# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'ProfD Wen Hao Hu' _publ_contact_author_address ; Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences Chengdu 610041 CHINA ; _publ_contact_author_email HUWH@CIOC.AC.CN _publ_section_title ; Rhodium Catalyzed Three-Component Reaction of Diazoacetates, Titanium(IV) Alkoxides and Aldehydes ; loop_ _publ_author_name 'Wenhao Hu' 'Zhi Yong Chen' 'Hui Liu' 'Chong Dao Lu' 'Ai-Qiao Mi' data_hwh42 _database_code_depnum_ccdc_archive 'CCDC 261327' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H16 O4' _chemical_formula_weight 296.31 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 8.8668(12) _cell_length_b 8.7122(12) _cell_length_c 19.668(3) _cell_angle_alpha 90.00 _cell_angle_beta 94.189(3) _cell_angle_gamma 90.00 _cell_volume 1515.3(4) _cell_formula_units_Z 4 _cell_measurement_temperature 294(2) _cell_measurement_reflns_used 7050 _cell_measurement_theta_min 1 _cell_measurement_theta_max 27.5 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.50 _exptl_crystal_size_min 0.42 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.299 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 624 _exptl_absorpt_coefficient_mu 0.092 _exptl_absorpt_correction_type 'multi scans' _exptl_absorpt_correction_T_min 0.773 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details 'SADABS; Sheldrick 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 294(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 CCD Area Detector' _diffrn_measurement_method 'omega and phi scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13787 _diffrn_reflns_av_R_equivalents 0.0395 _diffrn_reflns_av_sigmaI/netI 0.0344 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 27.56 _reflns_number_total 3507 _reflns_number_gt 2434 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0711P)^2^+0.2125P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3507 _refine_ls_number_parameters 201 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0731 _refine_ls_R_factor_gt 0.0476 _refine_ls_wR_factor_ref 0.1402 _refine_ls_wR_factor_gt 0.1246 _refine_ls_goodness_of_fit_ref 1.059 _refine_ls_restrained_S_all 1.059 _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 0.00634(9) 0.83235(10) 0.04981(5) 0.0579(3) Uani 1 1 d . . . O2 O 0.00502(9) 1.04207(10) 0.11487(5) 0.0539(2) Uani 1 1 d . . . O3 O 0.24915(10) 0.60006(11) 0.01518(4) 0.0549(2) Uani 1 1 d . . . O4 O 0.15915(9) 0.56401(9) 0.11785(4) 0.0478(2) Uani 1 1 d . . . C1 C 0.23711(12) 0.91475(12) 0.10958(5) 0.0345(3) Uani 1 1 d . . . C2 C 0.30966(12) 0.78139(12) 0.10404(5) 0.0336(2) Uani 1 1 d . . . C3 C 0.31617(11) 1.05850(11) 0.13392(5) 0.0335(2) Uani 1 1 d . . . C4 C 