Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _publ_contact_author_email declan.gilheany@ucd.ie _publ_contact_author_name 'Dr Declan Gilheany' _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_address ; Chemistry University College Dublin The Centre for Synthesis and Chemic University College Dublin Belfield Dublin County Dublin Dublin 4 REPUBLIC OF IRELAND ; _publ_contact_author_phone 0035317162308 _publ_contact_author_fax 0035317062127 _publ_section_title ; A novel azulene synthesis from the Ramirez ylide involving two different modes of its reaction with activated alkynes. ; loop_ _publ_author_name 'Declan Gilheany' 'David M. Corr' 'Lee J. Higham' 'P Gabriel Kelly' 'Helge Muller-Bunz' ; B.Walker ; data_gil05 _database_code_depnum_ccdc_archive 'CCDC 225162' _chemical_name_common 1,5,6-tricarbomethoxy-3-methoxyazulene _audit_creation_method SHELXL-97 _chemical_name_systematic 1,5,6-tricarbomethoxy-3-methoxyazulene _chemical_melting_point 422 _chemical_formula_moiety ? _chemical_formula_sum 'C17 H16 O7' _chemical_formula_weight 332.30 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 orthorhombic _symmetry_space_group_name_H-M Pna21 _symmetry_Int_Tables_number 33 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x+1/2, -y+1/2, z' '-x+1/2, y+1/2, z+1/2' _cell_length_a 7.3017(7) _cell_length_b 19.2542(18) _cell_length_c 11.0940(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1559.7(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.77 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.415 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 696 _exptl_absorpt_coefficient_mu 0.111 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_min 0.9194 _exptl_absorpt_correction_T_max 0.9945 _exptl_absorpt_process_details SADBAS _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_source 'fine-focus sealed tube' _diffrn_radiation_type MoK\a _diffrn_radiation_probe x-ray _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10842 _diffrn_reflns_av_R_equivalents 0.0195 _diffrn_reflns_av_sigmaI/netI 0.0187 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -23 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.12 _diffrn_reflns_theta_max 26.64 _reflns_number_total 3019 _reflns_number_gt 2797 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _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^)+(0.0434P)^2^+0.2371P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.3(9) _refine_ls_number_reflns 3019 _refine_ls_number_parameters 281 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0418 _refine_ls_R_factor_gt 0.0376 _refine_ls_wR_factor_ref 0.0907 _refine_ls_wR_factor_gt 0.0887 _refine_ls_goodness_of_fit_ref 1.135 _refine_ls_restrained_S_all 1.135 _refine_ls_shift/su_max 0.007 _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 C1 C 0.4775(3) 0.67379(10) 0.31192(19) 0.0374(4) Uani 1 1 d . . . C11 C 0.4902(3) 0.59831(11) 