# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Zhen-Yuan Xu' 'Yi Guo' 'Zhao-Bo Li' 'Shu Ping Luo' 'Ai-Bao Xia' _publ_contact_author_name 'Dan-Qian Xu' _publ_contact_author_email CHRC@ZJUT.EDU.CN _publ_section_title ; The highly enantioselective Michael addition of ketones to nitrodienes catalyzed by the efficient organocatalyst system of pyrrolidinyl-thioimidazole and chiral thioureido acid ; # Attachment 'CIF_20090716_.cif' data_LZB-Cy-Cl _database_code_depnum_ccdc_archive 'CCDC 744505' #TrackingRef 'CIF_20090716_.cif' #============================================================================== # CHEMICAL DATA _chemical_formula_sum 'C16 H18 Cl N O3 ' _chemical_formula_moiety 'C16 H18 Cl N O3 ' _chemical_formula_weight 307.78 _chemical_melting_point ? _chemical_absolute_configuration 'CHOOSE rm ad rmad syn or unk' #============================================================================== # CRYSTAL DATA _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' _symmetry_space_group_name_Hall 'P 2ac 2ab' _symmetry_Int_Tables_number 19 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 +X,+Y,+Z 2 1/2+X,1/2-Y,-Z 3 -X,1/2+Y,1/2-Z 4 1/2-X,-Y,1/2+Z #------------------------------------------------------------------------------ _cell_length_a 5.5300(3) _cell_length_b 8.5175(6) _cell_length_c 34.0903(18) _cell_angle_alpha 90.0000 _cell_angle_beta 90.0000 _cell_angle_gamma 90.0000 _cell_volume 1605.71(17) _cell_formula_units_Z 4 _cell_measurement_reflns_used 9533 _cell_measurement_theta_min 3.0 _cell_measurement_theta_max 27.4 _cell_measurement_temperature 296(1) #------------------------------------------------------------------------------ _exptl_crystal_description chunk _exptl_crystal_colour colorless _exptl_crystal_size_max 0.48 _exptl_crystal_size_mid 0.32 _exptl_crystal_size_min 0.28 _exptl_crystal_density_diffrn 1.273 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 648.00 _exptl_absorpt_coefficient_mu 0.246 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; Higashi, T. (1995). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. ; _exptl_absorpt_correction_T_min 0.879 _exptl_absorpt_correction_T_max 0.933 #============================================================================== # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71075 _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 10.00 _diffrn_reflns_number 15644 _diffrn_reflns_av_R_equivalents 0.034 _diffrn_reflns_theta_max 27.43 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.43 _diffrn_measured_fraction_theta_full 0.998 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -43 _diffrn_reflns_limit_l_max 44 #============================================================================== # REFINEMENT DATA _refine_special_details ; Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F^2^. R-factor (gt) are based on F. The threshold expression of F^2^ > 2.0 sigma(F^2^) is used only for calculating R-factor (gt). ; _reflns_number_total 2148 _reflns_number_gt 1391 _reflns_threshold_expression F^2^>2.0\s(F^2^) _refine_ls_structure_factor_coef Fsqd _refine_ls_R_factor_gt 0.0436 _refine_ls_wR_factor_ref 0.1238 _refine_ls_hydrogen_treatment constr _refine_ls_number_reflns 2148 _refine_ls_number_parameters 192 _refine_ls_goodness_of_fit_ref 1.000 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[\s^2^(Fo^2^)+(0.0320P)^2^+1.2000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_shift/su_max 0.0010 _refine_diff_density_max 0.22 _refine_diff_density_min -0.27 _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.027(2) _refine_ls_abs_structure_details 'Flack, H. D. (1983), Acta Cryst. A39, 876-881. 