Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Claudia Tomasini' 'Gaetano Angelici' 'Simone Contaldi' 'Sarah Lynn Green' _publ_contact_author_name 'Claudia Tomasini' _publ_contact_author_address ; Dipartimento di Chimica University of Bologna Via Selmi 2 Bologna 40126 ITALY ; _publ_contact_author_email CLAUDIA.TOMASINI@UNIBO.IT _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; Synthesis of 2-oxaimidazolidinone-4-carboxylate and of 2-(tetrahydro)pyrimidinone-6-carboxylate via an efficient modification of the Hofmann rearrangement ; data_compd2a _database_code_depnum_ccdc_archive 'CCDC 676653' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C13 H14 N2 O5' _chemical_formula_weight 278.26 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 9.6240(11) _cell_length_b 7.9566(9) _cell_length_c 9.8099(11) _cell_angle_alpha 90.00 _cell_angle_beta 118.0930(10) _cell_angle_gamma 90.00 _cell_volume 662.68(13) _cell_formula_units_Z 2 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description platelet _exptl_crystal_colour colorless _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.395 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 292 _exptl_absorpt_coefficient_mu 0.109 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.941 _exptl_absorpt_correction_T_max 0.996 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5616 _diffrn_reflns_av_R_equivalents 0.0189 _diffrn_reflns_av_sigmaI/netI 0.0188 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 3.48 _diffrn_reflns_theta_max 27.99 _reflns_number_total 1655 _reflns_number_gt 1433 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT+' _computing_structure_solution 'SIR-97 (Giacovazzo, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SCHAKAL-99 (Keller, 1999)' _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^)+(0.0448P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _chemical_absolute_configuration 'syn R' _refine_ls_number_reflns 1655 _refine_ls_number_parameters 186 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0391 _refine_ls_R_factor_gt 0.0320 _refine_ls_wR_factor_ref 0.0837 _refine_ls_wR_factor_gt 0.0799 _refine_ls_goodness_of_fit_ref 1.234 _refine_ls_restrained_S_all 1.234 _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 C9 C 1.0228(2) -0.0946(2) 0.6531(2) 0.0423(4) Uani 1 1 d . . . C8 C 0.8750(2) -0.0878(3) 0.6674(3) 0.0553(6) Uani 1 1 d . . . H8A H 0.7837 -0.0978 0.5663 0.066 Uiso 1 1 calc R . . H8B H 0.8730 -0.1792 0.7318 0.066 Uiso 1 1 calc R . . C14 C 1.1504(3) -0.1860(3) 0.7558(2) 0.0501(5) Uani 1 1 d . . . H14 H 1.1448 -0.2443 0.8353 0.060 Uiso 1 1 calc R . . C10 C 1.0327(3) -0.0093(3) 0.5359(3) 0.0627(7) Uani 1 1 d . . . H10 H 0.9474 0.0535 