0.29396(19) 0.0414(5) Uani 1 1 d . . . O1 O 0.5383(3) 0.55640(9) 0.36771(16) 0.0684(6) Uani 1 1 d . . . O2 O 0.4423(3) 0.58045(8) 0.18160(13) 0.0550(5) Uani 1 1 d . . . C12 C 0.4611(6) 0.50856(15) 0.1502(3) 0.0667(8) Uani 1 1 d . . . H12A H 0.401(5) 0.499(2) 0.083(5) 0.112(14) Uiso 1 1 d . . . H12B H 0.592(6) 0.499(2) 0.133(4) 0.108(13) Uiso 1 1 d . . . H12C H 0.409(5) 0.485(2) 0.214(4) 0.117(14) Uiso 1 1 d . . . C2 C 0.4311(3) 0.72168(11) 0.22286(19) 0.0382(5) Uani 1 1 d . . . H2 H 0.391(3) 0.7114(11) 0.146(2) 0.042(6) Uiso 1 1 d . . . C3 C 0.4457(3) 0.78840(10) 0.26935(18) 0.0373(5) Uani 1 1 d . . . O3 O 0.4137(3) 0.85004(8) 0.21558(14) 0.0516(4) Uani 1 1 d . . . C13 C 0.3722(5) 0.84812(15) 0.0904(2) 0.0578(7) Uani 1 1 d . . . H13A H 0.348(4) 0.8960(16) 0.075(3) 0.073(8) Uiso 1 1 d . . . H13B H 0.252(4) 0.8199(15) 0.077(3) 0.080(9) Uiso 1 1 d . . . H13C H 0.474(4) 0.8282(15) 0.046(3) 0.064(8) Uiso 1 1 d . . . C4 C 0.5191(3) 0.84142(10) 0.46595(18) 0.0355(4) Uani 1 1 d . . . H4 H 0.491(3) 0.8866(11) 0.4283(19) 0.027(5) Uiso 1 1 d . . . C5 C 0.5667(3) 0.84446(10) 0.58750(18) 0.0356(4) Uani 1 1 d . . . C14 C 0.5477(3) 0.91579(11) 0.6398(2) 0.0432(5) Uani 1 1 d . . . O4 O 0.5878(3) 0.96814(8) 0.58789(16) 0.0705(6) Uani 1 1 d . . . O5 O 0.4720(2) 0.91463(8) 0.74892(15) 0.0526(4) Uani 1 1 d . . . C15 C 0.4705(6) 0.98053(17) 0.8136(3) 0.0724(9) Uani 1 1 d . . . H15A H 0.596(6) 0.995(2) 0.831(4) 0.127(16) Uiso 1 1 d . . . H15B H 0.387(6) 0.974(2) 0.885(5) 0.130(15) Uiso 1 1 d . . . H15C H 0.431(3) 1.0163(15) 0.760(3) 0.061(8) Uiso 1 1 d . . . C6 C 0.6240(3) 0.78842(10) 0.66051(18) 0.0348(4) Uani 1 1 d . . . C16 C 0.7005(3) 0.80352(10) 0.78537(19) 0.0391(4) Uani 1 1 d . . . O6 O 0.6688(3) 0.76969(9) 0.87208(14) 0.0602(5) Uani 1 1 d . . . O7 O 0.8151(2) 0.85745(7) 0.78294(13) 0.0458(4) Uani 1 1 d . . . C17 C 0.8945(4) 0.87539(16) 0.8987(2) 0.0595(7) Uani 1 1 d . . . H17A H 0.790(5) 0.8805(18) 0.966(3) 0.102(11) Uiso 1 1 d . . . H17B H 0.979(5) 0.8366(17) 0.919(3) 0.086(11) Uiso 1 1 d . . . H17C H 0.954(5) 0.9219(19) 0.886(3) 0.099(11) Uiso 1 1 d . . . C7 C 0.6269(3) 0.71865(10) 0.63298(18) 0.0366(4) Uani 1 1 d . . . H7 H 0.664(3) 0.6911(10) 0.6965(18) 0.027(5) Uiso 1 1 d . . . C8 C 0.5765(3) 0.68306(11) 0.52751(19) 0.0370(4) Uani 1 1 d . . . H8 H 0.589(3) 0.6320(12) 0.535(2) 0.042(6) Uiso 1 1 d . . . C9 C 0.5219(3) 0.70965(10) 0.41921(18) 0.0336(4) Uani 1 1 d . . . C10 C 0.5005(3) 0.78506(10) 0.39054(17) 0.0329(4) Uani 1 1 d . . . 