0.29502(13) 1.12288(13) 0.19713(6) 0.0412(3) Uani 1 1 d . . . H4 H 0.2284 1.0774 0.2255 0.049 Uiso 1 1 calc R . . C5 C 0.37236(14) 1.25410(13) 0.21806(6) 0.0461(3) Uani 1 1 d . . . H5 H 0.3589 1.2951 0.2609 0.055 Uiso 1 1 calc R . . C6 C 0.46939(13) 1.32503(13) 0.17617(6) 0.0461(3) Uani 1 1 d . . . H6 H 0.5199 1.4143 0.1903 0.055 Uiso 1 1 calc R . . C7 C 0.49096(13) 1.26305(14) 0.11350(7) 0.0472(3) Uani 1 1 d . . . H7 H 0.5563 1.3103 0.0851 0.057 Uiso 1 1 calc R . . C8 C 0.41510(13) 1.12963(13) 0.09247(6) 0.0416(3) Uani 1 1 d . . . H8 H 0.4309 1.0876 0.0501 0.050 Uiso 1 1 calc R . . C9 C 0.46973(12) 0.75227(11) 0.12916(5) 0.0345(3) Uani 1 1 d . . . C10 C 0.52129(13) 0.79103(14) 0.19529(6) 0.0451(3) Uani 1 1 d . . . H10 H 0.4569 0.8404 0.2235 0.054 Uiso 1 1 calc R . . C11 C 0.66778(14) 0.75668(16) 0.21946(7) 0.0561(4) Uani 1 1 d . . . H11 H 0.7015 0.7836 0.2637 0.067 Uiso 1 1 calc R . . C12 C 0.76400(14) 0.68284(16) 0.17837(8) 0.0581(4) Uani 1 1 d . . . H12 H 0.8621 0.6591 0.1950 0.070 Uiso 1 1 calc R . . C13 C 0.71477(14) 0.64438(15) 0.11279(7) 0.0526(3) Uani 1 1 d . . . H13 H 0.7802 0.5961 0.0847 0.063 Uiso 1 1 calc R . . C14 C 0.56822(13) 0.67718(13) 0.08844(6) 0.0422(3) Uani 1 1 d . . . H14 H 0.5350 0.6487 0.0443 0.051 Uiso 1 1 calc R . . C15 C 0.07149(12) 0.92270(12) 0.08754(6) 0.0379(3) Uani 1 1 d . . . C16 C -0.15490(14) 1.06221(17) 0.09728(8) 0.0609(4) Uani 1 1 d . . . H16A H -0.1726 1.0705 0.0487 0.091 Uiso 1 1 calc R . . H16B H -0.1891 1.1540 0.1183 0.091 Uiso 1 1 calc R . . H16C H -0.2092 0.9755 0.1131 0.091 Uiso 1 1 calc R . . C17 C 0.23365(12) 0.64107(12) 0.07239(6) 0.0369(3) Uani 1 1 d . . . C18 C 0.08890(15) 0.42127(14) 0.09424(8) 0.0604(4) Uani 1 1 d . . . H18A H 0.0116 0.4426 0.0588 0.091 Uiso 1 1 calc R . . H18B H 0.0448 0.3713 0.1315 0.091 Uiso 1 1 calc R . . H18C H 0.1639 0.3555 0.0768 0.091 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 0.0434(4) 0.0497(5) 0.0788(6) -0.0175(4) -0.0072(4) -0.0020(4) O2 0.0392(4) 0.0506(5) 0.0708(5) -0.0146(4) -0.0025(4) 0.0099(4) O3 0.0564(5) 0.0578(5) 0.0506(5) -0.0214(4) 0.0046(4) -0.0081(4) O4 0.0555(5) 0.0344(4) 0.0526(5) 0.0028(4) -0.0018(4) -0.0095(4) C1 0.0382(5) 0.0311(5) 0.0344(5) -0.0003(4) 0.0035(4) -0.0012(4) C2 0.0381(5) 0.0329(5) 0.0299(5) -0.0021(4) 0.0022(4) -0.0016(4) C3 0.0341(5) 0.0273(5) 0.0387(5) -0.0008(4) -0.0001(4) 0.0022(4) C4 0.0479(6) 0.0355(5) 0.0410(6) -0.0012(5) 0.0079(5) -0.0019(5) C5 0.0561(7) 0.0386(6) 0.0430(6) -0.0089(5) -0.0014(5) 0.0037(5) C6 0.0445(6) 0.0319(5) 0.0598(7) -0.0024(5) -0.0095(5) -0.0031(5) C7 0.0401(6) 0.0414(6) 0.0603(7) 0.0061(5) 0.0055(5) -0.0062(5) C8 0.0443(6) 0.0380(6) 0.0431(6) -0.0024(5) 0.0069(5) 0.0006(5) C9 0.0372(5) 