Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Richard Hsung' 'Lingfen You' 'Xuejun Zhang' _publ_contact_author_name 'Richard Hsung' _publ_contact_author_address ; Division of Pharmaceutical Sciences University of Wisconsin School of Pharmacy And Department of Chemistry 777 Highland Avenue Madison WI 53705 UNITED STATES OF AMERICA ; _publ_contact_author_email RHSUNG@WISC.EDU _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; Tandem Azidination- and Hydroazidination-Huisgen [3 + 2] Cycloadditions of Ynamides. Syntheses of Chiral Amide Substituted Triazoles ; data_05315 _database_code_depnum_ccdc_archive 'CCDC 607119' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 05315 _chemical_melting_point ? _chemical_formula_moiety 'C18 H16 N4 O2' _chemical_formula_sum 'C18 H16 N4 O2' _chemical_formula_weight 320.35 _chemical_absolute_configuration rm 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 P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 8.7353(7) _cell_length_b 9.8100(8) _cell_length_c 18.0556(14) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1547.2(2) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 3441 _cell_measurement_theta_min 2.26 _cell_measurement_theta_max 24.11 _exptl_crystal_description plate _exptl_crystal_colour colorless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.375 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 672 _exptl_absorpt_coefficient_mu 0.093 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9726 _exptl_absorpt_correction_T_max 0.9862 _exptl_absorpt_process_details 'SADABS, R. Blessing, 1995' _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART Platform CCD' _diffrn_measurement_method 'area detector, omega scans per phi' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9507 _diffrn_reflns_av_R_equivalents 0.0299 _diffrn_reflns_av_sigmaI/netI 0.0217 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.26 _diffrn_reflns_theta_max 26.38 _reflns_number_total 1823 _reflns_number_gt 1600 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART, Bruker' _computing_cell_refinement 'SAINT, Bruker' _computing_data_reduction 'SAINT, Bruker' _computing_structure_solution SIR97 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL, Bruker' _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^)+(0.0340P)^2^+0.4894P] 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 riding _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0(10) _refine_ls_number_reflns 1823 _refine_ls_number_parameters 217 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0423 _refine_ls_R_factor_gt 0.0332 _refine_ls_wR_factor_ref 0.0837 _refine_ls_wR_factor_gt 0.0768 _refine_ls_goodness_of_fit_ref 1.014 _refine_ls_restrained_S_all 1.014 _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 0.6857(2) 0.61426(18) 0.30870(10) 0.0502(5) Uani 1 1 d . . . O2 O 0.5711(2) 0.4216(2) 0.26862(9) 0.0514(5) Uani 1 1 d . . . N1 N 0.6989(2) 0.41319(18) 0.37390(10) 0.0333(4) Uani 1 1 d . . . N2 N 0.8046(3) 0.37933(19) 0.49393(11) 0.0415(5) Uani 1 1 d . . . N3 N 0.8832(3) 0.4497(2) 0.54397(12) 0.0499(6) Uani 1 1 d . . . N4 N 0.9067(2) 0.57331(19) 0.51555(13) 0.0453(5) Uani 1 1 d . . . C1 C 0.6553(3) 0.4957(3) 0.31690(13) 0.0391(5) Uani 1 1 d . . . C2 C 0.5300(3) 0.2943(3) 0.30314(15) 0.0506(7) Uani 1 1 d . . . H2A H 0.5323 0.2189 0.2667 0.061 Uiso 1 1 calc R . . H2B H 0.4262 0.2996 0.3249 0.061 Uiso 1 1 calc R . . C3 C 0.6507(3) 0.2720(2) 0.36365(12) 0.0358(5) Uani 1 1 d . . . H3 H 0.6001 0.2382 0.4098 0.043 Uiso 1 1 calc R . . C4 C 0.7788(3) 0.1760(2) 0.34187(12) 0.0335(5) Uani 1 1 d . . . C5 C 0.9306(3) 0.2150(2) 0.33740(13) 0.0403(5) Uani 1 1 d . . . H5 H 0.9577 0.3073 0.3462 0.048 Uiso 1 1 calc R . . C6 C 1.0433(3) 0.1214(3) 0.32024(15) 0.0497(6) Uani 1 1 d . . . H6 H 1.1473 0.1494 0.3179 0.060 Uiso 1 1 calc R . . C7 C 1.0048(3) -0.0128(3) 0.30654(14) 0.0504(7) Uani 1 1 d . . . H7 H 1.0825 -0.0772 0.2951 0.060 Uiso 1 1 calc R . . C8 C 0.8538(4) -0.0533(3) 0.30951(13) 0.0492(6) Uani 1 1 d . . . H8 H 0.8269 -0.1453 0.2996 0.059 Uiso 1 1 calc R . . C9 C 0.7414(3) 0.0412(2) 0.32706(13) 0.0423(6) Uani 1 1 d . . . H9 H 0.6373 0.0133 0.3290 0.051 Uiso 1 1 calc R . . C10 C 0.7805(2) 0.4611(2) 0.43506(12) 0.0319(5) Uani 1 1 d . . . C11 C 0.8445(3) 0.5857(2) 0.44733(13) 0.0382(5) Uani 1 1 d . . . H11 H 0.8453 0.6629 0.4155 0.046 Uiso 1 1 calc R . . C12 C 0.9931(4) 0.6762(3) 0.55727(19) 0.0642(9) Uani 1 1 d . . . H12A H 1.0926 0.6924 0.5326 0.077 Uiso 1 1 calc R . . H12B H 1.0139 0.6415 0.6078 0.077 Uiso 1 1 calc R . . C13 C 0.9069(3) 0.8075(2) 0.56239(12) 0.0357(5) Uani 1 1 d . . . C14 C 0.7916(3) 0.8243(3) 0.61497(14) 0.0543(7) Uani 1 1 d . . . H14 H 0.7677 0.7526 0.6484 0.065 Uiso 1 1 calc R . . C15 C 0.7110(3) 0.9482(4) 0.61821(16) 0.0655(9) Uani 1 1 d . . . H15 H 0.6319 0.9604 0.6537 0.079 Uiso 1 1 calc R . . C16 C 0.7467(4) 1.0512(3) 0.57021(18) 0.0603(8) Uani 1 1 d . . . H16 H 0.6916 1.1346 0.5722 0.072 Uiso 1 1 calc R . . C17 C 0.8586(4) 1.0349(3) 0.52051(16) 0.0516(7) Uani 1 1 d . . . H17 H 0.8834 1.1077 0.4879 0.062 Uiso 1 1 calc R . . C18 C 0.9377(3) 0.9151(2) 0.51588(13) 0.0389(5) Uani 1 1 d . . . H18 H 1.0159 0.9059 0.4797 0.047 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 0.0513(11) 0.0441(10) 0.0552(11) 0.0155(8) -0.0016(9) 0.0072(9) O2 0.0445(10) 0.0633(12) 0.0463(9) -0.0054(9) -0.0132(8) 0.0074(10) N1 0.0333(9) 0.0324(10) 0.0343(9) -0.0011(8) -0.0034(8) -0.0003(8) N2 0.0569(13) 0.0266(9) 0.0409(11) -0.0018(8) -0.0103(10) -0.0001(9) N3 0.0680(15) 0.0303(10) 0.0513(12) -0.0029(9) -0.0213(11) 0.0088(11) N4 0.0477(12) 0.0255(10) 0.0628(13) -0.0051(10) -0.0235(11) 0.0061(9) C1 0.0303(11) 0.0492(14) 0.0378(12) 0.0003(11) 0.0015(10) 0.0071(11) C2 