Electronic Supplementary Material for Organic & Biomolecular Chemistry This journal is © The Royal Society of Chemistry 2005 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Alexander Khlebnikov' 'Mikhail S. Novikov' 'Ekaterina Yu Shinkevich' 'Denis Vidovic' _publ_contact_author_name 'Alexander Khlebnikov' _publ_contact_author_address ; Chemistry St. Petersburg State University Universitetskii pr., 26 St. Petersburg 198504 RUSSIAN FEDERATION ; _publ_contact_author_email ALEXANDER.KHLEBNIKOV@POBOX.SPBU.RU _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; Selective transannular ring transformations in azirino-fused eight-membered O,N- or S,N-heterocycles ; data_test _database_code_depnum_ccdc_archive 'CCDC 283218' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H22 N2 O' _chemical_formula_weight 354.44 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 ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.4130(19) _cell_length_b 10.281(2) _cell_length_c 11.618(2) _cell_angle_alpha 101.32(3) _cell_angle_beta 109.63(3) _cell_angle_gamma 112.28(3) _cell_volume 909.8(3) _cell_formula_units_Z 2 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.294 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 376 _exptl_absorpt_coefficient_mu 0.079 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 133(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9324 _diffrn_reflns_av_R_equivalents 0.0622 _diffrn_reflns_av_sigmaI/netI 0.0481 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.00 _diffrn_reflns_theta_max 24.87 _reflns_number_total 3128 _reflns_number_gt 2368 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _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^)+(0.0681P)^2^+0.0446P] 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 3128 _refine_ls_number_parameters 244 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0616 _refine_ls_R_factor_gt 0.0446 _refine_ls_wR_factor_ref 0.1196 _refine_ls_wR_factor_gt 0.1110 _refine_ls_goodness_of_fit_ref 1.028 _refine_ls_restrained_S_all 1.028 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O5 O 0.05277(14) 0.46571(12) 0.73788(11) 0.0306(3) Uani 1 1 d . . . N1 N -0.10673(18) 0.21741(15) 0.40426(13) 0.0318(3) Uani 1 1 d . . . N10 N -0.23241(17) 0.33697(15) 0.49096(13) 0.0305(3) Uani 1 1 d . . . C2 C 0.0409(2) 0.19538(19) 0.41170(18) 0.0362(4) Uani 1 1 d . . . H2A H 0.1105 0.2696 0.3836 0.043 Uiso 1 1 calc R . . H2B H -0.0022 0.0929 0.3492 0.043 Uiso 1 1 calc R . . C3 C 0.1554(2) 0.21259(19) 0.54719(18) 0.0359(4) Uani 1 1 d . . . H3A H 0.2675 0.2261 0.5522 0.043 Uiso 1 1 calc R . . H3B H 0.1012 0.1199 0.5642 0.043 Uiso 1 1 calc R . . C4 C 0.1839(2) 0.34808(18) 0.65039(17) 0.0326(4) Uani 1 1 d . . . H4A H 0.2375 0.4409 0.6334 0.039 Uiso 1 1 calc R . . H4B H 0.2626 0.3611 0.7387 0.039 Uiso 1 1 calc R . . C4A C 0.0122(2) 0.32372(17) 0.64586(16) 0.0286(4) Uani 1 1 d . . . C5A C -0.0888(2) 0.48158(17) 0.72844(16) 0.0287(4) Uani 1 1 d . . . C6 C -0.0817(2) 0.57026(18) 0.83845(17) 0.0341(4) Uani 1 1 d . . . H6A