Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Steven Ley' 'Ed Cleator' 'Peter R. Hewitt' _publ_contact_author_name 'Prof Steven Ley' _publ_contact_author_address ; Department of Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UNITED KINGDOM ; _publ_contact_author_email SVL1000@CAM.AC.UK _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; A rapid stereocontrolled synthesis of the 3a-hydroxy-pyrrolo[2,3-b]indole skeleton, a building block for 10b-hydroxy-pyrazino[1',2':1,5]pyrrolo[2,3-b] indole-1,4-diones ; data_sl0251 _database_code_CSD 215821 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H22 N2 O5,C H Cl3' _chemical_formula_sum 'C18 H23 Cl3 N2 O5' _chemical_formula_weight 453.73 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' Cl Cl 0.1484 0.1585 '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 12.2184(6) _cell_length_b 6.3844(3) _cell_length_c 14.8429(9) _cell_angle_alpha 90.00 _cell_angle_beta 108.081(2) _cell_angle_gamma 90.00 _cell_volume 1100.68(10) _cell_formula_units_Z 2 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 5923 _cell_measurement_theta_min 1.00 _cell_measurement_theta_max 25.03 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.46 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.369 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 472 _exptl_absorpt_coefficient_mu 0.446 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.940 _exptl_absorpt_correction_T_max 0.994 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_standards_number 0 _diffrn_reflns_number 5544 _diffrn_reflns_av_R_equivalents 0.0389 _diffrn_reflns_av_sigmaI/netI 0.0628 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 4.11 _diffrn_reflns_theta_max 25.03 _reflns_number_total 3372 _reflns_number_gt 2908 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius B.V. 1998)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick 1997)' _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^)+(0.1046P)^2^+0.5374P] 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 0.04(13) _refine_ls_number_reflns 3372 _refine_ls_number_parameters 263 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0705 _refine_ls_R_factor_gt 0.0577 _refine_ls_wR_factor_ref 0.1757 _refine_ls_wR_factor_gt 0.1560 _refine_ls_goodness_of_fit_ref 1.090 _refine_ls_restrained_S_all 1.090 _refine_ls_shift/su_max 0.011 _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 O1 O 0.7119(3) -0.1063(7) 0.7178(2) 0.0524(9) Uani 1 1 d . . . O2 O 0.5540(2) -0.1772(5) 0.76121(19) 0.0360(7) Uani 1 1 d . . . O3 O 0.5843(2) 0.4478(4) 0.95152(19) 0.0256(6) Uani 1 1 d . . . H3 H 0.530(4) 0.423(8) 0.985(3) 0.031 Uiso 1 1 d . . . O4 O 0.6590(3) -0.3128(6) 1.1472(2) 0.0472(9) Uani 1 1 d . . . O5 O 0.8155(3) -0.1253(6) 1.2162(2) 0.0473(9) Uani 1 1 d . . . N1 N 0.6856(3) 0.0408(5) 0.8491(2) 0.0268(7) Uani 1 1 d . . . N2 N 0.6145(3) -0.0864(5) 0.9790(2) 0.0224(7) Uani 1 1 d . . . H2 H 0.614(4) -0.199(9) 0.960(3) 0.027 Uiso 1 1 d . . . C1 C 0.3852(6) -0.3619(13) 0.6941(4) 0.078(2) Uani 1 1 d . . . H1A H 0.3445 -0.2317 0.6981 0.117 Uiso 1 1 calc R . . H1B H 0.3991 -0.4410 0.7532 0.117 Uiso 1 1 calc R . . H1C H 0.3382 -0.4462 0.6409 0.117 Uiso 1 1 calc R . . C2 C 0.5720(6) -0.5085(10) 0.6834(4) 0.0673(16) Uani 1 1 d . . . H2B H 0.6429 -0.4727 0.6692 0.101 Uiso 1 1 calc R . . H2C H 0.5279 -0.6105 0.6369 0.101 Uiso 1 1 calc R . . H2D H 0.5915 -0.5690 0.7471 0.101 Uiso 1 1 calc R . . C3 C 0.4997(4) -0.3105(8) 0.6787(3) 0.0404(11) Uani 1 1 d . . . C4 C 0.4806(5) -0.1886(10) 0.5875(3) 0.0593(15) Uani 1 1 d . . . H4A H 0.4423 -0.0558 0.5916 0.089 Uiso 1 1 calc R . . H4B H 0.4323 -0.2708 0.5342 0.089 Uiso 1 1 calc R . . H4C H 0.5550 -0.1605 0.5778 0.089 Uiso 1 1 calc R . . C5 C 0.6544(3) -0.0847(7) 0.7703(3) 0.0332(9) Uani 1 1 d . . . C6 C 0.7746(3) 0.1906(7) 0.8691(3) 0.0281(8) Uani 1 1 d . . . C7 C 0.8638(4) 0.2150(8) 0.8302(3) 0.0391(10) Uani 1 1 d . . . H7 H 0.8728 0.1197 0.7839 0.047 Uiso 1 1 calc R . . C8 C 0.9391(4) 0.3805(9) 0.8604(3) 0.0455(12) Uani 1 1 d . . . H8 H 0.9995 0.3998 0.8335 0.055 Uiso 1 1 calc R . . C9 C 0.9286(4) 0.5185(8) 0.9289(4) 0.0430(11) Uani 1 1 d . . . H9 H 0.9812 0.6316 0.9482 0.052 Uiso 1 1 calc R . . C10 C 0.8408(3) 0.4924(7) 0.9697(3) 0.0353(10) Uani 1 1 d . . . H10 H 0.8342 0.5848 1.0180 0.042 Uiso 1 1 calc R . . C11 C 0.7638(3) 0.3295(6) 0.9386(3) 0.0256(8) Uani 1 1 d . . . C12 C 0.6598(3) 0.2751(6) 0.9694(3) 0.0237(8) Uani 1 1 d . . . C13 C 0.6960(3) 0.1966(6) 1.0726(3) 0.0259(8) Uani 1 1 d . . . H13A H 0.7675 0.2657 1.1117 0.031 Uiso 1 1 calc R . . H13B H 0.6344 0.2198 1.1019 0.031 Uiso 1 1 calc R . . C14 C 0.7152(3) -0.0378(6) 1.0601(3) 0.0249(8) Uani 1 1 d . . . H14 H 0.7864 -0.0562 1.0413 0.030 Uiso 1 1 calc R . . C15 C 0.6091(3) 0.0767(6) 0.9097(2) 0.0220(8) Uani 1 1 d . . . H15 H 0.5278 0.1017 0.8695 0.026 Uiso 1 1 calc R . . C16 C 0.7231(3) -0.1737(6) 1.1440(3) 0.0281(9) Uani 1 1 d . . . C17 C 0.8355(5) -0.2537(11) 1.3012(4) 0.0583(14) Uani 1 1 d . . . H17A H 0.8994 -0.1947 1.3524 0.087 Uiso 1 1 calc R . . H17B H 0.8547 -0.3969 1.2878 0.087 Uiso 1 1 calc R . . H17C H 0.7658 -0.2556 1.3206 0.087 Uiso 1 1 calc R . . C18 C 0.8709(4) -0.2182(9) 0.6055(4) 0.0501(13) Uani 1 1 d . . . H18 H 0.8232 -0.1997 0.6488 0.060 Uiso 1 1 calc R . . Cl1 Cl 0.8104(2) -0.4205(4) 0.52797(15) 0.1123(9) Uani 1 1 d . . . Cl2 Cl 1.01086(17) -0.2747(4) 0.67552(18) 0.1063(8) Uani 1 1 d . . . Cl3 Cl 0.8683(2) 0.0138(4) 0.54692(16) 0.1200(9) 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 O1 0.0463(17) 0.072(3) 0.0488(18) -0.0276(19) 0.0291(15) -0.0140(19) O2 0.0374(15) 0.0402(19) 0.0331(15) -0.0113(13) 0.0149(12) -0.0128(13) O3 0.0258(13) 0.0160(14) 0.0391(14) 0.0026(11) 0.0161(11) 0.0021(10) O4 0.0449(18) 0.047(2) 0.0450(18) 0.0121(16) 0.0075(14) -0.0179(17) O5 0.0340(15) 0.058(2) 0.0402(17) 0.0186(16) -0.0020(13) -0.0070(16) N1 0.0271(16) 0.0282(19) 0.0293(16) -0.0068(14) 0.0146(13) -0.0009(14) N2 0.0228(15) 0.0137(16) 0.0326(17) -0.0039(14) 0.0116(13) -0.0023(13) C1 0.076(4) 0.108(6) 0.058(3) -0.033(3) 0.032(3) -0.060(4) C2 0.105(5) 0.038(3) 0.050(3) -0.013(3) 0.011(3) 0.001(3) C3 0.056(3) 0.038(3) 0.027(2) -0.005(2) 0.0126(19) -0.013(2) C4 0.069(3) 0.064(4) 0.037(3) 0.008(3) 0.005(2) -0.013(3) C5 