1486 Friedel Pairs' _refine_ls_abs_structure_Flack 0.27(18) loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.003 0.002 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; H H 0.000 0.000 ; International Tables for Crystallography (1992, Vol. C, Table 6.1.1.4) ; O O 0.011 0.006 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; N N 0.006 0.003 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; Cl Cl 0.148 0.159 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; #============================================================================== # ATOMIC COORDINATES AND THERMAL PARAMETERS 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 Cl1 Cl 0.6163(3) 0.6280(2) 1.07164(3) 0.1211(6) Uani 1.00 1 d . . . O1 O 0.9458(5) 0.1436(3) 0.77121(8) 0.0735(8) Uani 1.00 1 d . . . O2 O 1.2699(5) 0.5169(4) 0.83637(10) 0.0841(9) Uani 1.00 1 d . . . O3 O 0.9882(6) 0.6855(3) 0.84395(12) 0.1019(12) Uani 1.00 1 d . . . N1 N 1.0607(6) 0.5581(4) 0.83299(10) 0.0633(8) Uani 1.00 1 d . . . C1 C 0.8554(6) 0.3047(4) 0.84336(9) 0.0497(8) Uani 1.00 1 d . . . C2 C 0.6749(6) 0.1873(4) 0.82559(9) 0.0486(7) Uani 1.00 1 d . . . C3 C 0.6291(9) 0.0456(4) 0.85244(10) 0.0705(12) Uani 1.00 1 d . . . C4 C 0.4412(9) -0.0647(5) 0.83580(12) 0.0801(13) Uani 1.00 1 d . . . C5 C 0.5077(9) -0.1218(5) 0.79532(12) 0.0764(12) Uani 1.00 1 d . . . C6 C 0.5632(7) 0.0143(4) 0.76796(10) 0.0643(10) Uani 1.00 1 d . . . C7 C 0.7474(7) 0.1200(4) 0.78612(10) 0.0532(8) Uani 1.00 1 d . . . C8 C 0.8838(7) 0.4463(4) 0.81622(10) 0.0562(9) Uani 1.00 1 d . . . C9 C 0.7707(7) 0.3624(4) 0.88279(9) 0.0552(8) Uani 1.00 1 d . . . C10 C 0.8919(7) 0.3590(4) 0.91561(10) 0.0601(9) Uani 1.00 1 d . . . C11 C 0.8194(7) 0.4250(4) 0.95375(10) 0.0596(9) Uani 1.00 1 d . . . C12 C 0.6144(9) 0.5173(5) 0.95838(12) 0.0754(12) Uani 1.00 1 d . . . C13 C 0.5508(9) 0.5783(5) 0.99460(12) 0.0809(13) Uani 1.00 1 d . . . C14 C 0.6932(9) 0.5491(5) 1.02636(12) 0.0754(12) Uani 1.00 1 d . . . C15 C 0.8973(10) 0.4591(6) 1.02286(12) 0.0837(14) Uani 1.00 1 d . . . C16 C 0.9577(8) 0.3972(5) 0.98675(11) 0.0726(12) Uani 1.00 1 d . . . H1 H 1.0127 0.2531 0.8464 0.060 Uiso 1.00 1 c R . . H2 H 0.5206 0.2421 0.8221 0.058 Uiso 1.00 1 c R . . H9 H 0.6159 0.4048 0.8839 0.066 Uiso 1.00 1 c R . . H10 H 1.0415 0.3092 0.9148 0.072 Uiso 1.00 1 c R . . H12 H 0.5177 0.5386 0.9367 0.090 Uiso 1.00 1 c R . . H13 H 0.4118 0.6389 0.9972 0.097 Uiso 1.00 1 c R . . H15 H 0.9943 0.4398 1.0446 0.100 Uiso 1.00 1 c R . . H16 H 1.0952 0.3350 0.9846 0.087 Uiso 1.00 1 c R . . H31 H 0.7795 -0.0114 0.8558 0.085 Uiso 1.00 1 c R . . H32 H 0.5737 0.0833 0.8777 0.085 Uiso 1.00 1 c R . . H41 H 0.4259 -0.1546 0.8531 0.096 Uiso 1.00 1 c R . . H42 H 0.2875 -0.0101 0.8344 0.096 Uiso 1.00 1 c R . . H51 H 0.3737 -0.1816 0.7847 0.092 Uiso 1.00 1 c R . . H52 H 0.6493 -0.1886 0.7972 0.092 Uiso 1.00 1 c R . . H61 H 0.6255 -0.0263 0.7434 0.077 Uiso 1.00 1 c R . . H62 H 0.4162 0.0732 0.7631 0.077 Uiso 1.00 1 c R . . H81 H 0.9403 0.4111 0.7908 0.067 