0.4657 0.075 Uiso 1 1 calc R . . C11 C 1.1692(4) -0.0169(4) 0.5226(4) 0.0780(8) Uani 1 1 d . . . H11 H 1.1754 0.0404 0.4430 0.094 Uiso 1 1 calc R . . C13 C 1.2859(3) -0.1921(4) 0.7427(3) 0.0638(7) Uani 1 1 d . . . H13 H 1.3717 -0.2537 0.8137 0.077 Uiso 1 1 calc R . . C12 C 1.2957(3) -0.1087(4) 0.6262(4) 0.0717(8) Uani 1 1 d . . . H12 H 1.3875 -0.1139 0.6170 0.086 Uiso 1 1 calc R . . O3 O 0.60787(16) 0.0800(2) 0.60568(18) 0.0562(4) Uani 1 1 d . . . O1 O 0.87307(15) 0.07387(18) 0.73727(17) 0.0494(4) Uani 1 1 d . . . C3 C 0.7327(2) 0.1386(3) 0.6972(2) 0.0399(4) Uani 1 1 d . . . N3 N 0.74155(17) 0.2897(2) 0.76867(18) 0.0408(4) Uani 1 1 d . . . O4 O 0.55900(18) 0.1814(2) 0.90164(18) 0.0588(4) Uani 1 1 d . . . O5 O 0.36979(16) 0.3662(2) 0.76076(19) 0.0558(4) Uani 1 1 d . . . C2 C 0.8755(2) 0.3754(2) 0.8802(2) 0.0362(4) Uani 1 1 d . . . C6 C 0.5094(2) 0.2930(3) 0.8099(2) 0.0406(4) Uani 1 1 d . . . C4 C 0.5973(2) 0.3787(3) 0.7355(2) 0.0400(4) Uani 1 1 d . . . H4 H 0.5298 0.3881 0.6237 0.048 Uiso 1 1 calc R . . C5 C 0.6574(2) 0.5528(3) 0.8063(3) 0.0540(5) Uani 1 1 d . . . H5A H 0.6389 0.6356 0.7270 0.065 Uiso 1 1 calc R . . H5B H 0.6077 0.5899 0.8671 0.065 Uiso 1 1 calc R . . C7 C 0.2764(3) 0.3137(4) 0.8337(3) 0.0696(8) Uani 1 1 d . . . H7A H 0.2672 0.1935 0.8296 0.104 Uiso 1 1 calc R . . H7B H 0.1735 0.3631 0.7804 0.104 Uiso 1 1 calc R . . H7C H 0.3268 0.3498 0.9396 0.104 Uiso 1 1 calc R . . O2 O 1.00996(15) 0.32330(17) 0.94347(16) 0.0464(4) Uani 1 1 d . . . N1 N 0.8246(2) 0.5233(2) 0.9031(2) 0.0481(4) Uani 1 1 d . . . H1 H 0.894(3) 0.598(4) 0.972(3) 0.068(8) Uiso 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 C9 0.0422(10) 0.0369(10) 0.0462(10) -0.0110(9) 0.0194(8) 0.0002(9) C8 0.0485(12) 0.0458(13) 0.0732(15) -0.0240(11) 0.0300(11) -0.0078(10) C14 0.0532(12) 0.0542(13) 0.0426(10) -0.0011(10) 0.0222(9) 0.0081(10) C10 0.0756(17) 0.0537(14) 0.0598(14) 0.0085(11) 0.0328(13) 0.0153(12) C11 0.115(2) 0.0615(16) 0.0896(19) 0.0031(15) 0.075(2) -0.0041(17) C13 0.0472(12) 0.0745(16) 0.0623(13) -0.0120(13) 0.0196(10) 0.0161(12) C12 0.0676(16) 0.0725(17) 0.099(2) -0.0207(17) 0.0587(16) -0.0047(15) O3 0.0328(7) 0.0691(11) 0.0604(9) -0.0257(8) 0.0166(7) -0.0084(7) O1 0.0348(7) 0.0464(8) 0.0610(9) -0.0182(7) 0.0176(6) 0.0007(6) C3 0.0325(9) 0.0478(11) 0.0416(10) -0.0076(8) 0.0194(8) -0.0025(8) N3 0.0256(7) 0.0451(9) 0.0467(8) -0.0075(8) 0.0129(6) 0.0009(6) O4 0.0542(9) 0.0629(10) 0.0550(9) 0.0139(8) 0.0222(7) 0.0080(8) O5 0.0372(7) 0.0705(11) 0.0666(9) 0.0172(8) 0.0300(7) 0.0116(7) C2 0.0320(9) 0.0366(10) 0.0408(9) 0.0022(8) 0.0177(7) 0.0008(8) C6 0.0335(9) 0.0463(11) 0.0363(9) -0.0047(9) 0.0117(7) 0.0017(8) C4 0.0286(8) 0.0449(11) 0.0447(10) 0.0000(9) 0.0156(7) 0.0046(8) C5 