Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2001 data_1 _database_code_CSD 166488 ; (2S,7aS)-3-oxo-2-((2R)-3,3,3-trifluoro-2-methoxy-2-phenyl-propionyloxy) -tetrahydro-pyrrolizine-7a-carboxylic acid methyl ester ; _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' _publ_contact_author_name 'Dr Franca M Cordero' _publ_contact_author_address ; Dipartmento di Chimica Organica "Ugo Schiff", Centro di Studio CNR sulla Chimica Universita di Firenze Via G Capponi 9 Firenze 150121 ITALY ; _publ_contact_author_email 'CORDERO@CHIMORG.UNIFI.IT' loop_ _publ_author_name 'Franca M. Cordero' 'Silvia Valenza' 'Fabrizio Machetti' 'Alberto Brandi' _publ_section_title 'Design and Synthesis of a New Bicyclic Dipeptide Isostere.' _audit_creation_method SHELXL-97 _chemical_name_systematic ; (2S,7aS)-3-oxo-2-((2R)-3,3,3-trifluoro-2-methoxy-2-phenyl-propionyloxy)- tetrahydro-pyrrolizine-7a-carboxylic acid methyl ester ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19 H20 F3 N O6' _chemical_formula_weight 415.36 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'F' 'F' 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'orthorhombic' _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 8.2736(3) _cell_length_b 11.9643(6) _cell_length_c 19.746(2) _cell_angle_alpha 90.000 _cell_angle_beta 90.000 _cell_angle_gamma 90.000 _cell_volume 1954.4(17) _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 ? _exptl_crystal_colour 'colourless' _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.4 _exptl_crystal_size_min 0.3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.412 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 864 _exptl_absorpt_coefficient_mu 1.067 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Siemens P4' _diffrn_measurement_method 'profile data from (/2( scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 200 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.5 _diffrn_reflns_number 2168 _diffrn_reflns_av_R_equivalents 0.0318 _diffrn_reflns_av_sigmaI/netI 0.0187 _diffrn_reflns_limit_h_min -1 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 1 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 1 _diffrn_reflns_theta_min 4.32 _diffrn_reflns_theta_max 59.91 _reflns_number_total 1992 _reflns_number_gt 1975 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens P4' _computing_cell_refinement 'Siemens P4' _computing_data_reduction 'Siemens P4' _computing_structure_solution 'SIR97 (Altomare, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics Ortep3 _computing_publication_material Ciftab _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^)+(0.0869P)^2^+0.4414P] 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 noref _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0109(9) _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 0.1(3) _refine_ls_number_reflns 1992 _refine_ls_number_parameters 264 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0399 _refine_ls_R_factor_gt 0.0397 _refine_ls_wR_factor_ref 0.1177 _refine_ls_wR_factor_gt 0.1174 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _refine_ls_shift/su_max 0.027 _refine_ls_shift/su_mean 0.003 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 0.1154(3) 0.06374(19) 0.97961(12) 0.0446(6) Uani 1 1 d . . . O1 O -0.0736(5) -0.2052(2) 0.99387(17) 0.1081(12) Uani 1 1 d . . . O2 O 0.0983(3) -0.13326(19) 0.91923(11) 0.0687(7) Uani 1 1 d . . . O3 O 0.0535(3) 0.23875(16) 0.93998(10) 0.0553(6) Uani 1 1 d . . . O4 O -0.2310(2) 0.06255(15) 0.93038(10) 0.0457(5) Uani 1 1 d . . . O5 O -0.3229(4) 0.22943(18) 0.89612(12) 0.0746(8) Uani 1 1 d . . . O6 O -0.4757(3) -0.01495(18) 0.83973(11) 0.0595(6) Uani 1 1 d . . . F1 F -0.5842(3) 0.19064(19) 0.81128(12) 0.0866(7) Uani 1 1 d . . . F2 F -0.3672(3) 0.23490(18) 0.75819(11) 0.0803(7) Uani 1 1 d . . . F3 F -0.5135(3) 0.0977(2) 0.72375(10) 0.0917(8) Uani 1 1 d . . . C1 C -0.4553(4) 0.1482(3) 0.77898(17) 0.0632(9) Uani 1 1 d . . . C2 C -0.3586(3) 0.0677(2) 0.82336(15) 0.0465(7) Uani 1 1 d . . . C3 C -0.2153(3) 0.0224(2) 0.78301(14) 0.0465(7) Uani 1 1 d . . . C4 C -0.0614(4) 0.0651(3) 0.79075(17) 0.0635(9) Uani 1 1 d . . . H4 H -0.0426 0.1237 0.8207 0.076 Uiso 1 1 calc . . . C5 C 0.0653(4) 0.0199(4) 0.7536(2) 0.0819(12) Uani 1 1 d . . . H5 H 0.1693 0.0480 0.7591 0.098 Uiso 1 1 calc . . . C6 C 0.0387(6) -0.0657(5) 0.7089(2) 0.0841(12) Uani 1 1 d . . . H6 H 0.1247 -0.0961 0.6848 0.101 Uiso 1 1 calc . . . C7 C -0.1148(6) -0.1067(3) 0.69964(19) 0.0769(11) Uani 1 1 d . . . H7 H -0.1332 -0.1638 0.6686 0.092 Uiso 1 1 calc . . . C8 C -0.2413(4) -0.0632(3) 0.73649(16) 0.0611(8) Uani 1 1 d . . . H8 H -0.3451 -0.0913 0.7303 0.073 Uiso 1 1 calc . . . C9 C -0.4245(5) -0.1153(3) 0.87299(19) 0.0664(9) Uani 1 1 d . . . H9A H -0.5163 -0.1627 0.8806 0.100 Uiso 1 1 calc . . . H9B H -0.3754 -0.0968 0.9156 0.100 Uiso 1 1 calc . . . H9C H -0.3475 -0.1537 0.8450 0.100 Uiso 1 1 calc . . . C10 C -0.3038(4) 0.1322(2) 0.88704(15) 0.0475(7) Uani 1 1 d . . . C11 C -0.1524(4) 0.1145(2) 0.98926(14) 0.0450(7) Uani 1 1 d . . . H11 H -0.2150 0.1766 1.0082 0.054 Uiso 1 1 calc . . . C12 C 0.0164(4) 0.1496(2) 0.96627(13) 0.0421(6) Uani 1 1 d . . . C13 C 0.2926(4) 0.0643(3) 0.9819(2) 0.0599(8) Uani 1 1 d . . . H13A H 0.3333 0.1368 0.9957 0.072 Uiso 1 1 calc . . . H13B H 0.3382 0.0450 0.9382 0.072 Uiso 1 1 calc . . . C14 C 0.3317(5) -0.0251(3) 1.03500(19) 0.0711(10) Uani 1 1 d . . . H14A H 0.3733 -0.0920 1.0133 0.085 Uiso 1 1 calc . . . H14B H 0.4123 0.0023 1.0666 0.085 Uiso 1 1 calc . . . C15 C 0.1748(5) -0.0505(3) 1.07162(17) 0.0679(9) Uani 1 1 d . . . H15A H 0.1613 -0.0023 1.1107 0.081 Uiso 1 1 calc . . . H15B H 0.1714 -0.1278 1.0863 0.081 Uiso 1 1 calc . . . C16 C 0.0437(4) -0.0272(2) 1.01798(14) 0.0465(7) Uani 1 1 d . . . C17 C -0.1190(4) 0.0225(3) 1.04081(15) 0.0558(8) Uani 1 1 d . . . H17A H -0.2036 -0.0336 1.0399 0.067 Uiso 1 1 calc . . . H17B H -0.1112 0.0530 1.0862 0.067 Uiso 1 1 calc . . . C18 C 0.0146(5) -0.1315(2) 0.97562(17) 0.0579(8) Uani 1 1 d . . . C19 C 0.0833(7) -0.2332(3) 0.8777(2) 0.0906(13) Uani 1 1 d . . . H19A H 0.1496 -0.2256 0.8380 0.136 Uiso 1 1 calc . . . H19B H -0.0275 -0.2427 0.8644 0.136 Uiso 1 1 calc . . . H19C H 0.1179 -0.2971 0.9032 0.136 Uiso 1 1 calc . . . 