# Supplementary Material (ESI) for New Journal of Chemistry # This journal is (c) The Royal Society of Chemistry and # The Centre National de la Recherche Scientifique, 2006 data_global _journal_name_full 'New J.Chem.(Nouv.J.Chim.)' _journal_coden_cambridge 0440 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name _publ_author_address A.Avenoza ;Departamento de Qu\'imica C/Madre de Dios 51 ; J.H.Busto ;Departamento de Qu\'imica C/Madre de Dios 51 ; N.Canal ;Departamento de Qu\'imica C/Madre de Dios 51 ; J.Garcia ;Departamento de Qu\'imica C/Madre de Dios 51 ; G.Jimenez-Oses ;Departamento de Qu\'imica C/Madre de Dios 51 ; ; J.Peregrina ; ;Departamento de Qu\'imica C/Madre de Dios 51 ; M.Perez-Fernandez ;Departamento de Qu\'imica C/Madre de Dios 51 ; _publ_contact_author_address ;Departamento de Qu\'imica C/Madre de Dios 51 ; _publ_contact_author_email alberto.avenoza@dq.unirioja.es _publ_contact_author_name 'Prof. Alberto Avenoza Aznar' _publ_section_title ;Mechanistic Study of the Ring-Size Modulation in Michael-Dieckmann type Reactions of 2-Acylaminoacrylates with Ketene Diethyl Acetal ; data_publication_text _database_code_depnum_ccdc_archive 'CCDC 294888' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common mar147 _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H14 F3 N1 O5' _chemical_formula_weight 309.24 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' F F 0.0171 0.0103 '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 Triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.3685(2) _cell_length_b 9.1253(2) _cell_length_c 9.7248(3) _cell_angle_alpha 69.2894(10) _cell_angle_beta 82.1053(10) _cell_angle_gamma 77.1832(14) _cell_volume 675.92(3) _cell_formula_units_Z 2 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 7284 _cell_measurement_theta_min 0.21 _cell_measurement_theta_max 27.88 _exptl_crystal_description Prism _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.22 _exptl_crystal_density_diffrn 1.520 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 320 _exptl_absorpt_coefficient_mu 0.143 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9439 _diffrn_reflns_av_R_equivalents 0.0338 _diffrn_reflns_av_sigmaI/netI 0.0408 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.24 _diffrn_reflns_theta_max 27.89 _reflns_number_total 3169 _reflns_number_gt 2495 _reflns_threshold_expression >2sigma(I) _computing_data_collection KappaCCD _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski , 1997' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ORTEP-III _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^)+(0.0374P)^2^+0.1912P] 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 ? _refine_ls_number_reflns 3169 _refine_ls_number_parameters 190 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0542 _refine_ls_R_factor_gt 0.0385 _refine_ls_wR_factor_ref 0.0979 _refine_ls_wR_factor_gt 0.0900 _refine_ls_goodness_of_fit_ref 1.045 _refine_ls_restrained_S_all 1.045 _refine_ls_shift/su_max 0.000 _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 0.79895(13) 0.26156(13) 