0.035(2) 0.031(2) 0.038(2) -0.0036(19) 0.0166(18) 0.0004(19) C6 0.0224(17) 0.030(2) 0.0324(19) 0.0006(18) 0.0102(15) 0.0016(17) C7 0.034(2) 0.047(3) 0.043(2) -0.005(2) 0.0229(19) -0.005(2) C8 0.030(2) 0.056(3) 0.055(3) -0.002(2) 0.019(2) -0.008(2) C9 0.032(2) 0.036(3) 0.065(3) 0.000(2) 0.021(2) -0.009(2) C10 0.029(2) 0.028(2) 0.053(2) -0.004(2) 0.0181(19) -0.001(2) C11 0.0212(17) 0.018(2) 0.041(2) 0.0054(17) 0.0149(16) 0.0017(15) C12 0.0234(17) 0.0188(19) 0.0313(19) 0.0017(16) 0.0120(15) 0.0033(15) C13 0.0285(18) 0.0185(19) 0.0309(19) -0.0010(17) 0.0093(15) 0.0013(16) C14 0.0195(16) 0.020(2) 0.035(2) -0.0003(16) 0.0092(15) 0.0020(15) C15 0.0182(16) 0.0216(19) 0.0278(18) -0.0035(16) 0.0092(14) 0.0016(15) C16 0.0251(18) 0.026(2) 0.036(2) 0.0017(17) 0.0133(16) 0.0058(17) C17 0.052(3) 0.065(4) 0.049(3) 0.022(3) 0.001(2) 0.000(3) C18 0.049(3) 0.059(3) 0.050(3) -0.005(3) 0.027(2) 0.006(2) Cl1 0.158(2) 0.0932(16) 0.0895(13) -0.0274(12) 0.0437(14) -0.0557(16) Cl2 0.0765(11) 0.0847(15) 0.1352(18) 0.0335(14) 0.0002(11) 0.0090(11) Cl3 0.150(2) 0.0649(14) 0.0990(14) 0.0199(11) -0.0294(13) -0.0018(13) _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 C5 1.207(5) . ? O2 C5 1.330(5) . ? O2 C3 1.469(5) . ? O3 C12 1.409(5) . ? O4 C16 1.195(5) . ? O5 C16 1.329(5) . ? O5 C17 1.461(6) . ? N1 C5 1.371(5) . ? N1 C6 1.409(5) . ? N1 C15 1.502(4) . ? N2 C15 1.451(5) . ? N2 C14 1.464(5) . ? C1 C3 1.522(7) . ? C2 C3 1.531(8) . ? C3 C4 1.515(7) . ? C6 C7 1.391(5) . ? C6 C11 1.399(6) . ? C7 C8 1.381(7) . ? C8 C9 1.380(7) . ? C9 C10 1.396(6) . ? C10 C11 1.383(6) . ? C11 C12 1.517(5) . ? C12 C13 1.541(5) . ? C12 C15 1.560(5) . ? C13 C14 1.535(6) . ? C14 C16 1.497(6) . ? C18 Cl3 1.713(6) . ? C18 Cl1 1.734(6) . ? C18 Cl2 1.741(5) . ? 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 C5 O2 C3 120.3(3) . . ? C16 O5 C17 116.0(4) . . ? C5 N1 C6 124.7(3) . . ? C5 N1 C15 122.7(3) . . ? C6 N1 C15 110.7(3) . . ? C15 N2 C14 105.8(3) . . ? O2 C3 C4 110.6(4) . . ? O2 C3 C1 101.4(4) . . ? C4 C3 C1 110.5(5) . . ? O2 C3 C2 109.6(4) . . ? C4 C3 C2 113.0(4) . . ? C1 C3 C2 111.0(5) . . ? O1 C5 O2 126.0(4) . . ? O1 C5 N1 123.6(4) . . ? O2 C5 N1 110.4(3) . . ? C7 C6 C11 120.0(4) . . ? C7 C6 N1 129.9(4) . . ? C11 C6 N1 110.0(3) . . ? C8 C7 C6 118.7(4) . . ? C9 C8 C7 121.5(4) . . ? C8 C9 C10 120.2(4) . . ? C11 C10 C9 118.7(4) . . ? C10 C11 C6 120.9(3) . . ? C10 C11 C12 128.2(4) . . ? C6 C11 C12 110.9(3) . . ? O3 C12 C11 108.9(3) . . ? O3 C12 C13 114.3(3) . . ? C11 C12 C13 111.4(3) . . ? O3 C12 C15 114.0(3) . . ? C11 C12 C15 103.7(3) . . ? C13 C12 C15 104.0(3) . . ? C14 C13 C12 101.8(3) . . ? N2 C14 C16 112.5(3) . . ? N2 C14 C13 100.7(3) . . ? C16 C14 C13 115.9(3) . . ? N2 C15 N1 114.5(3) . . ? N2 C15 C12 104.9(3) . . ? N1 C15 C12 104.7(3) . . ? O4 C16 O5 123.0(4) . . ? O4 C16 C14 126.2(4) . . ? O5 C16 C14 110.8(3) . . ? Cl3 C18 Cl1 111.7(3) . . ? Cl3 C18 Cl2 110.0(3) . . ? Cl1 C18 Cl2 112.3(3) . . ? _diffrn_measured_fraction_theta_max 0.987 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.987 _refine_diff_density_max 0.443 _refine_diff_density_min -0.531 _refine_diff_density_rms 0.076