1 calc R . . C3 C 0.70278(16) 0.51334(5) 0.74896(16) 0.0166(2) Uani 1 1 d . . . H3A H 0.7740 0.4900 0.8745 0.020 Uiso 1 1 calc R . . H3B H 0.5748 0.4940 0.6747 0.020 Uiso 1 1 calc R . . C4 C 0.81644(16) 0.51250(5) 0.61786(16) 0.0164(2) Uani 1 1 d . . . H4 H 0.7388 0.5321 0.4843 0.020 Uiso 1 1 calc R . . O4 O 0.85731(12) 0.45339(4) 0.58668(12) 0.0203(2) Uani 1 1 d D . . H4O H 0.900(2) 0.4539(7) 0.495(2) 0.030 Uiso 1 1 d D . . O5 O 0.99960(11) 0.54330(3) 0.71882(11) 0.01756(19) Uani 1 1 d . . . C6 C 0.97519(16) 0.60499(5) 0.77410(16) 0.0177(2) Uani 1 1 d . . . H6 H 1.1069 0.6234 0.8458 0.021 Uiso 1 1 calc R . . C6A C 0.86069(16) 0.64258(5) 0.59043(16) 0.0176(2) Uani 1 1 d . . . C7 C 0.95335(18) 0.67566(5) 0.49267(19) 0.0224(3) Uani 1 1 d . . . H7 H 1.0910 0.6739 0.5406 0.027 Uiso 1 1 calc R . . C8 C 0.8477(2) 0.71113(5) 0.32633(19) 0.0265(3) Uani 1 1 d . . . H8 H 0.9116 0.7339 0.2605 0.032 Uiso 1 1 calc R . . C9 C 0.6471(2) 0.71272(5) 0.25768(18) 0.0247(3) Uani 1 1 d . . . H9 H 0.5744 0.7369 0.1432 0.030 Uiso 1 1 calc R . . C10 C 0.54816(18) 0.68025(5) 0.34983(17) 0.0199(2) Uani 1 1 d . . . C101 C 0.33134(19) 0.68354(6) 0.27415(19) 0.0264(3) Uani 1 1 d . . . H10A H 0.2784 0.7071 0.1485 0.040 Uiso 1 1 calc R . . H10B H 0.2969 0.7027 0.3772 0.040 Uiso 1 1 calc R . . H10C H 0.2768 0.6430 0.2472 0.040 Uiso 1 1 calc R . . C10A C 0.65746(16) 0.64486(5) 0.52154(16) 0.0165(2) Uani 1 1 d . . . C11 C 0.87294(16) 0.60551(5) 0.91740(16) 0.0180(2) Uani 1 1 d . . . H11A H 0.8607 0.6472 0.9582 0.022 Uiso 1 1 calc R . . H11B H 0.9487 0.5821 1.0413 0.022 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 N1 0.0163(5) 0.0206(5) 0.0143(4) 0.0026(3) 0.0057(4) -0.0007(4) C2 0.0189(5) 0.0191(5) 0.0115(5) 0.0007(4) 0.0072(4) 0.0004(4) C21 0.0269(6) 0.0240(6) 0.0179(5) -0.0002(4) 0.0139(5) 0.0000(5) C3 0.0183(5) 0.0181(5) 0.0136(5) 0.0011(4) 0.0069(4) -0.0001(4) C4 0.0178(5) 0.0172(5) 0.0142(5) -0.0012(4) 0.0064(4) -0.0009(4) O4 0.0262(4) 0.0181(4) 0.0202(4) -0.0014(3) 0.0131(3) 0.0006(3) O5 0.0167(4) 0.0190(4) 0.0169(4) -0.0024(3) 0.0068(3) 0.0000(3) C6 0.0178(5) 0.0193(5) 0.0161(5) -0.0039(4) 0.0069(4) -0.0024(4) C6A 0.0231(6) 0.0158(5) 0.0171(5) -0.0031(4) 0.0114(4) -0.0017(4) C7 0.0285(6) 0.0185(5) 0.0277(6) -0.0044(4) 0.0189(5) -0.0030(4) C8 0.0433(7) 0.0188(6) 0.0287(6) 0.0006(5) 0.0263(6) -0.0025(5) C9 0.0410(7) 0.0183(5) 0.0185(5) 0.0025(4) 0.0159(5) 0.0016(5) C10 0.0284(6) 0.0167(5) 0.0149(5) -0.0014(4) 0.0090(4) 0.0003(4) C101 0.0283(6) 0.0260(6) 0.0195(6) 0.0056(4) 0.0043(5) 0.0014(5) C10A 0.0236(6) 0.0145(5) 0.0136(5) -0.0024(4) 0.0098(4) -0.0012(4) C11 0.0201(5) 0.0213(5) 0.0120(5) -0.0023(4) 0.0060(4) -0.0004(4) _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 N1 C10A 1.3851(14) . ? N1 C2 1.4710(13) . ? N1 H1N 0.867(12) . ? C2 C21 1.5229(14) . ? C2 C11 1.5242(15) . ? C2 C3 1.5380(15) . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? C3 C4 1.5135(14) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 O4 1.3927(13) . ? C4 O5 1.4432(13) . ? C4 H4 1.0000 . ? O4 H4O 0.850(13) . ? O5 C6 1.4647(13) . ? C6 C6A 1.5052(15) . ? C6 C11 1.5211(15) . ? C6 H6 1.0000 . ? C6A C7 1.3899(15) . ? C6A C10A 1.4040(16) . ? C7 C8 1.3842(18) . ? C7 H7 0.9500 . ? C8 C9 1.3851(19) . ? C8 H8 0.9500 . ? C9 C10 1.3881(16) . ? C9 H9 0.9500 . ? C10 C10A 1.4139(15) . ? C10 C101 1.4972(17) . ? C101 H10A 0.9800 . ? C101 H10B 0.9800 . ? C101 H10C 0.9800 . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? 