Uiso 1.00 1 c R . . H82 H 0.7287 0.4981 0.8133 0.067 Uiso 1.00 1 c 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_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Cl1 0.1546(14) 0.1453(13) 0.0635(6) -0.0040(13) 0.0179(8) -0.0299(7) O1 0.0658(17) 0.0833(19) 0.0716(16) -0.0074(17) 0.0162(14) -0.0129(15) O2 0.0494(16) 0.086(2) 0.117(2) -0.0064(16) -0.0101(17) 0.006(2) O3 0.087(2) 0.0605(17) 0.158(3) -0.005(2) -0.018(2) -0.023(2) N1 0.0585(19) 0.0535(18) 0.078(2) -0.0089(18) -0.0045(18) 0.0029(17) C1 0.0521(19) 0.0498(18) 0.0472(16) -0.0037(18) -0.0020(16) -0.0009(15) C2 0.0516(18) 0.0480(18) 0.0462(15) -0.0035(17) 0.0013(15) -0.0015(14) C3 0.101(3) 0.061(2) 0.0486(18) -0.032(2) 0.001(2) 0.0005(17) C4 0.109(3) 0.067(2) 0.064(2) -0.037(2) -0.000(2) -0.003(2) C5 0.095(3) 0.058(2) 0.076(2) -0.010(2) -0.009(2) -0.009(2) C6 0.072(2) 0.068(2) 0.0534(19) -0.009(2) -0.0023(19) -0.0126(18) C7 0.057(2) 0.053(2) 0.0501(17) 0.0003(19) -0.0022(17) -0.0014(16) C8 0.060(2) 0.050(2) 0.0583(19) -0.014(2) -0.0097(18) 0.0038(16) C9 0.058(2) 0.055(2) 0.0526(17) -0.0046(19) -0.0029(17) -0.0023(17) C10 0.063(2) 0.064(2) 0.0537(18) 0.005(2) -0.0053(18) -0.0025(17) C11 0.064(2) 0.060(2) 0.0547(19) -0.005(2) -0.0032(18) -0.0040(17) C12 0.079(2) 0.089(3) 0.058(2) 0.010(2) -0.006(2) -0.006(2) C13 0.085(3) 0.089(3) 0.069(2) 0.014(3) 0.002(2) -0.012(2) C14 0.090(3) 0.079(2) 0.058(2) -0.012(3) 0.006(2) -0.007(2) C15 0.097(3) 0.101(3) 0.053(2) -0.006(3) -0.011(2) -0.005(2) C16 0.075(2) 0.085(3) 0.059(2) 0.004(2) -0.011(2) -0.003(2) #============================================================================== _computing_data_collection 'PROCESS-AUTO (Rigaku,2006)' _computing_cell_refinement 'PROCESS-AUTO (Rigaku,2006)' _computing_data_reduction 'CrystalStructure (Rigaku,2007)' _computing_structure_solution 'SIR97 (Altomare,1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'CrystalStructure 3.7.0 (Rigaku,2007)' _computing_molecular_graphics 'Ortep3 for windows (Farrugia,1997)' #============================================================================== # MOLECULAR GEOMETRY _geom_special_details ; ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_publ_flag _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 Cl1 C14 1.736(4) ? . . O1 C7 1.226(4) ? . . O2 N1 1.214(4) ? . . O3 N1 1.216(4) ? . . N1 C8 1.480(5) ? . . C1 C2 1.537(4) ? . . C1 C8 1.528(4) ? . . C1 C9 1.506(4) ? . . C2 C3 1.536(5) ? . . C2 C7 1.516(4) ? . . C3 C4 1.512(6) ? . . C4 C5 1.509(5) ? . . C5 C6 1.519(5) ? . . C6 C7 1.494(5) ? . . C9 C10 1.305(4) ? . . C10 C11 1.472(5) ? . . C11 C12 1.389(6) ? . . C11 C16 1.381(5) ? . . C12 C13 1.385(6) ? . . C13 C14 1.362(6) ? . . C14 C15 1.370(7) ? . . C15 C16 1.380(5) ? . . C1 H1 0.980 ? . . C2 H2 0.980 ? . . C3 H31 0.970 ? . . C3 H32 0.970 ? . . C4 H41 0.970 ? . . C4 H42 0.970 ? . . C5 H51 0.970 ? . . C5 H52 0.970 ? . . C6 H61 0.970 ? . . C6 H62 0.970 ? . . C8 H81 0.970 ? . . C8 H82 0.970 ? . . C9 H9 0.930 ? . . C10 H10 0.930 ? . . C12 H12 0.930 ? . . C13 H13 0.930 ? . . C15 H15 0.930 ? . . C16 H16 0.930 ? . . loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_publ_flag _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 O2 N1 O3 122.9(3) ? . . . O2 N1 C8 118.7(3) ? . . . O3 N1 C8 118.4(3) ? . . . C2 C1 C8 110.0(2) ? . . . C2 C1 C9 111.2(2) ? . . . C8 C1 