0.0281(5) 0.0379(5) 0.0004(4) 0.0018(4) -0.0026(4) C10 0.0458(6) 0.0464(6) 0.0427(6) -0.0061(5) 0.0007(5) 0.0036(5) C11 0.0531(7) 0.0627(8) 0.0500(7) -0.0055(6) -0.0126(6) 0.0000(6) C12 0.0383(6) 0.0572(8) 0.0769(9) -0.0036(7) -0.0087(6) 0.0032(6) C13 0.0394(6) 0.0503(7) 0.0687(8) -0.0117(6) 0.0069(6) 0.0021(5) C14 0.0431(6) 0.0393(6) 0.0444(6) -0.0071(5) 0.0040(5) -0.0021(5) C15 0.0391(5) 0.0317(5) 0.0431(6) 0.0024(5) 0.0037(5) -0.0007(4) C16 0.0393(6) 0.0607(8) 0.0823(9) -0.0022(7) 0.0022(6) 0.0124(6) C17 0.0345(5) 0.0329(5) 0.0425(6) -0.0046(5) -0.0035(5) 0.0021(4) C18 0.0558(7) 0.0351(6) 0.0877(10) 0.0042(6) -0.0130(7) -0.0092(6) _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 C15 1.2006(14) . ? O2 C15 1.3282(14) . ? O2 C16 1.4455(14) . ? O3 C17 1.1980(14) . ? O4 C17 1.3314(14) . ? O4 C18 1.4519(15) . ? C1 C2 1.3364(15) . ? C1 C3 1.4967(14) . ? C1 C15 1.5020(15) . ? C2 C9 1.4901(15) . ? C2 C17 1.5083(14) . ? C3 C8 1.3866(16) . ? C3 C4 1.3889(15) . ? C4 C5 1.3805(16) . ? C4 H4 0.9300 . ? C5 C6 1.3801(17) . ? C5 H5 0.9300 . ? C6 C7 1.3718(18) . ? C6 H6 0.9300 . ? C7 C8 1.3907(16) . ? C7 H7 0.9300 . ? C8 H8 0.9300 . ? C9 C10 1.3885(15) . ? C9 C14 1.3908(16) . ? C10 C11 1.3829(17) . ? C10 H10 0.9300 . ? C11 C12 1.377(2) . ? C11 H11 0.9300 . ? C12 C13 1.373(2) . ? C12 H12 0.9300 . ? C13 C14 1.3815(17) . ? C13 H13 0.9300 . ? C14 H14 0.9300 . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C18 H18A 0.9600 . ? C18 H18B 0.9600 . ? C18 H18C 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 C15 O2 C16 117.05(9) . . ? C17 O4 C18 116.07(10) . . ? C2 C1 C3 122.45(9) . . ? C2 C1 C15 118.88(9) . . ? C3 C1 C15 118.61(9) . . ? C1 C2 C9 125.00(9) . . ? C1 C2 C17 122.34(9) . . ? C9 C2 C17 112.64(9) . . ? C8 C3 C4 118.58(10) . . ? C8 C3 C1 119.18(9) . . ? C4 C3 C1 122.25(10) . . ? C5 C4 C3 120.32(11) . . ? C5 C4 H4 119.8 . . ? C3 C4 H4 119.8 . . ? C6 C5 C4 120.70(11) . . ? C6 C5 H5 119.7 . . ? C4 C5 H5 119.7 . . ? C7 C6 C5 119.61(11) . . ? C7 C6 H6 120.2 . . ? C5 C6 H6 120.2 . . ? C6 C7 C8 120.01(11) . . ? C6 C7 H7 120.0 . . ? C8 C7 H7 120.0 . . ? C3 C8 C7 120.78(11) . . ? C3 C8 H8 119.6 . . ? C7 C8 H8 119.6 . . ? C10 C9 C14 118.44(10) . . ? C10 C9 C2 120.64(10) . . ? C14 C9 C2 120.81(9) . . ? C11 C10 C9 120.40(11) . . ? C11 C10 H10 119.8 . . ? C9 C10 H10 119.8 . . ? C12 C11 C10 120.40(12) . . ? C12 C11 H11 119.8 . . ? C10 C11 H11 119.8 . . ? C13 C12 C11 119.83(12) . . ? C13 C12 H12 120.1 . . ? C11 C12 H12 120.1 . . ? C12 C13 C14 120.12(12) . . ? C12 C13 H13 119.9 . . ? C14 C13 H13 119.9 . . ? C13 C14 C9 120.79(11) . . ? C13 C14 H14 119.6 . . ? C9 C14 H14 119.6 . . ? O1 C15 O2 123.76(10) . . ? O1 C15 C1 124.35(10) . . ? O2 C15 C1 111.89(9) . . ? O2 