0.0366(10) 0.0433(12) 0.0775(14) -0.0014(11) 0.0231(10) 0.0060(9) C7 0.0533(13) 0.092(2) 0.0808(17) 0.0118(16) 0.0456(13) 0.0043(14) O2 0.0293(6) 0.0442(8) 0.0557(8) -0.0045(6) 0.0118(6) 0.0038(6) N1 0.0349(9) 0.0381(9) 0.0639(11) -0.0072(8) 0.0170(8) -0.0004(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 C9 C14 1.374(3) . ? C9 C10 1.377(3) . ? C9 C8 1.494(3) . ? C8 O1 1.462(3) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C14 C13 1.370(3) . ? C14 H14 0.9300 . ? C10 C11 1.382(4) . ? C10 H10 0.9300 . ? C11 C12 1.372(4) . ? C11 H11 0.9300 . ? C13 C12 1.362(4) . ? C13 H13 0.9300 . ? C12 H12 0.9300 . ? O3 C3 1.204(2) . ? O1 C3 1.321(2) . ? C3 N3 1.374(3) . ? N3 C2 1.413(2) . ? N3 C4 1.452(2) . ? O4 C6 1.193(3) . ? O5 C6 1.329(2) . ? O5 C7 1.449(3) . ? C2 O2 1.215(2) . ? C2 N1 1.333(3) . ? C6 C4 1.515(3) . ? C4 C5 1.535(3) . ? C4 H4 0.9800 . ? C5 N1 1.451(3) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C7 H7A 0.9600 . ? C7 H7B 0.9600 . ? C7 H7C 0.9600 . ? N1 H1 0.91(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 C14 C9 C10 119.0(2) . . ? C14 C9 C8 120.8(2) . . ? C10 C9 C8 120.2(2) . . ? O1 C8 C9 107.42(16) . . ? O1 C8 H8A 110.2 . . ? C9 C8 H8A 110.2 . . ? O1 C8 H8B 110.2 . . ? C9 C8 H8B 110.2 . . ? H8A C8 H8B 108.5 . . ? C13 C14 C9 120.8(2) . . ? C13 C14 H14 119.6 . . ? C9 C14 H14 119.6 . . ? C9 C10 C11 120.0(2) . . ? C9 C10 H10 120.0 . . ? C11 C10 H10 120.0 . . ? C12 C11 C10 120.3(2) . . ? C12 C11 H11 119.8 . . ? C10 C11 H11 119.8 . . ? C12 C13 C14 120.4(2) . . ? C12 C13 H13 119.8 . . ? C14 C13 H13 119.8 . . ? C13 C12 C11 119.6(2) . . ? C13 C12 H12 120.2 . . ? C11 C12 H12 120.2 . . ? C3 O1 C8 116.15(15) . . ? O3 C3 O1 126.32(19) . . ? O3 C3 N3 121.29(18) . . ? O1 C3 N3 112.35(16) . . ? C3 N3 C2 129.24(16) . . ? C3 N3 C4 119.31(16) . . ? C2 N3 C4 111.41(16) . . ? C6 O5 C7 116.77(19) . . ? O2 C2 N1 127.06(18) . . ? O2 C2 N3 126.49(18) . . ? N1 C2 N3 106.44(16) . . ? O4 C6 O5 125.3(2) . . ? O4 C6 C4 125.63(18) . . ? O5 C6 C4 109.07(17) . . ? N3 C4 C6 111.37(17) . . ? N3 C4 C5 102.83(15) . . ? C6 C4 C5 111.42(17) . . ? N3 C4 H4 110.3 . . ? C6 C4 H4 110.3 . . ? C5 C4 H4 110.3 . . ? N1 C5 C4 102.45(17) . . ? N1 C5 H5A 111.3 . . ? C4 C5 H5A 111.3 . . ? N1 C5 H5B 111.3 . . ? C4 C5 H5B 111.3 . . ? H5A C5 H5B 109.2 . . ? O5 C7 H7A 109.5 . . ? O5 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? O5 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C2 N1 C5 114.48(18) . . ? C2 N1 H1 120.2(18) . . ? C5 N1 H1 125.2(18) . . ? _diffrn_measured_fraction_theta_max 0.967 _diffrn_reflns_theta_full 27.99 _diffrn_measured_fraction_theta_full 0.967 _refine_diff_density_max 0.137 _refine_diff_density_min -0.126 _refine_diff_density_rms 0.028 #===END