0.20150(11) 0.0240(2) Uani 1 1 d . . . H1 H 0.8988 0.2413 0.1593 0.029 Uiso 1 1 d R . . O2 O 1.02712(11) 0.34247(11) 0.37468(10) 0.0268(2) Uani 1 1 d . . . F3 F 0.88550(11) -0.02217(11) 0.13978(11) 0.0473(3) Uani 1 1 d . . . O4 O 0.87679(12) 0.76402(12) -0.06408(11) 0.0327(2) Uani 1 1 d . . . O5 O 0.66931(13) 0.35684(12) 0.53349(11) 0.0340(2) Uani 1 1 d . . . O6 O 0.54865(12) 0.18706(13) 0.26277(11) 0.0351(3) Uani 1 1 d . . . O7 O 0.78955(12) 0.12991(11) 0.49122(10) 0.0303(2) Uani 1 1 d . . . C8 C 0.92656(15) 0.43593(15) 0.26945(14) 0.0234(3) Uani 1 1 d . . . C9 C 0.68512(16) 0.17941(16) 0.20121(14) 0.0259(3) Uani 1 1 d . . . F10 F 0.63354(13) -0.02402(13) 0.12579(13) 0.0560(3) Uani 1 1 d . . . C11 C 0.83978(16) 0.65742(16) 0.04735(14) 0.0263(3) Uani 1 1 d . . . C12 C 0.95623(16) 0.56831(15) 0.15906(14) 0.0261(3) Uani 1 1 d . . . H12 H 1.0563 0.6056 0.1537 0.031 Uiso 1 1 d R . . F13 F 0.75027(14) 0.15619(13) -0.03549(10) 0.0551(3) Uani 1 1 d . . . C14 C 0.62874(16) 0.51329(16) 0.22651(15) 0.0267(3) Uani 1 1 d . . . H14A H 0.5306 0.4741 0.2289 0.032 Uiso 1 1 d R . . H14B H 0.6099 0.5795 0.2871 0.032 Uiso 1 1 d R . . C15 C 0.76909(15) 0.37170(15) 0.28564(14) 0.0229(3) Uani 1 1 d . . . C16 C 0.73368(16) 0.28571(16) 0.45194(14) 0.0247(3) Uani 1 1 d . . . C17 C 0.67283(17) 0.61348(17) 0.06881(15) 0.0299(3) Uani 1 1 d . . . H17A H 0.5907 0.7089 0.0423 0.036 Uiso 1 1 d R . . H17B H 0.6690 0.5522 0.0073 0.036 Uiso 1 1 d R . . C18 C 1.18577(17) 0.38249(18) 0.37476(16) 0.0315(3) Uani 1 1 d . . . H18A H 1.2528 0.3720 0.2891 0.038 Uiso 1 1 d R . . H18B H 1.1703 0.4904 0.3735 0.038 Uiso 1 1 d R . . C19 C 0.73929(18) 0.06995(18) 0.10742(16) 0.0314(3) Uani 1 1 d . . . C20 C 1.26226(18) 0.26853(19) 0.51326(16) 0.0357(3) Uani 1 1 d . . . H20A H 1.3679 0.2905 0.5183 0.043 Uiso 1 1 d R . . H20B H 1.2748 0.1615 0.5128 0.043 Uiso 1 1 d R . . H20C H 1.1924 0.2799 0.5972 0.043 Uiso 1 1 d R . . C21 C 0.7749(2) 0.04273(19) 0.64825(16) 0.0406(4) Uani 1 1 d . . . H21A H 0.8186 -0.0684 0.6657 0.049 Uiso 1 1 d R . . H21B H 0.6613 0.0559 0.6830 0.049 Uiso 1 1 d R . . H21C H 0.8352 0.0829 0.6997 0.049 Uiso 1 1 d 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 N1 0.0216(5) 0.0277(6) 0.0241(6) -0.0111(5) 0.0014(4) -0.0050(4) O2 0.0228(5) 0.0289(5) 0.0272(5) -0.0055(4) -0.0039(4) -0.0068(4) F3 0.0392(5) 0.0482(6) 0.0612(6) -0.0328(5) -0.0067(4) 0.0045(4) O4 0.0331(5) 0.0285(5) 0.0284(5) -0.0032(4) 0.0042(4) -0.0037(4) O5 0.0382(6) 0.0354(6) 0.0269(5) -0.0127(4) 0.0053(4) -0.0042(4) O6 0.0267(5) 0.0432(6) 0.0411(6) -0.0206(5) 0.0061(4) -0.0125(4) O7 0.0405(6) 0.0247(5) 0.0233(5) -0.0046(4) -0.0030(4) -0.0064(4) C8 0.0225(6) 0.0254(6) 0.0235(6) -0.0105(5) -0.0004(5) -0.0034(5) C9 0.0248(7) 0.0291(7) 0.0242(6) -0.0087(5) -0.0017(5) -0.0059(5) F10 0.0483(6) 0.0665(7) 0.0794(8) -0.0514(6) 0.0129(5) -0.0290(5) C11 0.0276(7) 0.0238(6) 0.0256(7) -0.0096(6) 0.0033(5) -0.0019(5) C12 0.0242(6) 0.0266(7) 0.0278(7) -0.0095(6) 0.0016(5) -0.0072(5) F13 0.0823(8) 0.0570(6) 0.0276(5) -0.0194(5) -0.0006(5) -0.0098(6) C14 0.0223(6) 0.0276(7) 0.0280(7) -0.0079(6) -0.0001(5) -0.0038(5) C15 