H 0.0169 0.6142 0.9213 0.041 Uiso 1 1 calc R . . C7 C -0.2211(2) 0.59421(19) 0.82619(18) 0.0375(4) Uani 1 1 d . . . H7A H -0.2176 0.6558 0.9007 0.045 Uiso 1 1 calc R . . C8 C -0.3651(2) 0.52812(19) 0.70511(19) 0.0379(4) Uani 1 1 d . . . H8A H -0.4606 0.5438 0.6971 0.045 Uiso 1 1 calc R . . C9A C -0.2317(2) 0.41539(17) 0.60482(16) 0.0297(4) Uani 1 1 d . . . C9 C -0.3702(2) 0.43926(18) 0.59581(18) 0.0349(4) Uani 1 1 d . . . H9A H -0.4698 0.3940 0.5135 0.042 Uiso 1 1 calc R . . C10A C -0.1141(2) 0.29662(17) 0.50859(16) 0.0285(4) Uani 1 1 d . . . C11 C -0.2287(2) 0.18278(19) 0.26931(17) 0.0380(4) Uani 1 1 d . . . H11A H -0.1640 0.2351 0.2259 0.046 Uiso 1 1 calc R . . H11B H -0.3081 0.2229 0.2732 0.046 Uiso 1 1 calc R . . C12 C -0.3327(2) 0.01554(18) 0.18743(16) 0.0325(4) Uani 1 1 d . . . C13 C -0.3388(2) -0.0412(2) 0.06627(18) 0.0408(4) Uani 1 1 d . . . H13A H -0.2714 0.0252 0.0364 0.049 Uiso 1 1 calc R . . C14 C -0.4423(2) -0.1940(2) -0.01174(19) 0.0465(5) Uani 1 1 d . . . H14A H -0.4450 -0.2313 -0.0944 0.056 Uiso 1 1 calc R . . C15 C -0.5409(3) -0.2917(2) 0.0297(2) 0.0535(5) Uani 1 1 d . . . H15A H -0.6123 -0.3961 -0.0240 0.064 Uiso 1 1 calc R . . C17 C -0.4319(3) -0.0848(2) 0.22785(19) 0.0475(5) Uani 1 1 d . . . H17A H -0.4287 -0.0485 0.3109 0.057 Uiso 1 1 calc R . . C18 C -0.0687(2) 0.19545(17) 0.69044(15) 0.0283(4) Uani 1 1 d . . . C19 C -0.2374(2) 0.07990(18) 0.61693(17) 0.0331(4) Uani 1 1 d . . . H19A H -0.3066 0.0778 0.5346 0.040 Uiso 1 1 calc R . . C20 C -0.3070(2) -0.03294(19) 0.66164(18) 0.0369(4) Uani 1 1 d . . . H20A H -0.4227 -0.1115 0.6098 0.044 Uiso 1 1 calc R . . C21 C -0.2085(2) -0.03080(19) 0.78072(18) 0.0393(4) Uani 1 1 d . . . H21A H -0.2556 -0.1077 0.8116 0.047 Uiso 1 1 calc R . . C22 C -0.0407(3) 0.0839(2) 0.85522(19) 0.0467(5) Uani 1 1 d . . . H22A H 0.0277 0.0857 0.9377 0.056 Uiso 1 1 calc R . . C23 C 0.0290(2) 0.1965(2) 0.81079(18) 0.0415(4) Uani 1 1 d . . . H23A H 0.1446 0.2749 0.8632 0.050 Uiso 1 1 calc R . . C16 C -0.5351(3) -0.2364(2) 0.1502(2) 0.0619(6) Uani 1 1 d . . . H16A H -0.6026 -0.3031 0.1799 0.074 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 O5 0.0267(6) 0.0254(6) 0.0337(6) 0.0067(5) 0.0109(5) 0.0114(5) N1 0.0342(8) 0.0293(7) 0.0308(8) 0.0098(6) 0.0153(6) 0.0146(6) N10 0.0301(7) 0.0283(7) 0.0321(7) 0.0124(6) 0.0128(6) 0.0137(6) C2 0.0379(10) 0.0300(9) 0.0438(10) 0.0123(8) 0.0244(9) 0.0148(8) C3 0.0319(9) 0.0316(9) 0.0461(11) 0.0126(8) 0.0208(8) 0.0153(8) C4 0.0268(9) 0.0289(8) 0.0385(10) 0.0107(7) 0.0140(7) 0.0119(7) C4A 0.0291(9) 0.0233(8) 0.0305(9) 0.0070(7) 0.0127(7) 0.0121(7) C5A 0.0271(8) 0.0243(8) 0.0360(9) 0.0130(7) 0.0148(7) 0.0122(7) C6 0.0360(9) 0.0271(8) 0.0354(9) 0.0104(7) 0.0162(8) 0.0123(7) C7 0.0414(10) 0.0307(9) 0.0447(10) 0.0124(8) 0.0257(9) 0.0168(8) C8 0.0339(9) 0.0330(9) 0.0524(11) 0.0165(8) 0.0236(9) 0.0174(8) C9A 0.0308(9) 0.0248(8) 0.0352(9) 0.0132(7) 0.0155(7) 0.0134(7) C9 0.0305(9) 0.0321(9) 0.0434(10) 0.0173(8) 0.0163(8) 0.0151(7) C10A 0.0281(8) 0.0230(8) 0.0306(9) 0.0100(7) 0.0131(7) 0.0087(7) C11 