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 C10A N1 C2 122.37(9) . . ? C10A N1 H1N 119.0(9) . . ? C2 N1 H1N 114.7(9) . . ? N1 C2 C21 108.24(9) . . ? N1 C2 C11 107.93(9) . . ? C21 C2 C11 111.42(9) . . ? N1 C2 C3 111.80(8) . . ? C21 C2 C3 110.33(9) . . ? C11 C2 C3 107.11(9) . . ? C2 C21 H21A 109.5 . . ? C2 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C2 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C4 C3 C2 111.30(9) . . ? C4 C3 H3A 109.4 . . ? C2 C3 H3A 109.4 . . ? C4 C3 H3B 109.4 . . ? C2 C3 H3B 109.4 . . ? H3A C3 H3B 108.0 . . ? O4 C4 O5 107.62(8) . . ? O4 C4 C3 109.37(9) . . ? O5 C4 C3 110.35(8) . . ? O4 C4 H4 109.8 . . ? O5 C4 H4 109.8 . . ? C3 C4 H4 109.8 . . ? C4 O4 H4O 107.1(11) . . ? C4 O5 C6 112.55(8) . . ? O5 C6 C6A 111.97(8) . . ? O5 C6 C11 110.31(9) . . ? C6A C6 C11 109.05(9) . . ? O5 C6 H6 108.5 . . ? C6A C6 H6 108.5 . . ? C11 C6 H6 108.5 . . ? C7 C6A C10A 120.19(11) . . ? C7 C6A C6 121.06(10) . . ? C10A C6A C6 118.73(9) . . ? C8 C7 C6A 120.85(12) . . ? C8 C7 H7 119.6 . . ? C6A C7 H7 119.6 . . ? C7 C8 C9 118.72(11) . . ? C7 C8 H8 120.6 . . ? C9 C8 H8 120.6 . . ? C8 C9 C10 122.47(11) . . ? C8 C9 H9 118.8 . . ? C10 C9 H9 118.8 . . ? C9 C10 C10A 118.43(11) . . ? C9 C10 C101 121.30(11) . . ? C10A C10 C101 120.26(10) . . ? C10 C101 H10A 109.5 . . ? C10 C101 H10B 109.5 . . ? H10A C101 H10B 109.5 . . ? C10 C101 H10C 109.5 . . ? H10A C101 H10C 109.5 . . ? H10B C101 H10C 109.5 . . ? N1 C10A C6A 120.49(10) . . ? N1 C10A C10 120.14(10) . . ? C6A C10A C10 119.33(10) . . ? C6 C11 C2 107.92(8) . . ? C6 C11 H11A 110.1 . . ? C2 C11 H11A 110.1 . . ? C6 C11 H11B 110.1 . . ? C2 C11 H11B 110.1 . . ? H11A C11 H11B 108.4 . . ? 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 C10A N1 C2 C21 151.87(10) . . . . ? C10A N1 C2 C11 31.14(13) . . . . ? C10A N1 C2 C3 -86.41(12) . . . . ? N1 C2 C3 C4 59.55(12) . . . . ? C21 C2 C3 C4 -179.93(9) . . . . ? C11 C2 C3 C4 -58.49(11) . . . . ? C2 C3 C4 O4 174.23(8) . . . . ? C2 C3 C4 O5 56.03(11) . . . . ? O4 C4 O5 C6 -175.51(8) . . . . ? C3 C4 O5 C6 -56.24(11) . . . . ? C4 O5 C6 C6A -61.58(11) . . . . ? C4 O5 C6 C11 60.05(11) . . . . ? O5 C6 C6A C7 -91.60(12) . . . . ? C11 C6 C6A C7 146.04(10) . . . . ? O5 C6 C6A C10A 89.87(11) . . . . ? C11 C6 C6A C10A -32.49(13) . . . . ? C10A C6A C7 C8 -0.16(17) . . . . ? C6 C6A C7 C8 -178.67(10) . . . . ? C6A C7 C8 C9 -0.52(17) . . . . ? C7 C8 C9 C10 0.22(18) . . . . ? C8 C9 C10 C10A 0.74(17) . . . . ? C8 C9 C10 C101 179.09(11) . . . . ? C2 N1 C10A C6A -1.44(15) . . . . ? C2 N1 C10A C10 -179.12(9) . . . . ? C7 C6A C10A N1 -176.58(10) . . . . ? C6 C6A C10A N1 1.97(15) . . . . ? C7 C6A C10A C10 1.12(16) . . . . ? C6 C6A C10A C10 179.66(9) . . . . ? C9 C10 C10A N1 176.31(10) . . . . ? C101 C10 C10A N1 -2.05(16) . . . . ? C9 C10 C10A C6A -1.39(16) . . . . ? C101 C10 C10A C6A -179.76(10) . . . . ? O5 C6 C11 C2 -61.70(11) . . . . ? C6A C6 C11 C2 61.66(11) . . . . ? N1 C2 C11 C6 -60.34(11) . . . . ? C21 C2 C11 C6 -179.05(9) . . . . ? C3 C2 C11 C6 60.20(11) . . . . ? 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 N1 H1N O4 0.867(12) 2.449(13) 3.2822(13) 161.2(13) 3_666 O4 H4O O5 0.850(13) 1.973(14) 2.8226(11) 179.0(15) 3_766 C11 H11B O4 0.99 2.60 3.5628(14) 165.0 3_767 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.47 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.347 _refine_diff_density_min -0.203 _refine_diff_density_rms 0.046 #============================================================================== #_eof # End of Crystallographic Information File