0.0223(6) 0.0236(6) 0.0227(6) -0.0080(5) 0.0006(5) -0.0048(5) C16 0.0220(6) 0.0275(7) 0.0253(7) -0.0081(6) -0.0015(5) -0.0071(5) C17 0.0261(7) 0.0298(7) 0.0288(7) -0.0048(6) -0.0036(5) -0.0022(6) C18 0.0245(7) 0.0386(8) 0.0332(7) -0.0110(6) -0.0027(6) -0.0106(6) C19 0.0299(7) 0.0368(8) 0.0323(7) -0.0164(6) -0.0001(6) -0.0087(6) C20 0.0293(7) 0.0451(9) 0.0346(8) -0.0141(7) -0.0075(6) -0.0061(7) C21 0.0592(10) 0.0334(8) 0.0246(7) -0.0013(6) -0.0057(7) -0.0116(7) _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 C9 1.3373(17) . ? N1 C15 1.4683(17) . ? N1 H1 0.8896 . ? O2 C8 1.3355(16) . ? O2 C18 1.4531(15) . ? F3 C19 1.3285(17) . ? O4 C11 1.2298(16) . ? O5 C16 1.1968(16) . ? O6 C9 1.2140(16) . ? O7 C16 1.3250(16) . ? O7 C21 1.4534(16) . ? C8 C12 1.3475(18) . ? C8 C15 1.5248(17) . ? C9 C19 1.538(2) . ? F10 C19 1.3173(17) . ? C11 C12 1.4510(19) . ? C11 C17 1.5051(19) . ? C12 H12 0.9600 . ? F13 C19 1.3352(17) . ? C14 C17 1.5253(18) . ? C14 C15 1.5382(18) . ? C14 H14A 0.9600 . ? C14 H14B 0.9599 . ? C15 C16 1.5469(18) . ? C17 H17A 0.9601 . ? C17 H17B 0.9601 . ? C18 C20 1.502(2) . ? C18 H18A 0.9600 . ? C18 H18B 0.9601 . ? C20 H20A 0.9601 . ? C20 H20B 0.9600 . ? C20 H20C 0.9599 . ? C21 H21A 0.9601 . ? C21 H21B 0.9599 . ? C21 H21C 0.9599 . ? 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 C9 N1 C15 121.07(11) . . ? C9 N1 H1 120.0 . . ? C15 N1 H1 118.6 . . ? C8 O2 C18 119.04(10) . . ? C16 O7 C21 115.51(11) . . ? O2 C8 C12 126.47(12) . . ? O2 C8 C15 111.14(10) . . ? C12 C8 C15 122.37(11) . . ? O6 C9 N1 126.79(13) . . ? O6 C9 C19 119.77(12) . . ? N1 C9 C19 113.42(11) . . ? O4 C11 C12 121.24(12) . . ? O4 C11 C17 120.36(12) . . ? C12 C11 C17 118.38(11) . . ? C8 C12 C11 121.58(12) . . ? C8 C12 H12 119.7 . . ? C11 C12 H12 118.7 . . ? C17 C14 C15 110.69(11) . . ? C17 C14 H14A 109.3 . . ? C15 C14 H14A 109.4 . . ? C17 C14 H14B 108.6 . . ? C15 C14 H14B 109.3 . . ? H14A C14 H14B 109.5 . . ? N1 C15 C8 107.13(10) . . ? N1 C15 C14 111.97(11) . . ? C8 C15 C14 108.51(10) . . ? N1 C15 C16 111.84(10) . . ? C8 C15 C16 107.13(10) . . ? C14 C15 C16 110.04(10) . . ? O5 C16 O7 125.59(12) . . ? O5 C16 C15 122.08(12) . . ? O7 C16 C15 112.25(11) . . ? C11 C17 C14 113.85(11) . . ? C11 C17 H17A 109.4 . . ? C14 C17 H17A 107.7 . . ? C11 C17 H17B 109.3 . . ? C14 C17 H17B 107.0 . . ? H17A C17 H17B 109.5 . . ? O2 C18 C20 106.94(11) . . ? O2 C18 H18A 109.5 . . ? C20 C18 H18A 111.0 . . ? O2 C18 H18B 109.4 . . ? C20 C18 H18B 110.5 . . ? H18A C18 H18B 109.5 . . ? F10 C19 F3 107.64(12) . . ? F10 C19 F13 107.68(12) . . ? F3 C19 F13 107.01(12) . . ? F10 C19 C9 111.36(11) . . ? F3 C19 C9 112.38(11) . . ? F13 C19 C9 110.56(12) . . ? C18 C20 H20A 110.0 . . ? C18 C20 H20B 109.0 . . ? H20A C20 H20B 109.5 . . ? C18 C20 H20C 109.4 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? O7 C21 H21A 109.3 . . ? O7 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? O7 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 27.89 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 0.284 _refine_diff_density_min -0.199 _refine_diff_density_rms 0.039