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 C1 0.0422(11) 0.0356(11) 0.0344(10) -0.0044(8) 0.0013(9) 0.0005(8) C11 0.0584(12) 0.0328(11) 0.0330(11) -0.0013(9) 0.0005(10) -0.0006(9) O1 0.1288(17) 0.0363(9) 0.0402(9) -0.0012(8) -0.0131(10) 0.0062(9) O2 0.0934(13) 0.0332(8) 0.0383(9) -0.0090(7) -0.0131(9) 0.0043(8) C12 0.114(3) 0.0381(14) 0.0482(16) -0.0118(13) -0.0026(18) 0.0029(15) C2 0.0469(12) 0.0389(11) 0.0289(10) -0.0045(9) -0.0031(9) 0.0018(9) C3 0.0467(11) 0.0321(10) 0.0330(10) 0.0003(9) 0.0016(9) 0.0037(8) O3 0.0855(12) 0.0358(8) 0.0336(8) 0.0008(6) -0.0074(7) 0.0058(8) C13 0.091(2) 0.0495(16) 0.0326(12) 0.0077(11) -0.0018(13) 0.0121(15) C4 0.0424(11) 0.0304(11) 0.0336(10) 0.0031(8) 0.0019(9) 0.0013(8) C5 0.0397(10) 0.0352(11) 0.0318(10) -0.0030(8) 0.0012(8) -0.0020(8) C14 0.0596(13) 0.0340(11) 0.0359(11) -0.0015(9) -0.0086(11) -0.0009(10) O4 0.1337(18) 0.0316(9) 0.0463(10) 0.0005(8) -0.0060(11) -0.0091(10) O5 0.0757(11) 0.0394(8) 0.0428(9) -0.0101(7) 0.0074(8) 0.0074(7) C15 0.108(3) 0.0489(17) 0.0606(18) -0.0215(15) -0.0029(19) 0.0164(17) C6 0.0385(10) 0.0370(11) 0.0290(9) -0.0007(8) 0.0042(8) -0.0019(8) C16 0.0512(12) 0.0350(9) 0.0310(10) -0.0020(9) 0.0024(9) 0.0026(9) O6 0.0967(14) 0.0523(9) 0.0317(8) 0.0050(7) -0.0023(9) -0.0147(9) O7 0.0607(9) 0.0450(8) 0.0316(7) -0.0013(7) -0.0080(7) -0.0074(7) C17 0.0802(19) 0.0536(16) 0.0448(15) -0.0078(12) -0.0207(13) -0.0073(14) C7 0.0446(11) 0.0357(11) 0.0295(10) 0.0038(8) 0.0001(9) 0.0040(9) C8 0.0447(11) 0.0294(10) 0.0370(10) -0.0005(9) 0.0019(8) 0.0016(9) C9 0.0350(10) 0.0313(10) 0.0345(10) -0.0045(9) 0.0040(8) 0.0016(8) C10 0.0351(10) 0.0328(10) 0.0309(10) 0.0015(8) 0.0027(8) 0.0007(7) _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 C1 C2 1.393(3) . ? C1 C9 1.414(3) . ? C1 C11 1.470(3) . ? C11 O1 1.202(3) . ? C11 O2 1.339(3) . ? O2 C12 1.434(3) . ? C12 H12A 0.89(5) . ? C12 H12B 0.99(4) . ? C12 H12C 0.92(5) . ? C2 C3 1.388(3) . ? C2 H2 0.92(3) . ? C3 O3 1.349(2) . ? C3 C10 1.404(3) . ? O3 C13 1.422(3) . ? C13 H13A 0.95(3) . ? C13 H13B 1.04(3) . ? C13 H13C 0.97(3) . ? C4 C10 1.377(3) . ? C4 C5 1.394(3) . ? C4 H4 0.99(2) . ? C5 C6 1.413(3) . ? C5 C14 1.497(3) . ? C14 O4 1.197(3) . ? C14 O5 1.331(3) . ? O5 C15 1.458(3) . ? C15 H15A 0.98(4) . ? C15 H15B 1.01(5) . ? C15 H15C 0.95(3) . ? C6 C7 1.378(3) . ? C6 C16 1.522(3) . ? C16 O6 1.185(3) . ? C16 O7 1.334(2) . ? O7 C17 1.451(3) . ? C17 H17A 1.08(4) . ? C17 H17B 0.99(3) . ? C17 H17C 1.00(4) . ? C7 C8 1.405(3) . ? C7 H7 0.92(2) . ? C8 C9 1.366(3) . ? C8 H8 0.99(2) . ? C9 C10 1.495(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 C2 C1 C9 109.25(18) . . ? C2 C1 C11 124.99(19) . . ? C9 C1 C11 125.64(19) . . ? O1 C11 O2 122.50(19) . . ? O1 C11 C1 126.2(2) . . ? O2 C11 C1 111.33(18) . . ? C11 O2 C12 116.7(2) . . ? O2 C12 H12A 112(3) . . ? O2 C12 H12B 109(2) . . ? H12A C12 H12B 106(3) . . ? O2 C12 H12C 104(3) . . ? H12A C12 H12C 109(3) . . ? H12B C12 H12C 117(3) . . ? C3 C2 C1 109.28(18) . . ? C3 C2 H2 124.5(14) . . ? C1 C2 H2 126.1(14) . . ? O3 C3 C2 129.54(18) . . ? O3 C3 C10 120.87(17) . . ? C2 C3 C10 109.59(17) . . ? C3 O3 C13 116.49(18) . . ? O3 C13 H13A 100.7(19) . . ? O3 C13 H13B 109.6(18) . . ? H13A C13 H13B 109(2) . . ? O3 C13 H13C 109.8(17) . . ? H13A C13 H13C 116(2) . . ? H13B C13 H13C 112(2) . . ? C10 C4 C5 130.20(18) . . ? C10 C4 H4 114.6(12) . . ? C5 