0.0334(12) 0.0618(17) 0.0565(15) -0.0201(14) -0.0026(12) -0.0047(13) C3 0.0337(11) 0.0379(12) 0.0358(11) -0.0065(10) 0.0047(10) -0.0099(10) C4 0.0368(11) 0.0330(11) 0.0306(11) -0.0010(9) 0.0006(10) -0.0081(9) C5 0.0387(12) 0.0366(12) 0.0456(13) -0.0075(11) 0.0031(11) -0.0055(10) C6 0.0421(13) 0.0543(15) 0.0527(15) -0.0062(13) 0.0025(13) 0.0024(12) C7 0.0630(17) 0.0443(14) 0.0439(14) -0.0028(12) -0.0015(13) 0.0149(13) C8 0.0765(18) 0.0313(12) 0.0398(12) 0.0002(11) -0.0017(14) -0.0019(14) C9 0.0502(14) 0.0379(13) 0.0387(12) 0.0003(11) 0.0012(11) -0.0101(11) C10 0.0305(10) 0.0281(11) 0.0371(11) -0.0014(9) -0.0016(9) 0.0032(9) C11 0.0351(11) 0.0279(11) 0.0516(13) 0.0024(10) -0.0124(11) 0.0015(10) C12 0.0621(18) 0.0362(13) 0.095(2) -0.0142(15) -0.0478(18) 0.0098(13) C13 0.0403(12) 0.0281(11) 0.0387(12) -0.0031(10) -0.0149(11) -0.0018(10) C14 0.0625(17) 0.0633(17) 0.0370(13) 0.0088(13) -0.0054(13) -0.0235(16) C15 0.0463(15) 0.096(3) 0.0536(16) -0.0358(18) 0.0048(13) 0.0056(18) C16 0.0649(19) 0.0453(16) 0.0707(19) -0.0179(16) -0.0176(16) 0.0121(15) C17 0.0645(17) 0.0328(13) 0.0577(16) 0.0013(12) -0.0228(15) -0.0022(13) C18 0.0415(13) 0.0409(13) 0.0343(11) -0.0026(11) -0.0050(10) -0.0074(11) _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 C1 1.202(3) . ? O2 C1 1.353(3) . ? O2 C2 1.442(3) . ? N1 C1 1.364(3) . ? N1 C10 1.396(3) . ? N1 C3 1.459(3) . ? N2 N3 1.328(3) . ? N2 C10 1.348(3) . ? N3 N4 1.332(3) . ? N4 C11 1.352(3) . ? N4 C12 1.468(3) . ? C2 C3 1.534(3) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? C3 C4 1.514(3) . ? C3 H3 1.0000 . ? C4 C5 1.382(3) . ? C4 C9 1.388(3) . ? C5 C6 1.382(3) . ? C5 H5 0.9500 . ? C6 C7 1.381(4) . ? C6 H6 0.9500 . ? C7 C8 1.379(4) . ? C7 H7 0.9500 . ? C8 C9 1.387(4) . ? C8 H8 0.9500 . ? C9 H9 0.9500 . ? C10 C11 1.363(3) . ? C11 H11 0.9500 . ? C12 C13 1.496(3) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 C18 1.375(3) . ? C13 C14 1.393(4) . ? C14 C15 1.406(4) . ? C14 H14 0.9500 . ? C15 C16 1.366(4) . ? C15 H15 0.9500 . ? C16 C17 1.337(4) . ? C16 H16 0.9500 . ? C17 C18 1.366(4) . ? C17 H17 0.9500 . ? C18 H18 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 C1 O2 C2 108.83(18) . . ? C1 N1 C10 122.65(19) . . ? C1 N1 C3 112.80(18) . . ? C10 N1 C3 124.55(18) . . ? N3 N2 C10 107.91(18) . . ? N2 N3 N4 106.91(19) . . ? N3 N4 C11 111.8(2) . . ? N3 N4 C12 120.5(2) . . ? C11 N4 C12 127.7(2) . . ? O1 C1 O2 124.1(2) . . ? O1 C1 N1 127.3(2) . . ? O2 C1 N1 108.6(2) . . ? O2 C2 C3 105.06(19) . . ? O2 C2 H2A 110.7 . . ? C3 C2 H2A 110.7 . . ? O2 C2 H2B 110.7 . . ? C3 C2 H2B 110.7 . . ? H2A C2 H2B 108.8 . . ? N1 C3 C4 114.24(18) . . ? N1 C3 C2 98.84(19) . . ? C4 C3 C2 114.27(18) . . ? N1 C3 H3 109.7 . . ? C4 C3 H3 109.7 . . ? C2 C3 H3 109.7 . . ? C5 C4 C9 118.6(2) . . ? C5 C4 C3 123.5(2) . . ? C9 C4 C3 118.0(2) . . ? C6 C5 C4 120.9(2) . . ? C6 C5 H5 119.6 . . ? C4 