Supplementary Material (ESI) for Dalton Transactions This journal is (C) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name _publ_author_address 'Roesky, Peter W.' ; Freie Universit\"at Berlin Fabeckstr. 34-36 14195 Berlin Bundesrepublik Deutschland ; 'L\"ohnwitz, Karolin' ; Freie Universit\"at Berlin Fabeckstr. 34-36 14195 Berlin Bundesrepublik Deutschland ; 'Dochnahl, Maximilian' . 'Pissarek, J.-W.' . 'Blechert, Siegfried' ; Technische Universit\"at Berlin Strasse des 17. Juni 135 10623 Berlin Bundesrepublik Deutschland ; _publ_contact_author ; Prof. Dr. Peter Roesky Freie Universit\"at Berlin Fabeckstr. 34-36 14195 Berlin Bundesrepublik Deutschland ; _publ_contact_author_email roesky@chemie.fu-berlin.de _publ_contact_author_fax +49/(0)3083852440 _publ_contact_author_phone +49/(0)3083854004 _publ_requested_coeditor_name ? _publ_section_title ;Electronic modification of an aminotroponiminate zinc complex leading to an increased reactivity in the hydroamination of alkenes ; #END======================================================================= #END======================================================================= data_2 _database_code_depnum_ccdc_archive 'CCDC 653787' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H26 N2 S Zn' _chemical_formula_weight 391.86 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn 0.2839 1.4301 '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' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.7820(8) _cell_length_b 10.2833(9) _cell_length_c 11.2587(9) _cell_angle_alpha 106.262(7) _cell_angle_beta 97.856(7) _cell_angle_gamma 112.659(7) _cell_volume 964.31(14) _cell_formula_units_Z 2 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.459 _exptl_crystal_size_mid 0.370 _exptl_crystal_size_min 0.259 _exptl_crystal_density_diffrn 1.350 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 412 _exptl_absorpt_coefficient_mu 1.385 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.6261 _exptl_absorpt_correction_T_max 0.7215 _exptl_absorpt_process_details 'STOE X-RED & X-SHAPE' _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(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 'STOE IPDS 2T' _diffrn_measurement_method 'area detector' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6896 _diffrn_reflns_av_R_equivalents 0.0228 _diffrn_reflns_av_sigmaI/netI 0.0196 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.26 _diffrn_reflns_theta_max 25.02 _reflns_number_total 3364 _reflns_number_gt 3095 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-RED' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Diamond 2.1e' _computing_publication_material 'X-STEP32, Microsoft Word' _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^)+(0.0304P)^2^+0.3650P] 