# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2010 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Yu, Feng' 'Jin, Zhichao' 'Huang, Huicai' 'Ye, Tingting' 'Liang, Xinmiao' 'Ye, Jinxing' _publ_contact_author_name 'Ye, Jinxing' _publ_contact_author_email yejx@ecust.edu.cn _publ_section_title ; A Highly Efficient Asymmetric Michael Addition of \^I+-, \^I+-- Disubstituted Aldehydes to Maleimides Catalyzed by Primary Amine Thiourea Salt ; # Attachment '- cd201259.cif' data_cd201259 _database_code_depnum_ccdc_archive 'CCDC 778275' #TrackingRef '- cd201259.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C14 H14 Br N O3' _chemical_formula_weight 324.17 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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 6.607(3) _cell_length_b 10.212(4) _cell_length_c 20.641(8) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1392.7(9) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 2610 _cell_measurement_theta_min 4.450 _cell_measurement_theta_max 53.183 _exptl_crystal_description prismatic _exptl_crystal_colour colorless _exptl_crystal_size_max 0.367 _exptl_crystal_size_mid 0.351 _exptl_crystal_size_min 0.237 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.546 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 656 _exptl_absorpt_coefficient_mu 2.954 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.50343 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _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 7653 _diffrn_reflns_av_R_equivalents 0.0766 _diffrn_reflns_av_sigmaI/netI 0.0671 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 1.97 _diffrn_reflns_theta_max 26.00 _reflns_number_total 2719 _reflns_number_gt 2135 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0382P)^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 SHELXL _refine_ls_extinction_coef 0.0075(11) _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 0.022(13) _chemical_absolute_configuration ad _refine_ls_number_reflns 2719 _refine_ls_number_parameters 175 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0511 _refine_ls_R_factor_gt 0.0398 _refine_ls_wR_factor_ref 0.0850 _refine_ls_wR_factor_gt 0.0822 _refine_ls_goodness_of_fit_ref 0.913 _refine_ls_restrained_S_all 0.913 _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 Br1 Br 1.23702(7) 0.84842(4) 0.784914(17) 0.05981(18) Uani 1 1 d . . . N1 N 0.8159(4) 0.5950(3) 0.55606(13) 0.0338(7) Uani 1 1 d . . . O1 O 1.0502(4) 0.6604(3) 0.48169(12) 0.0577(8) Uani 1 1 d . . . O2 O 0.5445(4) 0.5017(3) 0.60752(12) 0.0498(7) Uani 1 1 d . . . O3 O 0.9324(6) 0.3257(3) 0.50693(16) 0.0867(12) Uani 1 1 d . . . C1 C 0.8934(6) 0.6066(3) 0.49380(17) 0.0396(9) Uani 1 1 d . . . C2 C 0.6328(5) 0.5303(4) 0.55849(17) 0.0362(8) Uani 1 1 d . . . C3 C 0.5663(6) 0.5065(3) 0.49042(17) 0.0435(9) Uani 1 1 d . . . H3A H 0.4504 0.5608 0.4799 0.052 Uiso 1 1 calc R . . H3B H 0.5292 0.4154 0.4845 0.052 Uiso 1 1 calc R . . C4 C 0.7459(6) 0.5418(3) 0.44743(14) 0.0382(8) Uani 1 1 d . . . H4 H 0.7002 0.6088 0.4168 0.046 Uiso 1 1 calc R . . C5 C 0.8322(6) 0.4282(4) 0.40793(18) 0.0469(10) Uani 1 1 d . . . C6 C 0.9084(8) 0.3209(4) 0.4505(2) 0.0700(14) Uani 1 1 d . . . H6 H 0.9403 0.2420 0.4304 0.084 Uiso 1 1 calc R . . C7 C 1.0151(8) 0.4711(4) 0.3659(2) 0.0707(13) Uani 1 1 d . . . H7A H 1.1181 0.5076 0.3933 0.106 Uiso 1 1 calc R . . H7B H 0.9719 0.5358 0.3351 0.106 Uiso 1 1 calc R . . H7C H 1.0684 0.3966 0.3433 0.106 Uiso 1 1 calc R . . C8 C 0.6705(7) 0.3700(4) 0.3634(2) 0.0696(13) Uani 1 1 d . . . H8A H 0.7254 0.2958 0.3409 0.104 Uiso 1 1 calc R . . H8B H 0.6284 0.4349 0.3325 0.104 Uiso 1 1 calc R . . H8C H 0.5562 0.3429 0.3887 0.104 Uiso 1 1 calc R . . C9 C 0.9144(5) 0.6490(3) 0.61201(15) 0.0338(7) Uani 1 1 d . . . C10 C 0.8133(6) 0.7399(4) 0.64884(17) 0.0444(10) Uani 1 1 d . . . H10 H 0.6810 0.7629 0.6385 0.053 Uiso 1 1 calc R . . C11 C 0.9083(6) 0.7970(4) 0.70115(17) 0.0503(10) Uani 1 1 d . . . H11 H 0.8413 0.8588 0.7263 0.060 Uiso 1 1 calc R . . C12 C 1.1014(6) 0.7614(3) 0.71533(17) 0.0424(9) Uani 1 1 d . . . C13 C 1.2027(5) 0.6685(3) 0.68054(18) 0.0425(9) Uani 1 1 d . . . H13 H 1.3340 0.6446 0.6917 0.051 Uiso 1 1 calc R . . C14 C 1.1059(5) 0.6106(3) 0.62828(17) 0.0414(9) Uani 1 1 d . . . H14 H 1.1710 0.5459 0.6044 0.050 Uiso 1 1 calc 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 Br1 0.0776(3) 0.0613(3) 0.0405(2) -0.00479(18) -0.0144(2) -0.0081(3) N1 0.0352(16) 0.0317(15) 0.0345(15) -0.0020(12) 0.0000(12) -0.0024(13) O1 0.0659(19) 0.0624(18) 0.0447(15) -0.0060(14) 0.0118(13) -0.0324(17) O2 0.0386(15) 0.0592(19) 0.0517(16) 0.0082(13) 0.0069(12) -0.0051(13) O3 0.147(3) 0.0511(19) 0.062(2) 0.0025(16) -0.021(2) 0.040(2) C1 0.051(2) 0.031(2) 0.037(2) 0.0006(15) 0.0035(17) -0.0067(18) C2 0.036(2) 0.0320(19) 0.041(2) 0.0029(17) -0.0029(17) 0.0047(17) C3 0.044(2) 0.036(2) 0.051(2) 0.0018(17) -0.0105(18) -0.0033(17) C4 0.051(2) 0.0277(16) 0.0356(16) 0.0050(13) -0.009(2) -0.001(2) C5 0.067(3) 0.031(2) 0.042(2) -0.0019(16) -0.0045(18) -0.0015(18) C6 0.109(4) 0.030(2) 0.071(3) -0.003(2) -0.003(3) 0.015(2) C7 0.093(4) 0.063(3) 0.056(3) -0.015(2) 0.016(3) -0.005(3) C8 0.096(4) 0.061(3) 0.051(3) -0.010(2) -0.006(2) -0.024(3) C9 0.0350(19) 0.0287(17) 0.0376(18) -0.0006(16) -0.0014(14) -0.0019(18) C10 0.042(2) 0.046(2) 0.045(2) -0.0026(17) -0.0057(17) 0.0104(17) C11 0.056(3) 0.054(2) 0.041(2) -0.0105(18) 0.0010(19) 0.015(2) C12 0.056(2) 0.039(2) 0.0323(18) -0.0009(17) -0.0050(19) -0.0029(18) C13 0.037(2) 0.044(2) 0.046(2) -0.0019(17) -0.0079(16) -0.0029(18) C14 0.041(2) 0.041(2) 0.042(2) -0.0020(17) 0.0042(17) 0.0064(17) _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 Br1 C12 1.912(4) . ? N1 C2 1.380(4) . ? N1 C1 1.388(4) . ? N1 C9 1.435(4) . ? O1 C1 1.199(4) . ? O2 C2 1.204(4) . ? O3 C6 1.176(5) . ? C1 C4 1.518(5) . ? C2 C3 1.492(5) . ? C3 C4 1.525(5) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 C5 1.528(5) . ? C4 H4 0.9800 . ? C5 C6 1.492(6) . ? C5 C8 1.530(5) . ? C5 C7 1.550(6) . ? C6 H6 0.9300 . ? C7 H7A 0.9600 . ? C7 H7B 0.9600 . ? C7 H7C 0.9600 . ? C8 H8A 0.9600 . ? C8 H8B 0.9600 . ? C8 H8C 0.9600 . ? C9 C14 1.366(5) . ? C9 C10 1.373(5) . ? C10 C11 1.378(5) . ? C10 H10 0.9300 . ? C11 C12 1.359(5) . ? C11 H11 0.9300 . ? C12 C13 1.365(5) . ? C13 C14 1.387(5) . ? C13 H13 0.9300 . ? C14 H14 0.9300 . ? 