C16 H16A 109.5 . . ? O2 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? O2 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? O3 C17 O4 125.23(10) . . ? O3 C17 C2 123.43(10) . . ? O4 C17 C2 111.11(9) . . ? O4 C18 H18A 109.5 . . ? O4 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? O4 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 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 C3 C1 C2 C9 8.40(16) . . . . ? C15 C1 C2 C9 -174.49(9) . . . . ? C3 C1 C2 C17 -173.19(10) . . . . ? C15 C1 C2 C17 3.93(15) . . . . ? C2 C1 C3 C8 70.18(14) . . . . ? C15 C1 C3 C8 -106.95(12) . . . . ? C2 C1 C3 C4 -109.22(13) . . . . ? C15 C1 C3 C4 73.65(13) . . . . ? C8 C3 C4 C5 -0.58(16) . . . . ? C1 C3 C4 C5 178.82(10) . . . . ? C3 C4 C5 C6 1.28(17) . . . . ? C4 C5 C6 C7 -1.03(18) . . . . ? C5 C6 C7 C8 0.09(17) . . . . ? C4 C3 C8 C7 -0.35(16) . . . . ? C1 C3 C8 C7 -179.78(10) . . . . ? C6 C7 C8 C3 0.60(17) . . . . ? C1 C2 C9 C10 50.06(16) . . . . ? C17 C2 C9 C10 -128.48(11) . . . . ? C1 C2 C9 C14 -133.96(12) . . . . ? C17 C2 C9 C14 47.49(13) . . . . ? C14 C9 C10 C11 0.63(17) . . . . ? C2 C9 C10 C11 176.70(11) . . . . ? C9 C10 C11 C12 -0.4(2) . . . . ? C10 C11 C12 C13 0.6(2) . . . . ? C11 C12 C13 C14 -1.2(2) . . . . ? C12 C13 C14 C9 1.43(19) . . . . ? C10 C9 C14 C13 -1.15(17) . . . . ? C2 C9 C14 C13 -177.21(11) . . . . ? C16 O2 C15 O1 -0.17(17) . . . . ? C16 O2 C15 C1 179.86(10) . . . . ? C2 C1 C15 O1 -19.83(17) . . . . ? C3 C1 C15 O1 157.40(11) . . . . ? C2 C1 C15 O2 160.13(10) . . . . ? C3 C1 C15 O2 -22.64(13) . . . . ? C18 O4 C17 O3 -1.70(16) . . . . ? C18 O4 C17 C2 -176.38(9) . . . . ? C1 C2 C17 O3 100.63(14) . . . . ? C9 C2 C17 O3 -80.78(13) . . . . ? C1 C2 C17 O4 -84.58(12) . . . . ? C9 C2 C17 O4 94.01(10) . . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.56 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.229 _refine_diff_density_min -0.256 _refine_diff_density_rms 0.078 data_hwh43 _database_code_depnum_ccdc_archive 'CCDC 261328' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19 H21 N O6' _chemical_formula_weight 359.37 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/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 13.289(2) _cell_length_b 8.1727(12) _cell_length_c 16.588(3) _cell_angle_alpha 90.00 _cell_angle_beta 91.999(3) _cell_angle_gamma 90.00 _cell_volume 1800.4(5) _cell_formula_units_Z 4 _cell_measurement_temperature 294(2) _cell_measurement_reflns_used 10145 _cell_measurement_theta_min 1 _cell_measurement_theta_max 27.5 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.50 _exptl_crystal_size_min 0.46 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.326 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 