# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Leroy Cronin' _publ_contact_author_email LEE@CHEM.GLA.AC.UK _publ_section_title ; A new C-C bond forming annulation reaction leading to pH switchable heterocycles ; loop_ _publ_author_name 'Leroy Cronin' 'Phil. J. Kitson' 'De-Liang Long.' 'Alexis D. C. Parenty' ; C.J.Richmond ; # Attachment 'compound 2(revised).cif' data_pk51 _database_code_depnum_ccdc_archive 'CCDC 724252' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H13 N3' _chemical_formula_weight 271.31 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 17.8112(8) _cell_length_b 6.4552(3) _cell_length_c 11.8419(5) _cell_angle_alpha 90.00 _cell_angle_beta 99.737(4) _cell_angle_gamma 90.00 _cell_volume 1341.91(10) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 1541 _cell_measurement_theta_min 3.12 _cell_measurement_theta_max 15.00 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.09 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.343 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 568 _exptl_absorpt_coefficient_mu 0.082 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.992 _exptl_absorpt_correction_T_max 0.997 _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Oxford Gemini CCD' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 7323 _diffrn_reflns_av_R_equivalents 0.0614 _diffrn_reflns_av_sigmaI/netI 0.0948 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.36 _diffrn_reflns_theta_max 24.00 _reflns_number_total 2111 _reflns_number_gt 1199 _reflns_threshold_expression >2\s(I) _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Crystal data are slightly too weak and the 2-theta max has been cut to 48 degrees to obtain reasonable goodness_of_fit factors. The molecular structure in the asymmetrical unit is well defined. 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^ > 2\s(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^)+(0.0316P)^2^+0.0000P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef none _refine_ls_number_reflns 2111 _refine_ls_number_parameters 190 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0824 _refine_ls_R_factor_gt 0.0389 _refine_ls_wR_factor_ref 0.0762 _refine_ls_wR_factor_gt 0.0694 _refine_ls_goodness_of_fit_ref 0.804 _refine_ls_restrained_S_all 0.804 _refine_ls_shift/su_max 0.001 _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 N1 N 0.72508(9) 0.2292(3) 0.58656(14) 0.0212(5) Uani 1 1 d . . . N2 N 0.52292(10) 0.1383(3) 0.79368(16) 0.0317(5) Uani 1 1 d . . . N3 N 0.58255(10) -0.1596(3) 0.48675(16) 0.0298(5) Uani 1 1 d . . . C1 C 0.80248(11) 0.2251(3) 0.58161(17) 0.0193(5) Uani 1 1 d . . . C2 C 0.83471(12) 0.3648(3) 0.51422(18) 0.0241(6) Uani 1 1 d . . . H2 H 0.8040 0.4692 0.4728 0.029 Uiso 1 1 calc R . . C3 