# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2003 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 loop_ _publ_author_name 'Roger Hunter' 'Philip Richards' _publ_contact_author_name 'Prof Roger Hunter' _publ_contact_author_address ; Chemistry University of Cape Town Rondebosch 7701 Cape Town South Africa 7701 SOUTH AFRICA ; _publ_contact_author_email ROGER@SCIENCE.UCT.AC.ZA _publ_section_title ; Stereoselective tetrapyrido[2,1-a]isoindolone synthesis via carbanionic and radical intermediates: a model study for the Tacaman alkaloid D/E ring fusion ; data_compound1 _database_code_CSD 208077 _audit_creation_method SHELXL-97 _chemical_name_systematic ; (3aS,11bS,11cR)-3a,4,5,11c-Tetrahydro-10b-hydroxy-furo-[3’,2’ :3,4] pyrido[2,1-a]isoindol-2(1H),7(11bH)-dione ; _chemical_name_common ; (3aS,11bS,11cR)-3a,4,5,11c-Tetrahydro-10b-hydroxy-furo-(3’,2’ :3,4) pyrido(2,1-a)isoindol-2(1H),7(11bH)-dione ; _chemical_melting_point 'Mp decomposes >140C' _chemical_formula_moiety 'C14 H13 N1 O4' _chemical_formula_sum 'C14 H13 N1 O4' _chemical_formula_weight 259.08 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) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 8.375(1) _cell_length_b 7.653(1) _cell_length_c 9.691(1) _cell_angle_alpha 90.00 _cell_angle_beta 100.634(1) _cell_angle_gamma 90.00 _cell_volume 610.5(1) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.37 _exptl_crystal_size_mid 0.31 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.410 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 272 _exptl_absorpt_coefficient_mu 0.104 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.9624 _exptl_absorpt_correction_T_max 0.9774 _exptl_absorpt_process_details none _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(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 'NOnius Kappa CCD' _diffrn_measurement_method 'phi- and omega-scans' _diffrn_reflns_number 3358 _diffrn_reflns_av_R_equivalents 0.0144 _diffrn_reflns_av_sigmaI/netI 0.0301 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.14 _diffrn_reflns_theta_max 27.39 _reflns_number_total 2511 _reflns_number_gt 2318 _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^)+(0.0294P)^2^+0.1067P] 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 0.033(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.5(8) _refine_ls_number_reflns 2511 _refine_ls_number_parameters 174 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0338 _refine_ls_R_factor_gt 0.0291 _refine_ls_wR_factor_ref 0.0701 _refine_ls_wR_factor_gt 0.0675 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.031 _refine_ls_shift/su_max 0.280 _refine_ls_shift/su_mean 0.018 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 O19 O 0.38396(12) 0.71322(16) 0.93832(10) 0.0339(3) Uani 1 1 d . . . N7 N 0.52683(13) 0.65221(17) 1.15833(11) 0.0239(3) Uani 1 1 d . . . O18 O 0.68166(14) 0.42506(14) 1.28450(10) 0.0312(3) Uani 1 1 d . . . H18 H 0.6530 0.3533 1.2190 0.037 Uiso 1 1 calc R . . O3 O 0.69548(13) 0.89596(16) 1.53018(10) 0.0360(3) Uani 1 1 d . . . O17 O 0.86798(14) 1.11327(18) 1.51510(13) 0.0452(3) Uani 1 1 d . . . C10 C 0.51182(17) 0.6788(2) 1.01929(13) 0.0238(3) Uani 1 1 d . . . C9 C 0.75368(17) 0.7093(2) 1.35448(13) 0.0249(3) Uani 1 1 d . . . H9 H 0.8436 0.6441 1.4154 0.030 Uiso 1 1 calc R . . C12 C 0.72814(19) 0.6792(2) 0.85966(15) 0.0305(3) Uani 1 1 d . . . H12 H 0.6555 0.7160 0.7776 0.037 Uiso 1 1 calc R . . C11 C 0.67622(16) 0.6558(2) 0.98597(13) 0.0244(3) Uani 1 1 d . . . C6 C 0.39949(16) 0.6776(2) 1.24073(14) 0.0287(3) Uani 1 1 d . . . H6A H 0.3721 0.5648 1.2805 0.034 Uiso 1 1 calc R . . H6B H 0.3004 0.7242 1.1803 0.034 Uiso 1 1 calc R . . C16 C 0.78121(16) 0.6052(2) 1.10711(14) 0.0252(3) Uani 1 1 d . . . C4 C 0.62445(18) 0.7495(2) 1.44327(14) 0.0287(3) Uani 1 1 d . . . H4 H 0.6100 0.6469 1.5037 0.034 Uiso 1 1 calc R . . C13 C 0.8912(2) 0.6466(2) 0.85798(16) 0.0381(4) Uani 1 1 d . . . H13 H 0.9313 0.6614 0.7732 0.046 Uiso 1 1 calc R . . C15 C 0.94267(18) 0.5718(2) 1.10538(16) 0.0341(4) Uani 1 1 d . . . H15 H 1.0151 0.5358 1.1878 0.041 Uiso 1 1 calc R . . C2 C 0.80182(18) 0.9833(2) 1.46423(17) 0.0328(4) Uani 1 1 d . . . C5 C 0.46109(18) 0.8059(2) 1.35837(16) 0.0311(3) Uani 1 1 d . . . H5A H 0.3808 0.8146 1.4213 0.037 Uiso 1 1 calc R . . H5B H 0.4722 0.9230 1.3178 0.037 Uiso 1 1 calc R . . C1 C 0.81696(18) 0.8905(2) 1.32983(15) 0.0296(3) Uani 1 1 d . . . H1A H 0.9313 0.8863 1.3166 0.036 Uiso 1 1 calc R . . H1B H 0.7496 0.9473 1.2473 0.036 Uiso 1 1 calc R . . C8 C 0.68891(16) 0.5937(2) 1.22810(13) 0.0234(3) Uani 1 1 d . . . C14 C 0.9957(2) 0.5929(3) 0.97796(18) 0.0406(4) Uani 1 1 d . . . H14 H 1.1062 0.5698 0.9736 0.049 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 O19 0.0297(5) 0.0425(7) 0.0265(5) 0.0094(5) -0.0026(4) 0.0006(5) N7 0.0238(5) 0.0295(7) 0.0182(5) 0.0025(5) 0.0037(4) -0.0001(5) O18 0.0490(6) 0.0237(6) 0.0195(5) 0.0006(4) 0.0025(4) 0.0010(5) O3 0.0424(6) 0.0393(7) 0.0268(5) -0.0116(5) 0.0075(4) -0.0059(5) O17 0.0369(6) 0.0415(8) 0.0534(7) -0.0188(6) -0.0017(5) -0.0068(5) C10 0.0284(7) 0.0216(7) 0.0204(6) 0.0031(6) 0.0024(5) -0.0026(6) C9 0.0291(7) 0.0264(8) 0.0177(6) -0.0013(5) 0.0002(5) 0.0029(6) C12 0.0420(8) 0.0288(9) 0.0218(6) -0.0019(6) 0.0087(6) -0.0050(7) C11 0.0291(7) 0.0229(8) 0.0212(6) -0.0021(6) 0.0047(5) -0.0033(6) C6 0.0259(7) 0.0353(9) 0.0264(7) 0.0007(6) 0.0086(5) -0.0029(6) C16 0.0286(7) 0.0249(8) 0.0219(6) -0.0046(6) 0.0046(5) -0.0004(6) C4 0.0383(8) 0.0277(9) 0.0209(6) -0.0040(6) 0.0078(6) -0.0053(7) C13 0.0455(9) 0.0414(11) 0.0325(8) -0.0107(8) 0.0203(7) -0.0089(8) C15 0.0298(8) 0.0388(10) 0.0325(8) -0.0100(7) 0.0026(6) 0.0054(7) C2 0.0277(7) 0.0345(9) 0.0337(8) -0.0059(7) -0.0012(6) 0.0020(7) C5 0.0325(8) 0.0311(9) 0.0320(7) -0.0019(6) 0.0120(6) -0.0017(6) C1 0.0265(7) 0.0332(9) 0.0293(7) -0.0036(7) 0.0053(6) -0.0032(6) C8 0.0261(7) 0.0256(8) 0.0177(6) -0.0001(6) 0.0023(5) 0.0029(6) C14 0.0323(8) 0.0498(12) 0.0430(9) -0.0157(8) 0.0157(7) -0.0014(8) _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 O19 C10 1.2336(17) . ? N7 C10 1.3455(16) . ? N7 C6 1.4584(17) . ? N7 C8 1.4702(17) . ? O18 C8 1.4073(19) . ? O3 C2 1.363(2) . ? O3 C4 1.4611(18) . ? O17 C2 1.200(2) . ? C10 C11 1.482(2) . ? C9 C1 1.519(2) . ? C9 C8 1.5268(18) . ? C9 C4 1.533(2) . ? C12 C11 1.3842(19) . ? C12 C13 1.391(2) . ? C11 C16 1.3856(19) . ? C6 C5 1.521(2) . ? C16 C15 1.379(2) . ? C16 C8 1.5214(19) . ? C4 C5 1.523(2) . ? C13 C14 1.383(3) . ? C15 C14 1.397(2) . ? C2 C1 1.509(2) . ? 