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 3364 _refine_ls_number_parameters 222 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0268 _refine_ls_R_factor_gt 0.0235 _refine_ls_wR_factor_ref 0.0599 _refine_ls_wR_factor_gt 0.0585 _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_restrained_S_all 1.057 _refine_ls_shift/su_max 0.016 _refine_ls_shift/su_mean 0.001 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 C1 C -0.11500(17) 0.27770(17) 0.33110(15) 0.0202(3) Uani 1 1 d . . . C2 C -0.21241(18) 0.32517(18) 0.39493(16) 0.0239(3) Uani 1 1 d . . . H2 H -0.2881 0.3331 0.3403 0.029 Uiso 1 1 calc R . . C3 C -0.21821(18) 0.36199(18) 0.52093(16) 0.0246(3) Uani 1 1 d . . . H3 H -0.2864 0.4038 0.5396 0.030 Uiso 1 1 calc R . . C4 C -0.13953(19) 0.34720(18) 0.62473(15) 0.0236(3) Uani 1 1 d . . . C5 C -0.03033(19) 0.29177(18) 0.62050(15) 0.0252(3) Uani 1 1 d . . . H5 H 0.0012 0.2732 0.6942 0.030 Uiso 1 1 calc R . . C6 C 0.03880(19) 0.25986(19) 0.52426(16) 0.0246(3) Uani 1 1 d . . . H6 H 0.1108 0.2244 0.5449 0.030 Uiso 1 1 calc R . . C7 C 0.02251(18) 0.27005(17) 0.40026(15) 0.0210(3) Uani 1 1 d . . . C8 C -0.27485(19) 0.2238(2) 0.12133(16) 0.0287(4) Uani 1 1 d . . . H8 H -0.3620 0.1833 0.1573 0.034 Uiso 1 1 calc R . . C9 C -0.2606(2) 0.3734(2) 0.1122(2) 0.0428(5) Uani 1 1 d . . . H9C H -0.3570 0.3573 0.0594 0.051 Uiso 1 1 calc R . . H9B H -0.1784 0.4123 0.0736 0.051 Uiso 1 1 calc R . . H9A H -0.2374 0.4457 0.1977 0.051 Uiso 1 1 calc R . . C10 C -0.3073(2) 0.1094(3) -0.01124(18) 0.0455(5) Uani 1 1 d . . . H10A H -0.3162 0.0150 -0.0036 0.055 Uiso 1 1 calc R . . H10B H -0.2235 0.1483 -0.0483 0.055 Uiso 1 1 calc R . . H10C H -0.4029 0.0919 -0.0664 0.055 Uiso 1 1 calc R . . C11 C 0.2613(2) 0.2539(2) 0.38521(18) 0.0333(4) Uani 1 1 d . . . H11 H 0.2952 0.3082 0.4796 0.040 Uiso 1 1 calc R . . C12 C 0.3874(2) 0.3330(3) 0.3274(2) 0.0559(6) Uani 1 1 d . . . H12A H 0.3995 0.4348 0.3418 0.067 Uiso 1 1 calc R . . H12B H 0.3585 0.2767 0.2357 0.067 Uiso 1 1 calc R . . H12C H 0.4839 0.3374 0.3682 0.067 Uiso 1 1 calc R . . C13 C 0.2312(3) 0.0919(3) 0.3577(2) 0.0577(6) Uani 1 1 d . . . H13A H 0.1989 0.0378 0.2654 0.069 Uiso 1 1 calc R . . H13B H 0.1505 0.0447 0.3948 0.069 Uiso 1 1 calc R . . H13C H 0.3247 0.0888 0.3953 0.069 Uiso 1 1 calc R . . C14 C 0.1087(2) 0.2038(2) -0.00945(18) 0.0410(5) Uani 1 1 d . . . H14A H 0.0943 0.2688 -0.0529 0.049 Uiso 1 1 calc R . . H14B H 0.0440 0.0988 -0.0642 0.049 Uiso 1 1 calc R . . H14C H 0.2158 0.2227 0.0087 0.049 Uiso 1 1 calc R . . C15 C -0.3736(2) 0.3093(2) 0.74942(16) 0.0262(3) Uani 1 1 d . . . C16 C -0.4543(2) 0.1584(2) 0.67028(18) 0.0331(4) Uani 1 1 d . . . H16 H -0.4039 0.1096 0.6238 0.040 Uiso 1 1 calc R . . C17 C -0.6089(2) 0.0794(2) 0.6593(2) 0.0416(5) Uani 1 1 d . . . H17 H -0.6633 -0.0230 0.6052 0.050 Uiso 1 1 calc R . . C18 C -0.6844(2) 0.1501(2) 0.7277(2) 0.0424(5) Uani 1 1 d . . . H18 H -0.7892 0.0957 0.7211 0.051 Uiso 1 1 calc R . . C19 C -0.6047(2) 0.3004(2) 0.8053(2) 0.0404(5) Uani 1 1 d . . . H19 H -0.6557 0.3490 0.8513 0.048 Uiso 1 1 calc R . . C20 C -0.4497(2) 0.3810(2) 0.81614(18) 0.0326(4) Uani 1 1 d . . . H20 H -0.3963 0.4840 0.8687 0.039 Uiso 1 1 calc R . . N1 N -0.13395(15) 0.24284(16) 0.20573(13) 0.0240(3) Uani 1 1 d . . . N2 N 0.12029(16) 0.26153(16) 0.33160(13) 0.0244(3) Uani 1 1 d . . . S1 S -0.17141(5) 0.41275(5) 0.77756(4) 0.02914(11) Uani 1 1 d . . . Zn1 Zn 0.05200(2) 0.24636(2) 0.151326(18) 0.02874(8) Uani 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 C1 0.0175(8) 0.0209(7) 0.0218(8) 0.0098(6) 0.0068(6) 0.0063(6) C2 0.0189(8) 0.0298(8) 0.0241(8) 0.0112(7) 0.0061(6) 0.0111(7) C3 0.0210(8) 0.0286(8) 0.0275(8) 0.0106(7) 0.0112(7) 0.0125(7) C4 0.0231(8) 0.0262(8) 0.0207(8) 0.0087(6) 0.0105(6) 0.0087(7) C5 0.0258(9) 0.0285(8) 0.0223(8) 0.0127(7) 0.0069(7) 0.0106(7) C6 0.0243(8) 0.0292(8) 0.0258(8) 0.0134(7) 0.0078(7) 0.0148(7) C7 0.0208(8) 0.0206(7) 0.0219(8) 0.0077(6) 0.0066(6) 0.0094(6) C8 0.0191(8) 0.0407(10) 0.0224(8) 0.0107(7) 0.0044(7) 0.0103(7) C9 0.0400(11) 0.0509(12) 0.0361(10) 0.0201(9) -0.0006(9) 0.0194(10) C10 0.0347(11) 0.0604(13) 0.0251(9) 0.0034(9) 0.0017(8) 0.0156(10) C11 0.0298(10) 0.0523(11) 0.0298(9) 0.0168(8) 0.0114(8) 0.0277(9) C12 0.0318(11) 0.104(2) 0.0577(14) 0.0440(14) 0.0250(10) 0.0415(13) C13 0.0768(17) 0.0637(15) 0.0541(14) 0.0190(12) 0.0157(12) 0.0552(15) C14 0.0444(12) 0.0467(11) 0.0288(10) 0.0096(8) 0.0192(9) 0.0170(10) C15 0.0292(9) 0.0322(9) 0.0228(8) 0.0152(7) 0.0127(7) 0.0139(7) C16 0.0375(10) 0.0317(9) 0.0353(10) 0.0142(8) 0.0182(8) 0.0164(8) C17 0.0395(11) 0.0333(10) 0.0439(11) 0.0145(9) 0.0159(9) 0.0067(9) C18 0.0306(10) 0.0523(12) 0.0482(12) 0.0274(10) 0.0197(9) 0.0130(9) C19 0.0405(11) 0.0526(12) 0.0447(11) 0.0247(10) 0.0272(9) 0.0272(10) C20 0.0370(10) 0.0339(9) 0.0313(9) 0.0132(8) 0.0180(8) 0.0164(8) N1 0.0197(7) 0.0308(7) 0.0190(7) 0.0087(6) 0.0053(5) 0.0093(6) N2 0.0213(7) 0.0332(8) 0.0250(7) 0.0124(6) 0.0099(6) 0.0158(6) S1 0.0272(2) 0.0366(2) 0.0199(2) 0.00741(17) 0.01084(17) 0.01108(19) Zn1 0.02726(12) 0.04247(14) 0.02148(11) 0.01230(9) 0.01303(8) 0.01791(10) _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 C1 N1 1.322(2) . ? C1 C2 1.418(2) . ? C1 C7 1.500(2) . ? C2 C3 1.377(2) . ? C3 C4 1.388(2) . ? C4 C5 1.391(2) . ? C4 S1 1.7808(16) . ? C5 C6 1.382(2) . ? C6 C7 1.421(2) . ? C7 N2 1.322(2) . ? C8 N1 1.473(2) . ? C8 C10 1.521(3) . ? C8 C9 1.524(3) . ? C11 N2 1.469(2) . ? C11 C13 1.505(3) . ? C11 C12 1.532(3) . ? C14 Zn1 1.9475(18) . ? C15 C16 1.383(3) . ? C15 C20 1.388(2) . ? C15 S1 1.7784(18) . ? C16 C17 1.382(3) . ? C17 C18 1.386(3) . ? C18 C19 1.374(3) . ? C19 C20 1.387(3) . ? N1 Zn1 1.9879(14) . ? N2 Zn1 1.9904(14) . ? 