C 0.91106(12) 0.3524(3) 0.50728(18) 0.0287(6) Uani 1 1 d . . . H3 H 0.9325 0.4470 0.4602 0.034 Uiso 1 1 calc R . . C4 C 0.95664(12) 0.2031(4) 0.56836(19) 0.0320(6) Uani 1 1 d . . . H4 H 1.0094 0.1968 0.5646 0.038 Uiso 1 1 calc R . . C5 C 0.92471(12) 0.0631(4) 0.63496(19) 0.0311(6) Uani 1 1 d . . . H5 H 0.9564 -0.0389 0.6768 0.037 Uiso 1 1 calc R . . C6 C 0.84710(12) 0.0673(3) 0.64240(17) 0.0222(5) Uani 1 1 d . . . C7 C 0.81012(12) -0.0866(3) 0.70749(17) 0.0205(5) Uani 1 1 d . . . C8 C 0.84754(12) -0.2670(3) 0.75271(18) 0.0271(6) Uani 1 1 d . . . H8 H 0.8972 -0.2962 0.7377 0.032 Uiso 1 1 calc R . . C9 C 0.81351(13) -0.4032(3) 0.81876(18) 0.0288(6) Uani 1 1 d . . . H9 H 0.8405 -0.5221 0.8507 0.035 Uiso 1 1 calc R . . C10 C 0.74045(12) -0.3670(3) 0.83843(17) 0.0248(6) Uani 1 1 d . . . H10 H 0.7175 -0.4592 0.8851 0.030 Uiso 1 1 calc R . . C11 C 0.70086(12) -0.1959(3) 0.78989(16) 0.0213(5) Uani 1 1 d . . . H11 H 0.6498 -0.1742 0.8006 0.026 Uiso 1 1 calc R . . C12 C 0.73511(11) -0.0549(3) 0.72548(16) 0.0183(5) Uani 1 1 d . . . C13 C 0.69615(11) 0.1453(3) 0.68430(17) 0.0192(5) Uani 1 1 d . . . H13 H 0.7058 0.2485 0.7481 0.023 Uiso 1 1 calc R . . C14 C 0.67601(11) 0.3971(3) 0.53420(18) 0.0248(6) Uani 1 1 d . . . H14A H 0.6701 0.3917 0.4496 0.030 Uiso 1 1 calc R . . H14B H 0.6972 0.5337 0.5609 0.030 Uiso 1 1 calc R . . C15 C 0.59974(11) 0.3585(3) 0.57398(18) 0.0237(5) Uani 1 1 d . . . H15A H 0.5576 0.3541 0.5078 0.028 Uiso 1 1 calc R . . H15B H 0.5891 0.4685 0.6273 0.028 Uiso 1 1 calc R . . C16 C 0.60952(11) 0.1446(3) 0.63566(17) 0.0194(5) Uani 1 1 d . . . C17 C 0.59296(11) -0.0280(3) 0.55310(19) 0.0207(5) Uani 1 1 d . . . C18 C 0.56021(12) 0.1338(3) 0.72398(19) 0.0213(5) 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 N1 0.0201(11) 0.0223(11) 0.0222(10) 0.0085(9) 0.0065(9) 0.0031(9) N2 0.0309(12) 0.0378(13) 0.0285(11) 0.0025(10) 0.0107(10) 0.0004(10) N3 0.0264(12) 0.0327(12) 0.0297(11) -0.0030(10) 0.0031(9) 0.0014(10) C1 0.0197(13) 0.0199(13) 0.0191(12) -0.0030(11) 0.0059(11) -0.0035(11) C2 0.0198(13) 0.0247(14) 0.0274(13) 0.0003(11) 0.0028(11) -0.0031(11) C3 0.0278(14) 0.0294(14) 0.0307(13) 0.0009(12) 0.0097(12) -0.0089(12) C4 0.0180(13) 0.0339(15) 0.0446(16) 0.0049(13) 0.0070(12) -0.0031(12) C5 0.0213(14) 0.0318(14) 0.0384(15) 0.0054(12) 0.0001(12) 0.0028(12) C6 0.0229(13) 0.0228(13) 0.0200(12) -0.0015(11) 0.0014(11) 0.0010(11) C7 0.0220(13) 0.0199(13) 0.0184(12) -0.0007(10) -0.0003(10) 0.0000(11) C8 0.0226(13) 0.0271(14) 0.0310(14) 0.0010(12) 0.0031(11) 0.0017(12) C9 0.0315(14) 0.0201(14) 0.0329(14) 0.0034(11) -0.0001(12) 0.0039(12) C10 0.0311(15) 0.0196(13) 0.0231(13) 0.0016(11) 0.0030(11) -0.0032(12) C11 0.0231(13) 0.0221(13) 0.0185(12) -0.0020(11) 0.0029(10) -0.0011(11) C12 0.0207(13) 0.0176(12) 