760 _exptl_absorpt_coefficient_mu 0.099 _exptl_absorpt_correction_type multi-scans _exptl_absorpt_correction_T_min 0.815 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details 'sadabs; sHELDRICK 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 294(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 CCD Area Detector' _diffrn_measurement_method 'omega and phi scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16387 _diffrn_reflns_av_R_equivalents 0.0357 _diffrn_reflns_av_sigmaI/netI 0.0294 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.46 _diffrn_reflns_theta_max 27.59 _reflns_number_total 4172 _reflns_number_gt 3171 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0585P)^2^+0.4268P] 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 4172 _refine_ls_number_parameters 241 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0563 _refine_ls_R_factor_gt 0.0399 _refine_ls_wR_factor_ref 0.1212 _refine_ls_wR_factor_gt 0.1091 _refine_ls_goodness_of_fit_ref 1.016 _refine_ls_restrained_S_all 1.016 _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 0.09320(8) 0.64293(12) 0.59902(6) 0.0474(3) Uani 1 1 d . . . H1 H 0.0659 0.6927 0.5613 0.071 Uiso 1 1 calc R . . O2 O 0.06162(9) 0.18631(16) 0.48899(7) 0.0621(3) Uani 1 1 d . . . O3 O 0.16822(10) 0.00585(15) 0.52892(8) 0.0669(4) Uani 1 1 d . . . O4 O 0.27445(7) 0.36260(11) 0.52013(6) 0.0413(2) Uani 1 1 d . . . O5 O 0.32555(9) 0.72061(16) 0.46466(7) 0.0588(3) Uani 1 1 d . . . O6 O 0.16596(8) 0.65277(12) 0.43497(6) 0.0436(3) Uani 1 1 d . . . N1 N 0.11722(9) 0.12606(15) 0.54079(7) 0.0419(3) Uani 1 1 d . . . C1 C 0.24550(9) 0.51896(16) 0.54918(8) 0.0335(3) Uani 1 1 d . . . C2 C 0.13284(9) 0.49338(16) 0.57060(8) 0.0340(3) Uani 1 1 d . . . H2 H 0.0942(6) 0.4593(6) 0.5219(8) 0.041 Uiso 1 1 calc R . . C3 C 0.12169(9) 0.36498(16) 0.63564(8) 0.0324(3) Uani 1 1 d . . . C4 C 0.11990(10) 0.19664(17) 0.62253(8) 0.0354(3) Uani 1 1 d . . . C5 C 0.11628(12) 0.08307(19) 0.68446(9) 0.0479(4) Uani 1 1 d . . . H5 H 0.1173 -0.0284 0.6733 0.058 Uiso 1 1 calc R . . C6 C 0.11120(14) 0.1379(2) 0.76272(10) 0.0559(4) Uani 1 1 d . . . H6 H 0.1078 0.0635 0.8050 0.067 Uiso 1 1 calc R . . C7 C 0.11118(13) 0.3037(2) 0.77811(9) 0.0535(4) Uani 1 1 d . . . H7 H 0.1071 0.3409 0.8309 0.064 Uiso 1 1 calc R . . C8 C 0.11715(11) 0.41482(19) 0.71579(8) 0.0426(3) Uani 1 1 d . . . H8 H 0.1182 0.5261 0.7276 0.051 Uiso 1 1 calc R . . C9 C 0.30777(9) 0.57720(17) 0.62270(8) 0.0368(3) Uani 1 1 d . . . C10 C 0.35007(11) 0.4646(2) 0.67683(9) 0.0492(4) Uani 1 1 d . . . H10 H 0.3453 0.3533 0.6658 0.059 Uiso 1 1 calc R . . C11 C 0.39949(13) 0.5174(3) 0.74743(10) 0.0635(5) Uani 1 1 d . . . H11 H 0.4280 0.4412 