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 0.0484(13) 0.0357(11) 0.0497(12) 0.0037(11) 0.0039(12) -0.0020(11) O1 0.154(3) 0.0569(14) 0.113(2) -0.0128(15) 0.051(2) -0.0460(19) O2 0.0963(18) 0.0501(11) 0.0597(12) -0.0114(10) 0.0142(14) -0.0098(14) O3 0.0652(13) 0.0369(10) 0.0638(11) 0.0092(9) -0.0069(12) -0.0058(10) O4 0.0489(10) 0.0390(9) 0.0493(10) -0.0038(9) -0.0037(10) 0.0019(9) O5 0.112(2) 0.0440(11) 0.0681(14) -0.0078(10) -0.0184(16) 0.0185(14) O6 0.0451(11) 0.0592(12) 0.0743(14) -0.0032(11) 0.0091(11) -0.0143(10) F1 0.0621(12) 0.0897(14) 0.1079(17) 0.0054(14) -0.0061(12) 0.0248(12) F2 0.0868(14) 0.0769(12) 0.0771(12) 0.0280(11) -0.0123(12) -0.0009(12) F3 0.0857(15) 0.1118(18) 0.0774(13) -0.0104(12) -0.0384(13) 0.0113(15) C1 0.0545(18) 0.069(2) 0.0665(19) 0.0029(18) -0.0082(18) 0.0034(18) C2 0.0411(14) 0.0457(14) 0.0526(14) -0.0001(14) -0.0008(13) -0.0041(14) C3 0.0424(15) 0.0536(16) 0.0436(14) -0.0008(13) 0.0029(12) -0.0007(13) C4 0.0538(18) 0.076(2) 0.0601(16) -0.0025(18) 0.0116(16) -0.0166(19) C5 0.0487(18) 0.113(3) 0.084(2) 0.006(3) 0.020(2) -0.008(2) C6 0.080(3) 0.109(3) 0.063(2) 0.003(2) 0.028(2) 0.021(3) C7 0.095(3) 0.079(2) 0.0567(19) -0.0150(19) 0.012(2) 0.009(2) C8 0.0635(18) 0.0659(18) 0.0539(16) -0.0108(17) 0.0049(16) -0.0035(19) C9 0.075(2) 0.0512(17) 0.0727(19) 0.0028(16) 0.007(2) -0.0200(19) C10 0.0490(15) 0.0446(15) 0.0491(15) -0.0005(13) 0.0049(14) 0.0015(14) C11 0.0511(15) 0.0415(13) 0.0426(13) -0.0080(12) 0.0009(14) 0.0023(13) C12 0.0543(15) 0.0349(13) 0.0370(12) -0.0041(11) -0.0051(13) -0.0030(13) C13 0.0498(16) 0.0430(14) 0.087(2) -0.0038(17) 0.0035(18) 0.0008(15) C14 0.063(2) 0.077(2) 0.073(2) -0.0035(19) -0.0071(19) 0.0125(19) C15 0.083(2) 0.0609(19) 0.0602(18) 0.0081(17) -0.012(2) 0.007(2) C16 0.0561(16) 0.0373(13) 0.0461(13) 0.0094(12) 0.0040(15) -0.0015(13) C17 0.0651(19) 0.0577(17) 0.0446(14) 0.0039(14) 0.0101(14) -0.0018(17) C18 0.074(2) 0.0389(14) 0.0610(17) 0.0070(13) 0.0079(19) -0.0002(17) C19 0.124(4) 0.063(2) 0.085(2) -0.031(2) 0.014(3) -0.008(3) _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 N1 C12 1.340(4) . ? N1 C16 1.453(4) . ? N1 C13 1.466(4) . ? O1 C18 1.200(4) . ? O2 C18 1.311(4) . ? O2 C19 1.455(4) . ? O3 C12 1.225(3) . ? O4 C10 1.338(4) . ? O4 C11 1.470(3) . ? O5 C10 1.188(4) . ? O6 C2 1.422(3) . ? O6 C9 1.433(4) . ? F1 C1 1.342(4) . ? F2 C1 1.332(4) . ? F3 C1 1.337(4) . ? C1 C2 1.529(5) . ? C2 C3 1.528(4) . ? C2 C10 1.543(4) . ? C3 C4 1.380(4) . ? C3 C8 1.393(4) . ? C4 C5 1.389(5) . ? C4 H4 0.9300 . ? C5 C6 1.370(7) . ? C5 H5 0.9300 . ? C6 C7 1.374(6) . ? C6 H6 0.9300 . ? C7 C8 1.377(5) . ? C7 H7 0.9300 . ? C8 H8 0.9300 . ? C9 H9A 0.9600 . ? C9 H9B 0.9600 . ? C9 H9C 0.9600 . ? C11 C17 1.524(4) . ? C11 C12 1.527(4) . ? C11 H11 0.9800 . ? C13 C14 1.532(5) . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 C15 1.517(6) . ? C14 H14A 0.9700 . ? C14 H14B 0.9700 . ? C15 C16 1.542(5) . ? C15 H15A 0.9700 . ? C15 H15B 0.9700 . ? C16 C18 1.521(4) . ? C16 C17 1.539(5) . ? C17 H17A 0.9700 . ? C17 H17B 0.9700 . ? C19 H19A 0.9600 . ? C19 H19B 0.9600 . ? C19 H19C 0.9600 . ? 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 C12 N1 C16 115.3(2) . . ? C12 N1 C13 127.8(3) . . ? C16 N1 C13 113.3(3) . . ? C18 O2 C19 116.5(3) . . ? C10 O4 C11 116.2(2) . . ? C2 O6 C9 119.1(2) . . ? F2 C1 F3 107.3(3) . . ? F2 C1 F1 106.7(3) . . ? F3 C1 F1 105.8(3) . . ? F2 C1 C2 112.4(3) . . ? F3 C1 C2 111.8(3) . . ? F1 C1 C2 112.5(3) . . ? O6 C2 C3 113.7(2) . . ? O6 C2 C1 102.2(2) . . ? C3 C2 C1 109.3(3) . . ? O6 C2 C10 111.3(2) . . ? C3 C2 C10 112.0(2) . . ? C1 C2 C10 107.8(2) . . ? C4 C3 C8 119.2(3) . . ? C4 C3 C2 121.8(3) . . ? C8 C3 C2 119.0(3) . . ? C3 C4 C5 119.6(3) . . ? C3 C4 H4 120.2 . . ? C5 C4 H4 120.2 . . ? C6 C5 C4 120.7(4) . . ? C6 C5 H5 119.7 . . ? C4 C5 H5 119.7 . . ? C7 C6 C5 120.1(4) . . ? C7 C6 H6 120.0 . . ? C5 C6 H6 120.0 . . ? C6 C7 C8 119.8(3) . . ? C6 C7 H7 120.1 . . ? C8 C7 H7 120.1 . . ? C7 C8 C3 120.6(3) . . ? C7 C8 H8 119.7 . . ? C3 C8 H8 119.7 . . ? O6 C9 H9A 109.5 . . ? O6 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? O6 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? O5 C10 O4 125.0(3) . . ? O5 C10 C2 125.0(3) . . ? O4 C10 C2 110.0(2) . . ? O4 C11 C17 107.7(2) . . ? O4 C11 C12 106.6(2) . . ? C17 C11 C12 103.4(2) . . ? O4 C11 H11 112.8 . . ? C17 C11 H11 112.8 . . ? C12 C11 H11 112.8 . . ? O3 C12 N1 126.7(3) . . ? O3 C12 C11 126.5(3) . . ? N1 C12 C11 106.8(2) . . ? N1 C13 C14 103.3(3) . . ? N1 C13 H13A 111.1 . . ? C14 C13 H13A 111.1 . . ? N1 C13 H13B 111.1 . . ? C14 C13 H13B 111.1 . . ? H13A C13 H13B 109.1 . . ? C15 C14 C13 106.5(3) . . ? C15 C14 H14A 110.4 . . ? C13 C14 H14A 110.4 . . ? C15 C14 H14B 110.4 . . ? C13 C14 H14B 110.4 . . ? H14A C14 H14B 108.6 . . ? C14 C15 C16 103.8(3) . . ? C14 C15 H15A 111.0 . . ? C16 C15 H15A 111.0 . . ? C14 C15 H15B 111.0 . . ? C16 C15 H15B 111.0 . . ? H15A C15 H15B 109.0 . . ? N1 C16 C18 113.1(2) . . ? N1 C16 C15 101.9(3) . . ? C18 C16 C15 109.9(2) . . ? N1 C16 C17 102.8(2) . . ? C18 C16 C17 109.9(3) . . ? C15 C16 C17 119.0(3) . . ? C11 C17 C16 104.0(2) . . ? C11 C17 H17A 111.0 . . ? C16 C17 H17A 111.0 . . ? C11 C17 H17B 111.0 . . ? C16 C17 H17B 111.0 . . ? H17A C17 H17B 109.0 . . ? O1 C18 O2 124.4(3) . . ? O1 C18 C16 122.2(3) . . ? O2 C18 C16 113.4(3) . . ? O2 C19 H19A 109.5 . . ? O2 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? O2 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.942 _diffrn_reflns_theta_full 59.91 _diffrn_measured_fraction_theta_full 0.942 _refine_diff_density_max 0.197 _refine_diff_density_min -0.183 _refine_diff_density_rms 0.057