0.0158(12) -0.0009(10) 0.0011(10) -0.0001(11) C13 0.0193(13) 0.0199(13) 0.0186(12) -0.0019(11) 0.0037(10) -0.0021(11) C14 0.0261(13) 0.0222(13) 0.0259(13) 0.0087(11) 0.0039(11) 0.0030(11) C15 0.0241(13) 0.0225(13) 0.0250(12) 0.0035(11) 0.0057(11) 0.0019(11) C16 0.0202(12) 0.0190(13) 0.0198(12) -0.0015(11) 0.0057(10) -0.0011(11) C17 0.0137(13) 0.0259(14) 0.0227(13) 0.0056(12) 0.0031(11) 0.0031(11) C18 0.0201(13) 0.0194(13) 0.0230(12) 0.0012(11) -0.0004(11) 0.0009(11) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 N1 C1 1.390(2) . ? N1 C13 1.449(2) . ? N1 C14 1.463(2) . ? N2 C18 1.144(2) . ? N3 C17 1.151(3) . ? C1 C2 1.391(3) . ? C1 C6 1.412(3) . ? C2 C3 1.379(3) . ? C3 C4 1.383(3) . ? C4 C5 1.384(3) . ? C5 C6 1.400(3) . ? C6 C7 1.479(3) . ? C7 C8 1.402(3) . ? C7 C12 1.403(3) . ? C8 C9 1.383(3) . ? C9 C10 1.380(3) . ? C10 C11 1.383(3) . ? C11 C12 1.393(3) . ? C12 C13 1.508(3) . ? C13 C16 1.553(3) . ? C14 C15 1.532(3) . ? C15 C16 1.558(3) . ? C16 C18 1.477(3) . ? C16 C17 1.478(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 C1 N1 C13 121.05(16) . . ? C1 N1 C14 121.47(17) . . ? C13 N1 C14 110.34(16) . . ? N1 C1 C2 121.35(19) . . ? N1 C1 C6 117.97(19) . . ? C2 C1 C6 120.59(19) . . ? C3 C2 C1 120.2(2) . . ? C2 C3 C4 120.5(2) . . ? C3 C4 C5 119.5(2) . . ? C4 C5 C6 121.9(2) . . ? C5 C6 C1 117.3(2) . . ? C5 C6 C7 123.45(19) . . ? C1 C6 C7 119.24(19) . . ? C8 C7 C12 117.83(19) . . ? C8 C7 C6 122.15(19) . . ? C12 C7 C6 120.02(19) . . ? C9 C8 C7 121.2(2) . . ? C10 C9 C8 120.3(2) . . ? C9 C10 C11 119.6(2) . . ? C10 C11 C12 120.7(2) . . ? C11 C12 C7 120.27(19) . . ? C11 C12 C13 121.11(19) . . ? C7 C12 C13 118.30(18) . . ? N1 C13 C12 111.83(16) . . ? N1 C13 C16 99.79(15) . . ? C12 C13 C16 119.41(17) . . ? N1 C14 C15 104.27(16) . . ? C14 C15 C16 104.70(16) . . ? C18 C16 C17 110.91(17) . . ? C18 C16 C13 114.21(16) . . ? C17 C16 C13 108.81(16) . . ? C18 C16 C15 109.93(17) . . ? C17 C16 C15 111.33(16) . . ? C13 C16 C15 101.32(15) . . ? N3 C17 C16 177.2(2) . . ? N2 C18 C16 175.7(2) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 24.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.143 _refine_diff_density_min -0.199 _refine_diff_density_rms 0.041 # Attachment 'compound 3.cif' data_pk514 _database_code_depnum_ccdc_archive 'CCDC 724253' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H17 N O2' _chemical_formula_weight 351.39 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source O O 0.0106 0.0060 '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' 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' _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 6.2544(4) _cell_length_b 11.5568(8) _cell_length_c 11.9526(6) _cell_angle_alpha 98.758(4) _cell_angle_beta 97.634(4) _cell_angle_gamma 