# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2003 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 loop_ _publ_author_name 'Ronald Grigg' 'Lixin Zhang' 'Simon Collard' 'Ann Keep' _publ_contact_author_name 'Prof. Ronald Grigg' _publ_contact_author_address ; Department of Chemistry MIDAS centre University of Leeds Leeds LS2 9JT UNITED KINGDOM ; _publ_contact_author_email R.Grigg@chem.leeds.ac.uk _publ_section_title ; Palladium catalysed [2+2+1] intramolecular cycloaddition for the preparation of bicyclo[3.3.0] octa-1.5-diene-3-ones from 1,6-diynes ; data_z122 _database_code_CSD 206592 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H12 O5' _chemical_formula_weight 236.22 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 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 5.70010(10) _cell_length_b 9.0939(3) _cell_length_c 11.3003(4) _cell_angle_alpha 77.7220(13) _cell_angle_beta 75.5740(13) _cell_angle_gamma 82.5810(19) _cell_volume 552.52(3) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needle _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.42 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 248 _exptl_absorpt_coefficient_mu 0.111 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.978 _exptl_absorpt_correction_T_max 0.9967 _exptl_absorpt_process_details ; ? ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_probe ? _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Fine-focus Sealed tube' _diffrn_radiation_collimation ? _diffrn_radiation_polarisn_norm ? _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius KappaCCD area-detector diffractometer' _diffrn_radiation_detector 'CCD plate' _diffrn_measurement_method 'phi-omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 'not measured' _diffrn_reflns_number 8959 _diffrn_reflns_av_R_equivalents 0.0531 _diffrn_reflns_av_sigmaI/netI 0.0477 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.89 _diffrn_reflns_theta_max 25.99 _reflns_number_total 2146 _reflns_number_gt 1760 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'DENZO-SMN and COLLECT (Otwinowski & Minor, 1996)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_data_reduction 'DENZO-SMN and COLLECT (Otwinowski & Minor, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1986)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1999)' _computing_molecular_graphics ORTEX _computing_publication_material 'WinCIF (Thornton-Pett, 2000)' _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^)+(0.0726P)^2^+0.1195P] 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 Shelxl _refine_ls_extinction_coef 0.10(2) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2146 _refine_ls_number_parameters 203 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0606 _refine_ls_R_factor_gt 0.0429 _refine_ls_wR_factor_ref 0.1451 _refine_ls_wR_factor_gt 0.1133 _refine_ls_goodness_of_fit_ref 1.23 _refine_ls_restrained_S_all 1.23 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 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 0.1782(4) 0.7234(2) 0.20137(19) 0.0236(5) Uani 1 1 d . . . C2 C 0.3168(4) 0.8052(2) 0.07620(19) 0.0251(5) Uani 1 1 d . . . H2 H 0.468(5) 0.849(3) 0.070(2) 0.028(6) Uiso 1 1 d . . . C3 C 0.2121(4) 0.7948(2) -0.0152(2) 0.0248(5) Uani 1 1 d . . . C4 C -0.0058(4) 0.7131(2) 0.0342(2) 0.0252(5) Uani 1 1 d . . . C5 C -0.0562(4) 0.6802(3) 0.1735(2) 0.0255(5) Uani 1 1 d . . . H5A H -0.193(5) 0.741(3) 0.209(3) 0.040(7) Uiso 1 1 d . . . H5B H -0.088(4) 0.576(3) 0.209(2) 0.029(6) Uiso 1 1 d . . . C6 C 0.2582(4) 0.8293(3) -0.1537(2) 0.0293(5) Uani 1 1 d . . . H5 H 0.244(5) 0.939(3) -0.193(3) 0.041(7) Uiso 1 1 d . . . H6 H 0.417(5) 0.790(3) -0.195(2) 0.037(7) Uiso 1 1 d . . . C7 C 0.0557(4) 0.7512(2) -0.1778(2) 0.0293(5) Uani 1 1 d . . . C8 C -0.0987(4) 0.6865(3) -0.0569(2) 0.0281(5) Uani 1 1 d . . . H8 H -0.235(6) 0.634(4) -0.048(3) 0.051(8) Uiso 1 1 d . . . C9 C 0.3230(4) 0.5770(2) 0.24660(19) 0.0237(5) Uani 1 1 d . . . C10 C 0.3547(5) 0.3888(3) 0.4235(2) 0.0367(6) Uani 1 1 d . . . H10B H 0.303(5) 0.378(3) 0.509(3) 0.047(8) Uiso 1 1 d . . . H10A H 0.289(6) 0.300(4) 0.402(3) 0.056(9) Uiso 1 1 d . . . H10C H 0.530(6) 0.377(4) 0.403(3) 0.058(9) Uiso 1 1 d . . . C11 C 0.1259(4) 0.8227(2) 0.29959(19) 0.0236(5) Uani 1 1 d . . . C12 C 0.3137(4) 0.9428(3) 0.4137(2) 0.0298(5) Uani 1 1 d . . . H12C H 0.228(5) 0.889(3) 0.495(3) 0.036(7) Uiso 1 1 d . . . H12B H 0.479(5) 0.960(3) 0.414(2) 0.035(7) Uiso 1 1 d . . . H12A H 0.217(5) 1.038(3) 0.394(3) 0.037(7) Uiso 1 1 d . . . O1 O 0.0319(3) 0.7432(2) -0.28094(15) 0.0400(5) Uani 1 1 d . . . O2 O 0.2479(3) 0.53316(17) 0.36940(14) 0.0314(4) Uani 1 1 d . . . O3 O 0.4746(3) 0.50812(17) 0.17970(15) 0.0319(4) Uani 1 1 d . . . O4 O 0.3354(3) 0.85639(17) 0.31650(14) 0.0280(4) Uani 1 1 d . . . O5 O -0.0726(3) 0.86641(17) 0.35330(14) 0.0295(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 0.0225(10) 0.0252(11) 0.0231(11) -0.0051(8) -0.0048(8) -0.0028(8) C2 0.0219(10) 0.0252(10) 0.0266(11) -0.0045(9) -0.0031(8) -0.0017(8) C3 0.0257(10) 0.0212(10) 0.0261(11) -0.0038(8) -0.0049(8) 0.0003(8) C4 0.0240(10) 0.0229(10) 0.0277(11) -0.0056(8) -0.0059(8) 0.0028(8) C5 0.0221(10) 0.0299(12) 0.0255(11) -0.0064(9) -0.0057(8) -0.0028(9) C6 0.0338(12) 0.0278(12) 0.0246(11) -0.0015(9) -0.0064(9) -0.0021(9) C7 0.0337(11) 0.0266(11) 0.0286(12) -0.0050(9) -0.0122(9) 0.0033(9) C8 0.0274(11) 0.0302(11) 0.0288(12) -0.0082(9) -0.0087(9) -0.0006(9) C9 0.0241(10) 0.0238(10) 0.0245(11) -0.0055(8) -0.0060(8) -0.0041(8) C10 0.0483(15) 