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 C10 N7 C6 125.84(11) . . ? C10 N7 C8 114.47(11) . . ? C6 N7 C8 119.68(10) . . ? C2 O3 C4 109.73(11) . . ? O19 C10 N7 125.38(13) . . ? O19 C10 C11 128.27(12) . . ? N7 C10 C11 106.35(11) . . ? C1 C9 C8 119.03(11) . . ? C1 C9 C4 102.00(12) . . ? C8 C9 C4 112.55(12) . . ? C11 C12 C13 117.15(14) . . ? C12 C11 C16 122.12(13) . . ? C12 C11 C10 129.31(13) . . ? C16 C11 C10 108.57(11) . . ? N7 C6 C5 108.38(11) . . ? C15 C16 C11 120.78(13) . . ? C15 C16 C8 129.59(13) . . ? C11 C16 C8 109.63(11) . . ? O3 C4 C5 108.87(13) . . ? O3 C4 C9 102.89(11) . . ? C5 C4 C9 114.24(12) . . ? C14 C13 C12 120.93(14) . . ? C16 C15 C14 117.51(14) . . ? O17 C2 O3 120.40(15) . . ? O17 C2 C1 129.72(16) . . ? O3 C2 C1 109.88(13) . . ? C6 C5 C4 111.62(13) . . ? C2 C1 C9 101.93(12) . . ? O18 C8 N7 110.83(12) . . ? O18 C8 C16 114.65(12) . . ? N7 C8 C16 100.67(10) . . ? O18 C8 C9 104.72(10) . . ? N7 C8 C9 110.71(11) . . ? C16 C8 C9 115.39(12) . . ? C13 C14 C15 121.49(15) . . ? 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 C6 N7 C10 O19 -7.1(3) . . . . ? C8 N7 C10 O19 173.41(16) . . . . ? C6 N7 C10 C11 173.72(14) . . . . ? C8 N7 C10 C11 -5.80(17) . . . . ? C13 C12 C11 C16 1.2(2) . . . . ? C13 C12 C11 C10 -179.50(16) . . . . ? O19 C10 C11 C12 5.1(3) . . . . ? N7 C10 C11 C12 -175.70(15) . . . . ? O19 C10 C11 C16 -175.50(16) . . . . ? N7 C10 C11 C16 3.68(17) . . . . ? C10 N7 C6 C5 -123.50(15) . . . . ? C8 N7 C6 C5 56.00(18) . . . . ? C12 C11 C16 C15 -1.6(2) . . . . ? C10 C11 C16 C15 178.93(14) . . . . ? C12 C11 C16 C8 179.05(13) . . . . ? C10 C11 C16 C8 -0.38(17) . . . . ? C2 O3 C4 C5 -96.32(14) . . . . ? C2 O3 C4 C9 25.24(15) . . . . ? C1 C9 C4 O3 -35.85(13) . . . . ? C8 C9 C4 O3 -164.56(11) . . . . ? C1 C9 C4 C5 81.98(15) . . . . ? C8 C9 C4 C5 -46.73(18) . . . . ? C11 C12 C13 C14 0.1(3) . . . . ? C11 C16 C15 C14 0.7(2) . . . . ? C8 C16 C15 C14 179.88(15) . . . . ? C4 O3 C2 O17 176.53(15) . . . . ? C4 O3 C2 C1 -3.87(17) . . . . ? N7 C6 C5 C4 -52.83(17) . . . . ? O3 C4 C5 C6 166.11(11) . . . . ? C9 C4 C5 C6 51.75(18) . . . . ? O17 C2 C1 C9 160.28(17) . . . . ? O3 C2 C1 C9 -19.27(15) . . . . ? C8 C9 C1 C2 157.53(12) . . . . ? C4 C9 C1 C2 33.04(13) . . . . ? C10 N7 C8 O18 -116.34(13) . . . . ? C6 N7 C8 O18 64.10(16) . . . . ? C10 N7 C8 C16 5.37(16) . . . . ? C6 N7 C8 C16 -174.19(13) . . . . ? C10 N7 C8 C9 127.90(13) . . . . ? C6 N7 C8 C9 -51.66(17) . . . . ? C15 C16 C8 O18 -63.0(2) . . . . ? C11 C16 C8 O18 116.26(14) . . . . ? C15 C16 C8 N7 178.05(16) . . . . ? C11 C16 C8 N7 -2.72(16) . . . . ? C15 C16 C8 C9 58.9(2) . . . . ? C11 C16 C8 C9 -121.92(14) . . . . ? C1 C9 C8 O18 164.85(12) . . . . ? C4 C9 C8 O18 -75.95(14) . . . . ? C1 C9 C8 N7 -75.65(15) . . . . ? C4 C9 C8 N7 43.54(16) . . . . ? C1 C9 C8 C16 37.84(18) . . . . ? C4 C9 C8 C16 157.04(13) . . . . ? C12 C13 C14 C15 -0.9(3) . . . . ? C16 C15 C14 C13 0.5(3) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.39 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.188 _refine_diff_density_min -0.151 _refine_diff_density_rms 0.031