97.453(3) _cell_volume 836.33(9) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 7219 _cell_measurement_theta_min 1.41 _cell_measurement_theta_max 25.35 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.395 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 368 _exptl_absorpt_coefficient_mu 0.089 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9756 _exptl_absorpt_correction_T_max 0.9877 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% none _diffrn_reflns_number 10103 _diffrn_reflns_av_R_equivalents 0.0427 _diffrn_reflns_av_sigmaI/netI 0.0655 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.75 _diffrn_reflns_theta_max 25.48 _reflns_number_total 3106 _reflns_number_gt 1965 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius BV, 1997-2000)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _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^)+(0.0390P)^2^+0.2417P] 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 riding _refine_ls_extinction_method none _refine_ls_extinction_coef none _refine_ls_number_reflns 3106 _refine_ls_number_parameters 244 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1007 _refine_ls_R_factor_gt 0.0481 _refine_ls_wR_factor_ref 0.1075 _refine_ls_wR_factor_gt 0.0909 _refine_ls_goodness_of_fit_ref 1.061 _refine_ls_restrained_S_all 1.061 _refine_ls_shift/su_max 0.001 _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 O1 O -0.3168(2) 0.51765(14) 0.38868(12) 0.0271(4) Uani 1 1 d . . . O2 O 0.2873(2) 0.81286(14) 0.40034(13) 0.0327(4) Uani 1 1 d . . . N1 N 0.1179(3) 0.63656(16) 0.16931(14) 0.0234(5) Uani 1 1 d . . . C1 C 0.1488(3) 0.66735(19) 0.06538(17) 0.0195(5) Uani 1 1 d . . . C2 C 0.3070(3) 0.62385(19) 0.00511(18) 0.0247(6) Uani 1 1 d . . . H2 H 0.3935 0.5709 0.0357 0.030 Uiso 1 1 calc R . . C3 C 0.3387(4) 0.6572(2) -0.09845(19) 0.0289(6) Uani 1 1 d . . . H3 H 0.4478 0.6276 -0.1380 0.035 Uiso 1 1 calc R . . C4 C 0.2123(4) 0.7334(2) -0.14494(19) 0.0293(6) Uani 1 1 d . . . H4 H 0.2310 0.7543 -0.2173 0.035 Uiso 1 1 calc R . . C5 C 0.0589(4) 0.7787(2) -0.08477(18) 0.0269(6) Uani 1 1 d . . . H5 H -0.0265 0.8315 -0.1164 0.032 Uiso 1 1 calc R . . C6 C 0.0262(3) 0.74901(19) 0.02133(17) 0.0201(5) Uani 1 1 d . . . C7 C -0.1262(3) 0.80227(19) 0.09079(17) 0.0194(5) Uani 1 1 d . . . C8 C -0.2262(3) 0.8976(2) 0.06264(18) 0.0246(5) Uani 1 1 d . . . H8 H -0.1904 0.9315 -0.0013 0.030 Uiso 1 1 calc R . . C9 C -0.3753(3) 0.9439(2) 0.12492(18) 0.0249(6) Uani 1 1 d . . . H9 H -0.4402 1.0090 0.1041 0.030 Uiso 1 1 calc R . . C10 C -0.4299(3) 0.89486(19) 0.21802(18) 0.0226(5) Uani 1 1 d . . . H10 H -0.5357 0.9245 0.2600 0.027 Uiso 1 1 calc R . . C11 C -0.3292(3) 0.80256(19) 0.24937(17) 0.0211(5) Uani 1 1 d . . . H11 H -0.3651 0.7700 0.3141 0.025 Uiso 1 1 calc R . . C12 C -0.1765(3) 0.75631(18) 0.18817(17) 0.0177(5) Uani 1 1 d . . . C13 C -0.0805(3) 0.64924(19) 0.21739(16) 0.0198(5) Uani 1 1 d . . . H13 H -0.1901 0.5773 0.1836 0.024 Uiso 1 1 calc R . . C14 C 0.2305(4) 0.5496(2) 0.21919(18) 0.0246(5) Uani 1 1 d . . . H14A H 0.3905 0.5749 0.2327 0.029 Uiso 1 1 calc R . . H14B H 0.1961 0.4713 0.1684 0.029 Uiso 1 1 calc R . . C15 C 0.1434(3) 0.5444(2) 0.33275(18) 0.0246(5) Uani 1 1 d . . . H15A H 0.2655 0.5594 0.3975 0.030 Uiso 1 1 calc R . . H15B H 0.0581 0.4656 0.3311 0.030 Uiso 1 1 calc R . . C16 C -0.0036(3) 0.64185(19) 0.34578(17) 0.0189(5) Uani 1 1 d . . . C17 C -0.1892(3) 0.6096(2) 0.41175(17) 0.0202(5) Uani 1 1 d . . . C18 C -0.1849(3) 0.70876(19) 0.50743(17) 0.0199(5) Uani 1 1 d . . . C19 C -0.3279(3) 0.7226(2) 0.58583(18) 0.0251(6) Uani 1 1 d . . . H19 H -0.4467 0.6625 0.5860 0.030 Uiso 1 1 calc R . . C20 C -0.2913(4) 0.8274(2) 0.66394(18) 0.0300(6) Uani 1 1 d . . . H20 H -0.3888 0.8400 0.7176 0.036 Uiso 1 1 calc R . . C21 C -0.1149(4) 0.9148(2) 0.66557(18) 0.0293(6) Uani 1 1 d . . . H21 H -0.0941 0.9858 0.7201 0.035 Uiso 1 1 calc R . . C22 C 0.0305(4) 0.8995(2) 0.58898(17) 0.0253(6) Uani 1 1 d . . . H22 H 0.1534 0.9580 0.5912 0.030 Uiso 1 1 calc R . . C23 C -0.0089(3) 0.79603(19) 0.50868(16) 0.0193(5) Uani 1 1 d . . . C24 C 0.1158(3) 0.7595(2) 0.41567(17) 0.0214(5) 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 0.0290(9) 0.0232(10) 0.0276(9) 0.0053(7) 0.0040(7) -0.0023(8) O2 0.0282(9) 0.0344(11) 0.0335(9) 0.0038(8) 0.0085(7) -0.0042(8) N1 0.0260(10) 0.0276(12) 0.0226(10) 0.0099(8) 0.0086(8) 0.0151(9) C1 0.0214(12) 0.0173(13) 0.0183(12) 0.0009(9) 0.0029(9) 0.0006(10) C2 0.0256(13) 0.0219(14) 0.0259(13) -0.0001(10) 0.0046(10) 0.0050(10) C3 0.0314(13) 0.0263(15) 0.0277(13) -0.0036(11) 0.0134(11) 0.0002(11) C4 0.0387(14) 0.0280(15) 0.0229(13) 0.0061(11) 0.0130(11) 0.0013(12) C5 0.0313(13) 0.0273(15) 0.0225(12) 0.0062(10) 0.0048(10) 0.0026(11) C6 0.0208(12) 0.0204(13) 0.0178(12) 0.0020(10) 0.0027(9) -0.0003(10) C7 0.0185(11) 0.0194(13) 0.0193(12) 0.0032(9) -0.0001(9) 0.0022(10) C8 0.0271(13) 0.0256(14) 0.0215(12) 0.0081(10) 0.0029(10) 0.0012(11) C9 0.0257(13) 0.0223(14) 0.0280(13) 0.0069(11) 0.0013(10) 0.0083(11) C10 0.0188(12) 0.0250(14) 0.0250(13) 0.0027(10) 0.0038(10) 0.0085(10) C11 0.0204(12) 0.0217(14) 0.0210(12) 0.0047(10) 0.0033(9) 0.0006(10) C12 0.0159(11) 0.0170(13) 0.0186(12) 0.0014(9) -0.0012(9) 0.0022(9) C13 0.0199(12) 0.0213(13) 0.0188(12) 0.0036(9) 0.0038(9) 0.0042(10) C14 0.0283(13) 0.0221(14) 0.0253(13) 0.0041(10) 0.0039(10) 0.0115(11) C15 0.0266(13) 0.0243(14) 0.0255(13) 0.0078(10) 0.0041(10) 0.0088(10) C16 0.0202(12) 0.0189(13) 0.0182(12) 0.0052(9) 0.0032(9) 0.0027(10) C17 0.0205(12) 0.0205(14) 0.0189(12) 0.0070(10) -0.0022(9) 0.0025(10) C18 