0.0494(11) 0.0327(9) 0.0290(9) 0.0124(7) 0.0159(8) 0.0182(8) C12 0.0326(9) 0.0314(9) 0.0321(9) 0.0116(7) 0.0133(7) 0.0153(7) C13 0.0394(10) 0.0399(10) 0.0379(10) 0.0096(8) 0.0196(8) 0.0149(8) C14 0.0427(11) 0.0448(11) 0.0385(10) 0.0009(9) 0.0111(9) 0.0219(9) C15 0.0472(12) 0.0323(10) 0.0501(13) 0.0070(9) 0.0018(10) 0.0121(9) C17 0.0488(12) 0.0440(11) 0.0379(11) 0.0151(9) 0.0202(9) 0.0110(9) C18 0.0297(8) 0.0263(8) 0.0301(9) 0.0091(7) 0.0135(7) 0.0152(7) C19 0.0295(9) 0.0326(9) 0.0339(9) 0.0126(7) 0.0121(7) 0.0138(7) C20 0.0347(10) 0.0307(9) 0.0430(10) 0.0132(8) 0.0188(8) 0.0127(8) C21 0.0478(11) 0.0310(9) 0.0434(11) 0.0178(8) 0.0248(9) 0.0173(8) C22 0.0507(12) 0.0434(11) 0.0352(10) 0.0203(9) 0.0118(9) 0.0166(9) C23 0.0365(10) 0.0379(10) 0.0349(10) 0.0140(8) 0.0083(8) 0.0103(8) C16 0.0579(14) 0.0439(12) 0.0543(14) 0.0212(11) 0.0176(11) 0.0024(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 O5 C5A 1.3739(19) . ? O5 C4A 1.4528(19) . ? N1 C10A 1.360(2) . ? N1 C2 1.469(2) . ? N1 C11 1.471(2) . ? N10 C10A 1.298(2) . ? N10 C9A 1.404(2) . ? C2 C3 1.509(3) . ? C3 C4 1.515(2) . ? C4 C4A 1.519(2) . ? C4A C10A 1.528(2) . ? C4A C18 1.536(2) . ? C5A C6 1.381(2) . ? C5A C9A 1.400(2) . ? C6 C7 1.391(2) . ? C7 C8 1.387(3) . ? C8 C9 1.386(3) . ? C9A C9 1.390(2) . ? C11 C12 1.509(3) . ? C12 C17 1.382(2) . ? C12 C13 1.387(2) . ? C13 C14 1.388(3) . ? C14 C15 1.373(3) . ? C15 C16 1.378(3) . ? C17 C16 1.378(3) . ? C18 C19 1.386(3) . ? C18 C23 1.387(2) . ? C19 C20 1.391(2) . ? C20 C21 1.373(3) . ? C21 C22 1.379(3) . ? C22 C23 1.387(3) . ? 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 C5A O5 C4A 114.14(13) . . ? C10A N1 C2 124.63(14) . . ? C10A N1 C11 119.99(14) . . ? C2 N1 C11 113.45(14) . . ? C10A N10 C9A 116.58(14) . . ? N1 C2 C3 113.78(14) . . ? C2 C3 C4 110.18(14) . . ? C3 C4 C4A 109.34(14) . . ? O5 C4A C4 104.35(13) . . ? O5 C4A C10A 108.93(12) . . ? C4 C4A C10A 110.77(13) . . ? O5 C4A C18 108.67(12) . . ? C4 C4A C18 113.59(13) . . ? C10A C4A C18 110.28(13) . . ? O5 C5A C6 119.32(15) . . ? O5 C5A C9A 118.47(14) . . ? C6 C5A C9A 122.06(15) . . ? C5A C6 C7 119.02(17) . . ? C8 C7 C6 119.99(16) . . ? C9 C8 C7 120.24(16) . . ? C9 C9A C5A 117.70(15) . . ? C9 C9A N10 120.17(16) . . ? C5A C9A N10 121.96(14) . . ? C8 C9 C9A 120.98(17) . . ? N10 C10A N1 120.81(15) . . ? N10 C10A C4A 121.77(14) . . ? N1 C10A C4A 117.21(14) . . ? N1 C11 C12 113.05(14) . . ? C17 C12 C13 117.94(17) . . ? C17 C12 C11 120.93(16) . . ? C13 C12 C11 121.05(16) . . ? C12 C13 C14 120.70(18) . . ? C15 C14 C13 120.46(19) . . ? C14 C15 C16 119.25(19) . . ? C16 C17 C12 121.39(19) . . ? C19 C18 C23 118.20(15) . . ? C19 C18 C4A 122.84(14) . . ? C23 C18 C4A 118.95(15) . . ? C18 C19 C20 121.15(16) . . ? C21 C20 C19 119.99(17) . . ? C20 C21 C22 119.51(16) . . ? C21 C22 C23 120.60(18) . . ? C22 C23 C18 120.55(18) . . ? C17 C16 C15 120.3(2) . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 24.87 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.168 _refine_diff_density_min -0.214 _refine_diff_density_rms 0.042 #===END