0.0278(12) 0.0319(14) 0.0033(10) -0.0136(11) -0.0007(10) C11 0.0250(10) 0.0219(10) 0.0233(11) -0.0014(8) -0.0072(8) -0.0019(8) C12 0.0305(12) 0.0333(12) 0.0298(13) -0.0134(10) -0.0077(9) -0.0042(10) O1 0.0487(10) 0.0469(11) 0.0277(9) -0.0067(7) -0.0152(7) -0.0036(8) O2 0.0380(9) 0.0273(8) 0.0252(8) -0.0016(6) -0.0058(6) 0.0021(7) O3 0.0313(8) 0.0295(8) 0.0321(9) -0.0075(7) -0.0031(7) 0.0021(7) O4 0.0243(8) 0.0337(8) 0.0294(8) -0.0136(7) -0.0061(6) -0.0023(6) O5 0.0241(8) 0.0315(8) 0.0329(9) -0.0108(7) -0.0048(6) 0.0022(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 C1 C2 1.525(3) . ? C1 C11 1.526(3) . ? C1 C9 1.533(3) . ? C1 C5 1.561(3) . ? C2 C3 1.340(3) . ? C2 H2 0.98(3) . ? C3 C4 1.457(3) . ? C3 C6 1.491(3) . ? C4 C8 1.346(3) . ? C4 C5 1.498(3) . ? C5 H5A 0.95(3) . ? C5 H5B 0.97(3) . ? C6 C7 1.536(3) . ? C6 H5 1.00(3) . ? C6 H6 0.97(3) . ? C7 O1 1.225(3) . ? C7 C8 1.476(3) . ? C8 H8 0.94(3) . ? C9 O3 1.203(3) . ? C9 O2 1.334(3) . ? C10 O2 1.451(3) . ? C10 H10B 0.93(3) . ? C10 H10A 1.03(3) . ? C10 H10C 0.96(3) . ? C11 O5 1.204(3) . ? C11 O4 1.337(2) . ? C12 O4 1.454(3) . ? C12 H12C 0.98(3) . ? C12 H12B 0.98(3) . ? C12 H12A 0.98(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 C11 111.22(17) . . ? C2 C1 C9 110.70(16) . . ? C11 C1 C9 108.95(16) . . ? C2 C1 C5 104.43(16) . . ? C11 C1 C5 113.39(17) . . ? C9 C1 C5 108.05(16) . . ? C3 C2 C1 110.76(18) . . ? C3 C2 H2 128.7(14) . . ? C1 C2 H2 120.4(14) . . ? C2 C3 C4 110.86(19) . . ? C2 C3 C6 140.0(2) . . ? C4 C3 C6 108.91(18) . . ? C8 C4 C3 111.87(19) . . ? C8 C4 C5 138.8(2) . . ? C3 C4 C5 109.35(17) . . ? C4 C5 C1 103.37(17) . . ? C4 C5 H5A 111.7(17) . . ? C1 C5 H5A 109.7(16) . . ? C4 C5 H5B 113.2(15) . . ? C1 C5 H5B 112.0(14) . . ? H5A C5 H5B 107(2) . . ? C3 C6 C7 102.09(18) . . ? C3 C6 H5 116.1(16) . . ? C7 C6 H5 108.5(16) . . ? C3 C6 H6 114.0(15) . . ? C7 C6 H6 110.8(16) . . ? H5 C6 H6 105(2) . . ? O1 C7 C8 126.5(2) . . ? O1 C7 C6 124.8(2) . . ? C8 C7 C6 108.64(18) . . ? C4 C8 C7 108.37(19) . . ? C4 C8 H8 127.6(19) . . ? C7 C8 H8 124.0(19) . . ? O3 C9 O2 125.01(19) . . ? O3 C9 C1 124.54(19) . . ? O2 C9 C1 110.37(17) . . ? O2 C10 H10B 107.7(19) . . ? O2 C10 H10A 111.7(17) . . ? H10B C10 H10A 105(3) . . ? O2 C10 H10C 115(2) . . ? H10B C10 H10C 108(3) . . ? H10A C10 H10C 109(3) . . ? O5 C11 O4 124.59(19) . . ? O5 C11 C1 125.79(18) . . ? O4 C11 C1 109.62(17) . . ? O4 C12 H12C 111.0(16) . . ? O4 C12 H12B 106.6(15) . . ? H12C C12 H12B 112(2) . . ? O4 C12 H12A 108.9(15) . . ? H12C C12 H12A 107(2) . . ? H12B C12 H12A 112(2) . . ? C9 O2 C10 116.29(18) . . ? C11 O4 C12 115.71(16) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.99 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.336 _refine_diff_density_min -0.291 _refine_diff_density_rms 0.09