# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Jian Sun' _publ_contact_author_address ; Chengdu Institute of Biology Chinese Academy of Sciences Chengdu 610041 CHINA ; _publ_contact_author_email SUNJIAN@CIB.AC.CN _publ_section_title ; Protonated N'-benzyl-N'-prolyl Proline Hydrazide as Highly Enantioselective Catalyst for Direct Asymmetric Aldol Reaction ; loop_ _publ_author_name 'Jian Sun' 'Chuanling Cheng' 'Fan Jiang' 'Chao Wang' 'Siyu Wei' ; Yun-Dong Wu ; 'Yu Zhang' # Attachment '12.CIF' data_y1859 _database_code_depnum_ccdc_archive 'CCDC 281902' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Pyrrolidine-2S-carboxylic acid N'-(pyrrolidine-2S-carbonyl)-hydrazide ; _chemical_name_common ;Pyrrolidine-2S-carboxylic acid N'-(pyrrolidine-2S-carbonyl)- hydrazide ; _chemical_melting_point 428.3-431.3 _chemical_formula_moiety ? _chemical_formula_sum C10H18N4O2 _chemical_formula_weight 226.28 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 0.0000 '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 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0000 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' _cell_length_a 9.705(1) _cell_length_b 7.660(1) _cell_length_c 7.818(1) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 581.23(17) _cell_formula_units_Z 2 _cell_measurement_temperature 286(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 2.61 _cell_measurement_theta_max 14.28 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.56 _exptl_crystal_size_mid 0.46 _exptl_crystal_size_min 0.42 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.293 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 244 _exptl_absorpt_coefficient_mu 0.093 _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 286(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 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 1.72 _diffrn_reflns_number 939 _diffrn_reflns_av_R_equivalents 0.0095 _diffrn_reflns_av_sigmaI/netI 0.0326 _diffrn_reflns_limit_h_min -1 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.61 _diffrn_reflns_theta_max 27.73 _reflns_number_total 823 _reflns_number_gt 614 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens 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^)+(0.0410P)^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 SHELXL _refine_ls_extinction_coef 0.060(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(10) _refine_ls_number_reflns 823 _refine_ls_number_parameters 82 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0512 _refine_ls_R_factor_gt 0.0351 _refine_ls_wR_factor_ref 0.0793 _refine_ls_wR_factor_gt 0.0751 _refine_ls_goodness_of_fit_ref 0.963 _refine_ls_restrained_S_all 0.963 _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 O O 0.51396(14) 0.2391(2) 0.28040(18) 0.0609(5) Uani 1 1 d . . . N1 N 0.26086(19) 0.4187(2) 0.2865(3) 0.0498(5) Uani 1 1 d . . . N2 N 0.43998(16) 0.0499(2) 0.4843(2) 0.0433(5) Uani 1 1 d . . . C2 C 0.27714(17) 0.2518(3) 0.3765(2) 0.0393(5) Uani 1 1 d . . . H2 H 0.2481 0.2670 0.4956 0.047 Uiso 1 1 calc R . . C3 C 0.1775(2) 0.1252(3) 0.2882(3) 0.0555(6) Uani 1 1 d . . . H3A H 0.2275 0.0288 0.2370 0.067 Uiso 1 1 calc R . . H3B H 0.1116 0.0787 0.3697 0.067 Uiso 1 1 calc R . . C4 C 0.1048(2) 0.2314(4) 0.1520(3) 0.0689(7) Uani 1 1 d . . . H4A H 0.0877 0.1619 0.0506 0.083 Uiso 1 1 calc R . . H4B H 0.0179 0.2770 0.1941 0.083 Uiso 1 1 calc R . . C5 C 0.2050(3) 0.3769(4) 0.1150(3) 0.0699(8) Uani 1 1 d . . . H5A H 0.2773 0.3385 0.0381 0.084 Uiso 1 1 calc R . . H5B H 0.1585 0.4770 0.0654 0.084 Uiso 1 1 calc R . . C6 C 0.42423(19) 0.1819(3) 0.3743(3) 0.0399(5) Uani 1 1 d . . . H1N H 0.346(2) 0.473(3) 0.288(3) 0.060(7) Uiso 1 1 d . . . H2N H 0.375(2) 0.015(3) 0.557(2) 0.049(6) 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 O 0.0405(8) 0.0759(11) 0.0662(9) 0.0185(10) 0.0170(8) 0.0045(8) N1 0.0441(10) 0.0474(10) 0.0580(10) 0.0067(9) 0.0098(10) 0.0059(9) N2 0.0290(7) 0.0455(10) 0.0555(10) 0.0050(9) 0.0084(8) 0.0028(8) C2 0.0349(9) 0.0443(10) 0.0388(10) 0.0031(11) 0.0036(8) 0.0039(9) C3 0.0421(11) 0.0630(14) 0.0616(13) -0.0013(13) -0.0087(11) -0.0017(11) C4 0.0615(14) 0.0876(18) 0.0576(14) -0.0086(15) -0.0131(12) 0.0153(15) C5 0.0764(16) 0.0831(19) 0.0503(14) 0.0164(14) 0.0064(13) 0.0205(16) C6 0.0333(10) 0.0436(11) 0.0428(10) -0.0052(10) 0.0031(9) 0.0000(9) _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 O C6 1.220(2) . ? N1 C2 1.467(3) . ? N1 C5 1.481(3) . ? N1 H1N 0.92(2) . ? N2 C6 1.336(2) . ? N2 N2 1.394(3) 2_655 ? N2 H2N 0.89(2) . ? C2 C6 1.525(2) . ? C2 C3 1.534(3) . ? C2 H2 0.9800 . ? C3 C4 1.515(3) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 C5 1.507(4) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? 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 C5 106.59(17) . . ? C2 N1 H1N 106.8(13) . . ? C5 N1 H1N 115.6(14) . . ? C6 N2 N2 120.74(15) . 2_655 ? C6 N2 H2N 123.9(13) . . ? N2 N2 H2N 115.3(13) 2_655 . ? N1 C2 C6 113.67(16) . . ? N1 C2 C3 105.50(16) . . ? C6 C2 C3 111.30(16) . . ? N1 C2 H2 108.7 . . ? C6 C2 H2 108.7 . . ? C3 C2 H2 108.7 . . ? C4 C3 C2 105.67(19) . . ? C4 C3 H3A 110.6 . . ? C2 C3 H3A 110.6 . . ? C4 C3 H3B 110.6 . . ? C2 C3 H3B 110.6 . . ? H3A C3 H3B 108.7 . . ? C5 C4 C3 103.41(19) . . ? C5 C4 H4A 111.1 . . ? C3 C4 H4A 111.1 . . ? C5 C4 H4B 111.1 . . ? C3 C4 H4B 111.1 . . ? H4A C4 H4B 109.0 . . ? N1 C5 C4 102.84(17) . . ? N1 C5 H5A 111.2 . . ? C4 C5 H5A 111.2 . . ? N1 C5 H5B 111.2 . . ? C4 C5 H5B 111.2 . . ? H5A C5 H5B 109.1 . . ? O C6 N2 125.25(18) . . ? O C6 C2 123.27(18) . . ? N2 C6 C2 111.46(16) . . ? 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 C5 N1 C2 C6 99.35(19) . . . . ? C5 N1 C2 C3 -22.9(2) . . . . ? N1 C2 C3 C4 -1.6(2) . . . . ? C6 C2 C3 C4 -125.35(19) . . . . ? C2 C3 C4 C5 24.7(2) . . . . ? C2 N1 C5 C4 38.6(2) . . . . ? C3 C4 C5 N1 -38.5(2) . . . . ? N2 N2 C6 O -8.4(3) 2_655 . . . ? N2 N2 C6 C2 170.25(17) 2_655 . . . ? N1 C2 C6 O -13.5(3) . . . . ? C3 C2 C6 O 105.4(2) . . . . ? N1 C2 C6 N2 167.81(15) . . . . ? C3 C2 C6 N2 -73.2(2) . . . . ? 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 N1 H1N O 0.92(2) 2.59(2) 3.413(2) 148.2(17) 2_665 N2 H2N N1 0.89(2) 1.94(2) 2.832(2) 175.1(19) 3_546 _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.73 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.129 _refine_diff_density_min -0.098 _refine_diff_density_rms 0.027