C5 H5 119.6 . . ? C7 C6 C5 120.0(3) . . ? C7 C6 H6 120.0 . . ? C5 C6 H6 120.0 . . ? C8 C7 C6 120.0(3) . . ? C8 C7 H7 120.0 . . ? C6 C7 H7 120.0 . . ? C7 C8 C9 119.6(2) . . ? C7 C8 H8 120.2 . . ? C9 C8 H8 120.2 . . ? C8 C9 C4 120.9(2) . . ? C8 C9 H9 119.5 . . ? C4 C9 H9 119.5 . . ? N2 C10 C11 109.96(19) . . ? N2 C10 N1 120.21(19) . . ? C11 C10 N1 129.8(2) . . ? N4 C11 C10 103.4(2) . . ? N4 C11 H11 128.3 . . ? C10 C11 H11 128.3 . . ? N4 C12 C13 111.4(2) . . ? N4 C12 H12A 109.3 . . ? C13 C12 H12A 109.3 . . ? N4 C12 H12B 109.3 . . ? C13 C12 H12B 109.3 . . ? H12A C12 H12B 108.0 . . ? C18 C13 C14 117.8(2) . . ? C18 C13 C12 121.6(2) . . ? C14 C13 C12 120.5(2) . . ? C13 C14 C15 119.5(2) . . ? C13 C14 H14 120.3 . . ? C15 C14 H14 120.3 . . ? C16 C15 C14 119.9(3) . . ? C16 C15 H15 120.1 . . ? C14 C15 H15 120.1 . . ? C17 C16 C15 120.3(3) . . ? C17 C16 H16 119.9 . . ? C15 C16 H16 119.9 . . ? C16 C17 C18 120.9(3) . . ? C16 C17 H17 119.5 . . ? C18 C17 H17 119.5 . . ? C17 C18 C13 121.6(2) . . ? C17 C18 H18 119.2 . . ? C13 C18 H18 119.2 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C10 N2 N3 N4 -0.1(3) . . . . ? N2 N3 N4 C11 0.1(3) . . . . ? N2 N3 N4 C12 -179.1(2) . . . . ? C2 O2 C1 O1 -167.7(2) . . . . ? C2 O2 C1 N1 13.0(2) . . . . ? C10 N1 C1 O1 4.3(4) . . . . ? C3 N1 C1 O1 -175.9(2) . . . . ? C10 N1 C1 O2 -176.47(19) . . . . ? C3 N1 C1 O2 3.4(3) . . . . ? C1 O2 C2 C3 -23.2(2) . . . . ? C1 N1 C3 C4 105.2(2) . . . . ? C10 N1 C3 C4 -75.0(3) . . . . ? C1 N1 C3 C2 -16.5(2) . . . . ? C10 N1 C3 C2 163.3(2) . . . . ? O2 C2 C3 N1 22.8(2) . . . . ? O2 C2 C3 C4 -98.9(2) . . . . ? N1 C3 C4 C5 4.7(3) . . . . ? C2 C3 C4 C5 117.6(3) . . . . ? N1 C3 C4 C9 -176.6(2) . . . . ? C2 C3 C4 C9 -63.7(3) . . . . ? C9 C4 C5 C6 -1.5(4) . . . . ? C3 C4 C5 C6 177.2(2) . . . . ? C4 C5 C6 C7 0.7(4) . . . . ? C5 C6 C7 C8 0.4(4) . . . . ? C6 C7 C8 C9 -0.7(4) . . . . ? C7 C8 C9 C4 -0.1(4) . . . . ? C5 C4 C9 C8 1.2(4) . . . . ? C3 C4 C9 C8 -177.6(2) . . . . ? N3 N2 C10 C11 0.1(3) . . . . ? N3 N2 C10 N1 -179.5(2) . . . . ? C1 N1 C10 N2 171.9(2) . . . . ? C3 N1 C10 N2 -7.9(3) . . . . ? C1 N1 C10 C11 -7.6(4) . . . . ? C3 N1 C10 C11 172.6(2) . . . . ? N3 N4 C11 C10 0.0(3) . . . . ? C12 N4 C11 C10 179.1(3) . . . . ? N2 C10 C11 N4 0.0(3) . . . . ? N1 C10 C11 N4 179.5(2) . . . . ? N3 N4 C12 C13 -128.3(3) . . . . ? C11 N4 C12 C13 52.6(4) . . . . ? N4 C12 C13 C18 -99.0(3) . . . . ? N4 C12 C13 C14 81.0(3) . . . . ? C18 C13 C14 C15 0.6(3) . . . . ? C12 C13 C14 C15 -179.3(2) . . . . ? C13 C14 C15 C16 -0.3(4) . . . . ? C14 C15 C16 C17 -0.5(4) . . . . ? C15 C16 C17 C18 1.0(4) . . . . ? C16 C17 C18 C13 -0.7(4) . . . . ? C14 C13 C18 C17 -0.1(3) . . . . ? C12 C13 C18 C17 179.8(2) . . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.38 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.195 _refine_diff_density_min -0.166 _refine_diff_density_rms 0.031