C9 108.3(2) ? . . . C1 C2 C3 112.5(2) ? . . . C1 C2 C7 115.1(2) ? . . . C3 C2 C7 106.0(2) ? . . . C2 C3 C4 112.2(3) ? . . . C3 C4 C5 112.1(3) ? . . . C4 C5 C6 111.4(3) ? . . . C5 C6 C7 110.1(3) ? . . . O1 C7 C2 122.9(3) ? . . . O1 C7 C6 122.5(3) ? . . . C2 C7 C6 114.5(3) ? . . . N1 C8 C1 110.0(2) ? . . . C1 C9 C10 126.8(3) ? . . . C9 C10 C11 127.5(3) ? . . . C10 C11 C12 122.6(3) ? . . . C10 C11 C16 120.2(3) ? . . . C12 C11 C16 117.2(3) ? . . . C11 C12 C13 121.4(4) ? . . . C12 C13 C14 119.6(4) ? . . . Cl1 C14 C13 119.6(3) ? . . . Cl1 C14 C15 119.7(3) ? . . . C13 C14 C15 120.6(4) ? . . . C14 C15 C16 119.4(4) ? . . . C11 C16 C15 121.8(4) ? . . . C2 C1 H1 109.1 ? . . . C8 C1 H1 109.1 ? . . . C9 C1 H1 109.1 ? . . . C1 C2 H2 107.6 ? . . . C3 C2 H2 107.6 ? . . . C7 C2 H2 107.6 ? . . . C2 C3 H31 108.8 ? . . . C2 C3 H32 108.8 ? . . . C4 C3 H31 108.8 ? . . . C4 C3 H32 108.8 ? . . . H31 C3 H32 109.5 ? . . . C3 C4 H41 108.8 ? . . . C3 C4 H42 108.8 ? . . . C5 C4 H41 108.8 ? . . . C5 C4 H42 108.8 ? . . . H41 C4 H42 109.5 ? . . . C4 C5 H51 109.0 ? . . . C4 C5 H52 109.0 ? . . . C6 C5 H51 109.0 ? . . . C6 C5 H52 109.0 ? . . . H51 C5 H52 109.5 ? . . . C5 C6 H61 109.3 ? . . . C5 C6 H62 109.3 ? . . . C7 C6 H61 109.3 ? . . . C7 C6 H62 109.3 ? . . . H61 C6 H62 109.5 ? . . . N1 C8 H81 109.3 ? . . . N1 C8 H82 109.3 ? . . . C1 C8 H81 109.3 ? . . . C1 C8 H82 109.3 ? . . . H81 C8 H82 109.5 ? . . . C1 C9 H9 116.6 ? . . . C10 C9 H9 116.6 ? . . . C9 C10 H10 116.2 ? . . . C11 C10 H10 116.2 ? . . . C11 C12 H12 119.3 ? . . . C13 C12 H12 119.3 ? . . . C12 C13 H13 120.2 ? . . . C14 C13 H13 120.2 ? . . . C14 C15 H15 120.3 ? . . . C16 C15 H15 120.3 ? . . . C11 C16 H16 119.1 ? . . . C15 C16 H16 119.1 ? . . . 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_publ_flag _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 O2 N1 C8 C1 64.7(4) ? . . . . O3 N1 C8 C1 -112.9(3) ? . . . . C2 C1 C8 N1 -179.0(2) ? . . . . C8 C1 C2 C3 -177.3(3) ? . . . . C8 C1 C2 C7 61.1(3) ? . . . . C2 C1 C9 C10 126.2(4) ? . . . . C9 C1 C2 C3 -57.3(4) ? . . . . C9 C1 C2 C7 -178.8(2) ? . . . . C8 C1 C9 C10 -112.8(4) ? . . . . C9 C1 C8 N1 59.2(3) ? . . . . C1 C2 C3 C4 176.8(3) ? . . . . C1 C2 C7 O1 7.5(5) ? . . . . C1 C2 C7 C6 -176.2(3) ? . . . . C3 C2 C7 O1 -117.6(4) ? . . . . C3 C2 C7 C6 58.7(4) ? . . . . C7 C2 C3 C4 -56.6(4) ? . . . . C2 C3 C4 C5 56.4(4) ? . . . . C3 C4 C5 C6 -52.9(5) ? . . . . C4 C5 C6 C7 52.5(5) ? . . . . C5 C6 C7 O1 118.3(4) ? . . . . C5 C6 C7 C2 -58.0(4) ? . . . . C1 C9 C10 C11 175.2(3) ? . . . . C9 C10 C11 C12 -7.3(6) ? . . . . C9 C10 C11 C16 173.2(4) ? . . . . C10 C11 C12 C13 -179.8(4) ? . . . . C10 C11 C16 C15 179.0(4) ? . . . . C12 C11 C16 C15 -0.6(6) ? . . . . C16 C11 C12 C13 -0.2(6) ? . . . . C11 C12 C13 C14 0.8(7) ? . . . . C12 C13 C14 Cl1 179.0(3) ? . . . . C12 C13 C14 C15 -0.5(7) ? . . . . Cl1 C14 C15 C16 -179.8(3) ? . . . . C13 C14 C15 C16 -0.3(6) ? . . . . C14 C15 C16 C11 0.8(7) ? . . . . #============================================================================== # Additional structures and associated data_? identifiers # should be added at this point if there is more than one # structure analysis in the CIF. #============================================================================== # End of CIF #==============================================================================