C4 H4 115.1(12) . . ? C4 C5 C6 126.62(18) . . ? C4 C5 C14 112.96(18) . . ? C6 C5 C14 120.40(18) . . ? O4 C14 O5 123.6(2) . . ? O4 C14 C5 124.3(2) . . ? O5 C14 C5 112.04(18) . . ? C14 O5 C15 115.9(2) . . ? O5 C15 H15A 110(3) . . ? O5 C15 H15B 106(3) . . ? H15A C15 H15B 117(4) . . ? O5 C15 H15C 109.1(17) . . ? H15A C15 H15C 102(3) . . ? H15B C15 H15C 113(3) . . ? C7 C6 C5 128.48(18) . . ? C7 C6 C16 112.48(17) . . ? C5 C6 C16 119.00(17) . . ? O6 C16 O7 124.5(2) . . ? O6 C16 C6 124.22(18) . . ? O7 C16 C6 111.15(17) . . ? C16 O7 C17 114.74(19) . . ? O7 C17 H17A 111(2) . . ? O7 C17 H17B 106(2) . . ? H17A C17 H17B 111(3) . . ? O7 C17 H17C 105(2) . . ? H17A C17 H17C 109(3) . . ? H17B C17 H17C 116(3) . . ? C6 C7 C8 131.00(19) . . ? C6 C7 H7 113.3(12) . . ? C8 C7 H7 115.6(12) . . ? C9 C8 C7 128.78(19) . . ? C9 C8 H8 117.9(13) . . ? C7 C8 H8 113.2(13) . . ? C8 C9 C1 128.66(19) . . ? C8 C9 C10 125.60(17) . . ? C1 C9 C10 105.74(17) . . ? C4 C10 C3 125.01(18) . . ? C4 C10 C9 128.76(17) . . ? C3 C10 C9 106.15(16) . . ? 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 C2 C1 C11 O1 176.2(2) . . . . ? C9 C1 C11 O1 0.7(4) . . . . ? C2 C1 C11 O2 -3.0(3) . . . . ? C9 C1 C11 O2 -178.6(2) . . . . ? O1 C11 O2 C12 -3.5(4) . . . . ? C1 C11 O2 C12 175.8(2) . . . . ? C9 C1 C2 C3 0.5(3) . . . . ? C11 C1 C2 C3 -175.7(2) . . . . ? C1 C2 C3 O3 -179.8(2) . . . . ? C1 C2 C3 C10 -0.6(3) . . . . ? C2 C3 O3 C13 -5.3(4) . . . . ? C10 C3 O3 C13 175.5(2) . . . . ? C10 C4 C5 C6 6.1(4) . . . . ? C10 C4 C5 C14 -172.5(2) . . . . ? C4 C5 C14 O4 -39.3(3) . . . . ? C6 C5 C14 O4 141.9(2) . . . . ? C4 C5 C14 O5 137.54(19) . . . . ? C6 C5 C14 O5 -41.2(3) . . . . ? O4 C14 O5 C15 -11.1(4) . . . . ? C5 C14 O5 C15 172.1(2) . . . . ? C4 C5 C6 C7 -7.7(4) . . . . ? C14 C5 C6 C7 170.9(2) . . . . ? C4 C5 C6 C16 169.9(2) . . . . ? C14 C5 C6 C16 -11.5(3) . . . . ? C7 C6 C16 O6 -42.0(3) . . . . ? C5 C6 C16 O6 140.1(2) . . . . ? C7 C6 C16 O7 134.78(18) . . . . ? C5 C6 C16 O7 -43.1(2) . . . . ? O6 C16 O7 C17 -3.3(3) . . . . ? C6 C16 O7 C17 -180.0(2) . . . . ? C5 C6 C7 C8 0.4(4) . . . . ? C16 C6 C7 C8 -177.3(2) . . . . ? C6 C7 C8 C9 5.1(4) . . . . ? C7 C8 C9 C1 177.5(2) . . . . ? C7 C8 C9 C10 -1.3(4) . . . . ? C2 C1 C9 C8 -179.2(2) . . . . ? C11 C1 C9 C8 -3.1(4) . . . . ? C2 C1 C9 C10 -0.3(2) . . . . ? C11 C1 C9 C10 175.89(19) . . . . ? C5 C4 C10 C3 177.8(2) . . . . ? C5 C4 C10 C9 1.7(4) . . . . ? O3 C3 C10 C4 2.9(3) . . . . ? C2 C3 C10 C4 -176.4(2) . . . . ? O3 C3 C10 C9 179.74(18) . . . . ? C2 C3 C10 C9 0.4(2) . . . . ? C8 C9 C10 C4 -4.4(3) . . . . ? C1 C9 C10 C4 176.6(2) . . . . ? C8 C9 C10 C3 179.0(2) . . . . ? C1 C9 C10 C3 -0.1(2) . . . . ? _diffrn_measured_fraction_theta_max 0.958 _diffrn_reflns_theta_full 26.64 _diffrn_measured_fraction_theta_full 0.958 _refine_diff_density_max 0.188 _refine_diff_density_min -0.162 _refine_diff_density_rms 0.037 _ccdc_chemical_compound_source_recrystallisation methanol