0.0202(12) 0.0219(13) 0.0186(12) 0.0073(10) 0.0020(9) 0.0044(10) C19 0.0255(13) 0.0259(14) 0.0247(13) 0.0076(10) 0.0033(10) 0.0035(11) C20 0.0319(14) 0.0391(17) 0.0227(13) 0.0079(11) 0.0077(10) 0.0121(12) C21 0.0377(15) 0.0261(15) 0.0230(13) 0.0010(10) 0.0011(11) 0.0080(12) C22 0.0282(13) 0.0223(14) 0.0233(13) 0.0048(10) -0.0018(10) 0.0011(10) C23 0.0228(12) 0.0201(13) 0.0155(11) 0.0065(9) -0.0003(9) 0.0044(10) C24 0.0213(12) 0.0234(14) 0.0211(12) 0.0096(10) 0.0023(9) 0.0038(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 O1 C17 1.214(2) . ? O2 C24 1.216(2) . ? N1 C1 1.374(3) . ? N1 C13 1.450(2) . ? N1 C14 1.455(3) . ? C1 C2 1.400(3) . ? C1 C6 1.410(3) . ? C2 C3 1.382(3) . ? C3 C4 1.387(3) . ? C4 C5 1.382(3) . ? C5 C6 1.397(3) . ? C6 C7 1.478(3) . ? C7 C8 1.397(3) . ? C7 C12 1.407(3) . ? C8 C9 1.380(3) . ? C9 C10 1.385(3) . ? C10 C11 1.381(3) . ? C11 C12 1.390(3) . ? C12 C13 1.511(3) . ? C13 C16 1.565(3) . ? C14 C15 1.535(3) . ? C15 C16 1.546(3) . ? C16 C24 1.526(3) . ? C16 C17 1.526(3) . ? C17 C18 1.486(3) . ? C18 C19 1.385(3) . ? C18 C23 1.390(3) . ? C19 C20 1.385(3) . ? C20 C21 1.391(3) . ? C21 C22 1.382(3) . ? C22 C23 1.387(3) . ? C23 C24 1.481(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 C1 N1 C13 122.52(17) . . ? C1 N1 C14 123.08(17) . . ? C13 N1 C14 110.37(17) . . ? N1 C1 C2 121.3(2) . . ? N1 C1 C6 119.29(18) . . ? C2 C1 C6 119.3(2) . . ? C3 C2 C1 120.7(2) . . ? C2 C3 C4 120.4(2) . . ? C5 C4 C3 119.2(2) . . ? C4 C5 C6 121.8(2) . . ? C5 C6 C1 118.48(19) . . ? C5 C6 C7 122.8(2) . . ? C1 C6 C7 118.69(19) . . ? C8 C7 C12 117.82(19) . . ? C8 C7 C6 122.2(2) . . ? C12 C7 C6 120.00(19) . . ? C9 C8 C7 122.0(2) . . ? C8 C9 C10 119.6(2) . . ? C11 C10 C9 119.5(2) . . ? C10 C11 C12 121.3(2) . . ? C11 C12 C7 119.6(2) . . ? C11 C12 C13 120.92(19) . . ? C7 C12 C13 119.14(17) . . ? N1 C13 C12 112.09(17) . . ? N1 C13 C16 101.16(15) . . ? C12 C13 C16 119.48(17) . . ? N1 C14 C15 104.23(16) . . ? C14 C15 C16 106.25(17) . . ? C24 C16 C17 103.40(16) . . ? C24 C16 C15 113.44(17) . . ? C17 C16 C15 112.14(18) . . ? C24 C16 C13 113.08(18) . . ? C17 C16 C13 114.16(16) . . ? C15 C16 C13 101.04(15) . . ? O1 C17 C18 126.7(2) . . ? O1 C17 C16 124.89(19) . . ? C18 C17 C16 108.44(18) . . ? C19 C18 C23 121.10(19) . . ? C19 C18 C17 129.4(2) . . ? C23 C18 C17 109.53(18) . . ? C20 C19 C18 117.5(2) . . ? C19 C20 C21 121.5(2) . . ? C22 C21 C20 120.9(2) . . ? C21 C22 C23 117.8(2) . . ? C22 C23 C18 121.16(19) . . ? C22 C23 C24 128.8(2) . . ? C18 C23 C24 110.07(18) . . ? O2 C24 C23 125.5(2) . . ? O2 C24 C16 126.19(19) . . ? C23 C24 C16 108.30(17) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.48 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.20 _refine_diff_density_min -0.23 _refine_diff_density_rms 0.05