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 C2 N1 C1 113.4(3) . . ? C2 N1 C9 123.5(3) . . ? C1 N1 C9 123.0(3) . . ? O1 C1 N1 123.4(3) . . ? O1 C1 C4 128.5(3) . . ? N1 C1 C4 108.1(3) . . ? O2 C2 N1 124.8(3) . . ? O2 C2 C3 127.6(3) . . ? N1 C2 C3 107.6(3) . . ? C2 C3 C4 106.3(3) . . ? C2 C3 H3A 110.5 . . ? C4 C3 H3A 110.5 . . ? C2 C3 H3B 110.5 . . ? C4 C3 H3B 110.5 . . ? H3A C3 H3B 108.7 . . ? C1 C4 C3 103.6(3) . . ? C1 C4 C5 115.3(3) . . ? C3 C4 C5 114.9(3) . . ? C1 C4 H4 107.5 . . ? C3 C4 H4 107.5 . . ? C5 C4 H4 107.5 . . ? C6 C5 C4 111.7(3) . . ? C6 C5 C8 107.7(3) . . ? C4 C5 C8 110.8(3) . . ? C6 C5 C7 105.9(4) . . ? C4 C5 C7 112.0(3) . . ? C8 C5 C7 108.5(3) . . ? O3 C6 C5 126.7(4) . . ? O3 C6 H6 116.7 . . ? C5 C6 H6 116.7 . . ? C5 C7 H7A 109.5 . . ? C5 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C5 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C5 C8 H8A 109.5 . . ? C5 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C5 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C14 C9 C10 120.5(3) . . ? C14 C9 N1 120.5(3) . . ? C10 C9 N1 119.0(3) . . ? C9 C10 C11 119.9(3) . . ? C9 C10 H10 120.1 . . ? C11 C10 H10 120.1 . . ? C12 C11 C10 118.9(4) . . ? C12 C11 H11 120.5 . . ? C10 C11 H11 120.5 . . ? C11 C12 C13 122.2(3) . . ? C11 C12 Br1 118.6(3) . . ? C13 C12 Br1 119.2(3) . . ? C12 C13 C14 118.6(3) . . ? C12 C13 H13 120.7 . . ? C14 C13 H13 120.7 . . ? C9 C14 C13 119.7(3) . . ? C9 C14 H14 120.1 . . ? C13 C14 H14 120.1 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C2 N1 C1 O1 179.5(4) . . . . ? C9 N1 C1 O1 1.4(5) . . . . ? C2 N1 C1 C4 -0.1(4) . . . . ? C9 N1 C1 C4 -178.2(3) . . . . ? C1 N1 C2 O2 175.0(4) . . . . ? C9 N1 C2 O2 -6.9(5) . . . . ? C1 N1 C2 C3 -6.3(4) . . . . ? C9 N1 C2 C3 171.9(3) . . . . ? O2 C2 C3 C4 -171.4(4) . . . . ? N1 C2 C3 C4 9.9(4) . . . . ? O1 C1 C4 C3 -173.5(4) . . . . ? N1 C1 C4 C3 6.1(4) . . . . ? O1 C1 C4 C5 60.1(5) . . . . ? N1 C1 C4 C5 -120.3(3) . . . . ? C2 C3 C4 C1 -9.5(4) . . . . ? C2 C3 C4 C5 117.2(3) . . . . ? C1 C4 C5 C6 59.5(4) . . . . ? C3 C4 C5 C6 -60.9(5) . . . . ? C1 C4 C5 C8 179.6(3) . . . . ? C3 C4 C5 C8 59.1(4) . . . . ? C1 C4 C5 C7 -59.0(4) . . . . ? C3 C4 C5 C7 -179.5(3) . . . . ? C4 C5 C6 O3 -11.4(8) . . . . ? C8 C5 C6 O3 -133.3(6) . . . . ? C7 C5 C6 O3 110.7(6) . . . . ? C2 N1 C9 C14 122.5(3) . . . . ? C1 N1 C9 C14 -59.6(5) . . . . ? C2 N1 C9 C10 -57.6(5) . . . . ? C1 N1 C9 C10 120.3(4) . . . . ? C14 C9 C10 C11 2.6(6) . . . . ? N1 C9 C10 C11 -177.3(3) . . . . ? C9 C10 C11 C12 -0.2(6) . . . . ? C10 C11 C12 C13 -1.8(6) . . . . ? C10 C11 C12 Br1 176.5(3) . . . . ? C11 C12 C13 C14 1.3(6) . . . . ? Br1 C12 C13 C14 -177.0(2) . . . . ? C10 C9 C14 C13 -3.2(5) . . . . ? N1 C9 C14 C13 176.7(3) . . . . ? C12 C13 C14 C9 1.2(5) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A C3 H3B O3 0.97 2.55 3.506(5) 168.7 4_456 C6 H6 O2 0.93 2.70 3.619(5) 170.2 4_556 C13 H13 O2 0.93 2.66 3.205(5) 118.1 1_655 C14 H14 O2 0.93 2.51 3.134(5) 124.7 1_655 _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.446 _refine_diff_density_min -0.389 _refine_diff_density_rms 0.078