0.7830 0.076 Uiso 1 1 calc R . . C12 C 0.40645(14) 0.6818(3) 0.76495(11) 0.0654(5) Uani 1 1 d . . . H12 H 0.4391 0.7166 0.8124 0.078 Uiso 1 1 calc R . . C13 C 0.36512(13) 0.7933(3) 0.71221(11) 0.0601(5) Uani 1 1 d . . . H13 H 0.3700 0.9045 0.7237 0.072 Uiso 1 1 calc R . . C14 C 0.31593(11) 0.7418(2) 0.64165(9) 0.0461(3) Uani 1 1 d . . . H14 H 0.2879 0.8192 0.6064 0.055 Uiso 1 1 calc R . . C15 C 0.25170(11) 0.64473(16) 0.47941(8) 0.0374(3) Uani 1 1 d . . . C16 C 0.16563(14) 0.7648(2) 0.36730(9) 0.0532(4) Uani 1 1 d . . . H16A H 0.1839 0.8722 0.3860 0.080 Uiso 1 1 calc R . . H16B H 0.0995 0.7681 0.3421 0.080 Uiso 1 1 calc R . . H16C H 0.2132 0.7283 0.3289 0.080 Uiso 1 1 calc R . . C17 C 0.37471(12) 0.3427(2) 0.48902(12) 0.0552(4) Uani 1 1 d . . . H17 H 0.4193(9) 0.4277(18) 0.5118(5) 0.066 Uiso 1 1 calc R . . C18 C 0.3710(2) 0.3559(3) 0.39810(14) 0.0914(8) Uani 1 1 d . . . H18A H 0.3275 0.2726 0.3757 0.137 Uiso 1 1 calc R . . H18B H 0.4376 0.3420 0.3784 0.137 Uiso 1 1 calc R . . H18C H 0.3457 0.4617 0.3824 0.137 Uiso 1 1 calc R . . C19 C 0.41207(16) 0.1766(3) 0.51653(18) 0.0893(8) Uani 1 1 d . . . H19A H 0.4092 0.1692 0.5742 0.134 Uiso 1 1 calc R . . H19B H 0.4803 0.1620 0.5008 0.134 Uiso 1 1 calc R . . H19C H 0.3704 0.0930 0.4921 0.134 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 0.0490(6) 0.0412(6) 0.0529(6) 0.0097(5) 0.0129(5) 0.0181(4) O2 0.0661(8) 0.0709(8) 0.0480(6) -0.0051(6) -0.0171(6) 0.0156(6) O3 0.0878(9) 0.0479(7) 0.0646(8) -0.0131(6) -0.0021(7) 0.0228(6) O4 0.0337(5) 0.0345(5) 0.0562(6) -0.0035(4) 0.0103(4) 0.0028(4) O5 0.0521(7) 0.0714(8) 0.0532(7) 0.0181(6) 0.0064(5) -0.0185(6) O6 0.0468(6) 0.0451(6) 0.0387(5) 0.0126(4) 0.0007(4) -0.0012(4) N1 0.0440(6) 0.0378(6) 0.0437(7) -0.0008(5) -0.0007(5) 0.0004(5) C1 0.0330(6) 0.0308(6) 0.0370(7) 0.0033(5) 0.0055(5) 0.0026(5) C2 0.0322(6) 0.0340(7) 0.0360(7) 0.0054(5) 0.0043(5) 0.0042(5) C3 0.0278(6) 0.0358(7) 0.0338(6) 0.0052(5) 0.0039(5) 0.0016(5) C4 0.0324(6) 0.0369(7) 0.0370(7) 0.0032(5) 0.0024(5) 0.0009(5) C5 0.0535(9) 0.0381(8) 0.0524(9) 0.0106(7) 0.0042(7) 0.0007(6) C6 0.0686(11) 0.0556(10) 0.0440(8) 0.0203(7) 0.0084(7) 0.0005(8) C7 0.0645(10) 0.0630(10) 0.0336(7) 0.0051(7) 0.0100(7) -0.0006(8) C8 0.0489(8) 0.0419(8) 0.0375(7) -0.0003(6) 0.0075(6) 0.0001(6) C9 0.0303(6) 0.0433(8) 0.0371(7) 0.0048(6) 0.0046(5) 0.0006(5) C10 0.0425(8) 0.0539(9) 0.0511(9) 0.0138(7) -0.0001(6) 0.0029(7) C11 0.0436(9) 0.0980(15) 0.0483(9) 0.0232(10) -0.0038(7) 0.0051(9) C12 0.0479(9) 0.1020(16) 0.0458(9) -0.0097(10) -0.0037(7) -0.0046(9) C13 0.0517(10) 0.0691(11) 0.0593(10) -0.0178(9) -0.0003(8) -0.0039(8) C14 0.0426(8) 0.0478(9) 0.0478(8) -0.0012(7) 0.0013(6) 0.0015(6) C15 0.0422(7) 0.0358(7) 0.0344(7) 0.0014(5) 0.0072(5) 0.0000(6) C16 0.0658(10) 0.0537(9) 0.0402(8) 0.0153(7) 0.0036(7) 0.0021(8) C17 0.0358(8) 0.0508(9) 0.0800(12) -0.0154(8) 0.0165(7) 0.0023(7) C18 0.0957(17) 0.1019(18) 0.0794(15) -0.0215(13) 0.0441(13) 0.0122(14) C19 0.0576(12) 0.0670(13) 0.144(2) -0.0149(14) 0.0088(13) 0.0262(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 C2 1.4181(16) . ? O1 H1 0.8200 . ? O2 N1 1.2174(16) . ? O3 N1 1.2135(16) . ? O4 C1 1.4234(16) . ? O4 C17 1.4547(17) . ? O5 C15 1.1934(17) . ? O6 C15 1.3369(17) . ? O6 C16 1.4484(17) . ? N1 C4 1.4728(18) . ? C1 C9 1.5258(19) . ? C1 C15 1.5522(18) . ? C1 C2 1.5648(18) . ? C2 C3 1.5161(17) . ? C2 H2 0.9819 . ? C3 C4 1.3930(19) . ? C3 C8 1.3938(19) . ? C4 C5 1.3866(19) . ? C5 C6 1.377(2) . ? C5 H5 0.9300 . ? C6 C7 1.379(3) . ? C6 H6 0.9300 . ? C7 C8 1.380(2) . ? C7 H7 0.9300 . ? C8 H8 0.9300 . ? C9 C14 1.385(2) . ? C9 C10 1.390(2) . ? C10 C11 1.391(2) . ? C10 H10 0.9300 . ? C11 C12 1.376(3) . ? C11 H11 0.9300 . ? C12 C13 1.366(3) . ? C12 H12 0.9300 . ? C13 C14 1.386(2) . ? C13 H13 0.9300 . ? C14 H14 0.9300 . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C17 C18 1.511(3) . ? C17 C19 1.511(3) . ? C17 H17 0.9808 . ? C18 H18A 0.9600 . ? C18 H18B 0.9600 . ? C18 H18C 0.9600 . ? C19 H19A 0.9600 . ? C19 H19B 0.9600 . ? C19 H19C 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 C2 O1 H1 109.5 . . ? C1 O4 C17 118.83(11) . . ? C15 O6 C16 115.97(12) . . ? O3 N1 O2 122.79(13) . . ? O3 N1 C4 118.08(12) . . ? O2 N1 C4 119.07(12) . . ? O4 C1 C9 113.91(11) . . ? O4 C1 C15 108.67(10) . . ? C9 C1 C15 110.36(11) . . ? O4 C1 C2 103.23(10) . . ? C9 C1 C2 110.90(10) . . ? C15 C1 C2 109.50(10) . . ? O1 C2 C3 108.25(10) . . ? O1 C2 C1 109.26(11) . . ? C3 C2 C1 111.84(10) . . ? O1 C2 H2 109.1 . . ? C3 C2 H2 109.1 . . ? C1 C2 H2 109.1 . . ? C4 C3 C8 115.88(12) . . ? C4 C3 C2 125.03(12) . . ? C8 C3 C2 119.02(12) . . ? C5 C4 C3 123.11(13) . . ? C5 C4 N1 114.81(13) . . ? C3 C4 N1 122.03(11) . . ? C6 C5 C4 118.98(15) . . ? C6 C5 H5 120.5 . . ? C4 C5 H5 120.5 . . ? C5 C6 C7 119.65(14) . . ? C5 C6 H6 120.2 . . ? C7 C6 H6 120.2 . . ? C8 C7 C6 120.50(15) . . ? C8 C7 H7 119.7 . . ? C6 C7 H7 119.7 . . ? C7 C8 C3 121.84(14) . . ? C7 C8 H8 119.1 . . ? C3 C8 H8 119.1 . . ? C14 C9 C10 117.99(14) . . ? C14 C9 C1 121.36(12) . . ? C10 C9 C1 120.37(13) . . ? C11 C10 C9 120.45(17) . . ? C11 C10 H10 119.8 . . ? C9 C10 H10 119.8 . . ? C12 C11 C10 120.44(17) . . ? C12 C11 H11 119.8 . . ? C10 C11 H11 119.8 . . ? C13 C12 C11 119.59(17) . . ? C13 C12 H12 120.2 . . ? C11 C12 H12 120.2 . . ? C12 C13 C14 120.35(18) . . ? C12 C13 H13 119.8 . . ? C14 C13 H13 119.8 . . ? C9 C14 C13 121.18(15) . . ? C9 C14 H14 119.4 . . ? C13 C14 H14 119.4 . . ? O5 C15 O6 123.54(13) . . ? O5 C15 C1 124.22(13) . . ? O6 C15 C1 112.17(11) . . ? O6 C16 H16A 109.5 . . ? O6 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? O6 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? O4 C17 C18 110.36(16) . . ? O4 C17 C19 106.78(15) . . ? C18 C17 C19 111.39(18) . . ? O4 C17 H17 109.4 . . ? C18 C17 H17 109.4 . . ? C19 C17 H17 109.4 . . ? C17 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C17 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C17 C19 H19A 109.5 . . ? C17 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C17 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 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 C17 O4 C1 C9 -63.71(16) . . . . ? C17 O4 C1 C15 59.77(16) . . . . ? C17 O4 C1 C2 175.96(12) . . . . ? O4 C1 C2 O1 -178.68(10) . . . . ? C9 C1 C2 O1 58.95(13) . . . . ? C15 C1 C2 O1 -63.08(13) . . . . ? O4 C1 C2 C3 61.48(13) . . . . ? C9 C1 C2 C3 -60.88(14) . . . . ? C15 C1 C2 C3 177.09(11) . . . . ? O1 C2 C3 C4 157.58(12) . . . . ? C1 C2 C3 C4 -82.00(16) . . . . ? O1 C2 C3 C8 -25.44(16) . . . . ? C1 C2 C3 C8 94.99(14) . . . . ? C8 C3 C4 C5 -1.49(19) . . . . ? C2 C3 C4 C5 175.57(13) . . . . ? C8 C3 C4 N1 175.74(12) . . . . ? C2 C3 C4 N1 -7.2(2) . . . . ? O3 N1 C4 C5 -43.05(18) . . . . ? O2 N1 C4 C5 134.28(15) . . . . ? O3 N1 C4 C3 139.49(15) . . . . ? O2 N1 C4 C3 -43.18(19) . . . . ? C3 C4 C5 C6 2.0(2) . . . . ? N1 C4 C5 C6 -175.44(14) . . . . ? C4 C5 C6 C7 -0.9(3) . . . . ? C5 C6 C7 C8 -0.6(3) . . . . ? C6 C7 C8 C3 1.1(2) . . . . ? C4 C3 C8 C7 -0.1(2) . . . . ? C2 C3 C8 C7 -177.30(14) . . . . ? O4 C1 C9 C14 156.90(12) . . . . ? C15 C1 C9 C14 34.35(16) . . . . ? C2 C1 C9 C14 -87.17(15) . . . . ? O4 C1 C9 C10 -29.26(16) . . . . ? C15 C1 C9 C10 -151.81(12) . . . . ? C2 C1 C9 C10 86.67(15) . . . . ? C14 C9 C10 C11 -0.4(2) . . . . ? C1 C9 C10 C11 -174.46(14) . . . . ? C9 C10 C11 C12 0.5(2) . . . . ? C10 C11 C12 C13 -0.5(3) . . . . ? C11 C12 C13 C14 0.4(3) . . . . ? C10 C9 C14 C13 0.3(2) . . . . ? C1 C9 C14 C13 174.26(14) . . . . ? C12 C13 C14 C9 -0.3(3) . . . . ? C16 O6 C15 O5 -1.8(2) . . . . ? C16 O6 C15 C1 -178.74(12) . . . . ? O4 C1 C15 O5 -88.78(17) . . . . ? C9 C1 C15 O5 36.79(18) . . . . ? C2 C1 C15 O5 159.14(14) . . . . ? O4 C1 C15 O6 88.16(13) . . . . ? C9 C1 C15 O6 -146.27(11) . . . . ? C2 C1 C15 O6 -23.92(15) . . . . ? C1 O4 C17 C18 -97.42(17) . . . . ? C1 O4 C17 C19 141.36(16) . . . . ? 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 O1 H1 O2 0.82 2.11 2.8464(15) 149.6 3_566 _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.59 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.228 _refine_diff_density_min -0.175 _refine_diff_density_rms 0.036