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 N1 C1 C2 122.58(14) . . ? N1 C1 C7 114.21(14) . . ? C2 C1 C7 123.14(14) . . ? C3 C2 C1 132.85(15) . . ? C2 C3 C4 130.35(15) . . ? C3 C4 C5 124.87(15) . . ? C3 C4 S1 118.30(12) . . ? C5 C4 S1 116.74(12) . . ? C6 C5 C4 129.74(15) . . ? C5 C6 C7 132.69(15) . . ? N2 C7 C6 123.15(14) . . ? N2 C7 C1 114.04(14) . . ? C6 C7 C1 122.60(14) . . ? N1 C8 C10 108.75(15) . . ? N1 C8 C9 111.82(15) . . ? C10 C8 C9 110.61(16) . . ? N2 C11 C13 110.42(17) . . ? N2 C11 C12 108.62(15) . . ? C13 C11 C12 111.37(18) . . ? C16 C15 C20 119.45(17) . . ? C16 C15 S1 122.20(14) . . ? C20 C15 S1 118.22(14) . . ? C17 C16 C15 120.16(18) . . ? C16 C17 C18 120.42(19) . . ? C19 C18 C17 119.50(19) . . ? C18 C19 C20 120.47(18) . . ? C19 C20 C15 119.98(18) . . ? C1 N1 C8 120.87(13) . . ? C1 N1 Zn1 113.69(10) . . ? C8 N1 Zn1 124.97(10) . . ? C7 N2 C11 121.00(14) . . ? C7 N2 Zn1 114.46(11) . . ? C11 N2 Zn1 124.42(11) . . ? C15 S1 C4 103.97(8) . . ? C14 Zn1 N1 137.18(8) . . ? C14 Zn1 N2 139.64(8) . . ? N1 Zn1 N2 81.52(5) . . ? 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 N1 C1 C2 C3 177.62(17) . . . . ? C7 C1 C2 C3 -5.5(3) . . . . ? C1 C2 C3 C4 -8.6(3) . . . . ? C2 C3 C4 C5 1.7(3) . . . . ? C2 C3 C4 S1 178.10(15) . . . . ? C3 C4 C5 C6 9.7(3) . . . . ? S1 C4 C5 C6 -166.80(15) . . . . ? C4 C5 C6 C7 -0.8(3) . . . . ? C5 C6 C7 N2 166.61(18) . . . . ? C5 C6 C7 C1 -18.9(3) . . . . ? N1 C1 C7 N2 13.6(2) . . . . ? C2 C1 C7 N2 -163.50(15) . . . . ? N1 C1 C7 C6 -161.32(15) . . . . ? C2 C1 C7 C6 21.6(2) . . . . ? C20 C15 C16 C17 -0.9(3) . . . . ? S1 C15 C16 C17 174.80(15) . . . . ? C15 C16 C17 C18 -0.2(3) . . . . ? C16 C17 C18 C19 0.9(3) . . . . ? C17 C18 C19 C20 -0.5(3) . . . . ? C18 C19 C20 C15 -0.7(3) . . . . ? C16 C15 C20 C19 1.4(3) . . . . ? S1 C15 C20 C19 -174.52(14) . . . . ? C2 C1 N1 C8 -11.6(2) . . . . ? C7 C1 N1 C8 171.25(14) . . . . ? C2 C1 N1 Zn1 160.95(12) . . . . ? C7 C1 N1 Zn1 -16.17(17) . . . . ? C10 C8 N1 C1 -149.89(17) . . . . ? C9 C8 N1 C1 87.68(19) . . . . ? C10 C8 N1 Zn1 38.4(2) . . . . ? C9 C8 N1 Zn1 -84.03(17) . . . . ? C6 C7 N2 C11 -5.4(2) . . . . ? C1 C7 N2 C11 179.74(14) . . . . ? C6 C7 N2 Zn1 170.74(12) . . . . ? C1 C7 N2 Zn1 -4.14(17) . . . . ? C13 C11 N2 C7 89.7(2) . . . . ? C12 C11 N2 C7 -147.95(18) . . . . ? C13 C11 N2 Zn1 -86.07(18) . . . . ? C12 C11 N2 Zn1 36.3(2) . . . . ? C16 C15 S1 C4 39.23(16) . . . . ? C20 C15 S1 C4 -144.99(14) . . . . ? C3 C4 S1 C15 57.59(15) . . . . ? C5 C4 S1 C15 -125.67(14) . . . . ? C1 N1 Zn1 C14 177.64(13) . . . . ? C8 N1 Zn1 C14 -10.13(19) . . . . ? C1 N1 Zn1 N2 11.11(11) . . . . ? C8 N1 Zn1 N2 -176.66(14) . . . . ? C7 N2 Zn1 C14 -169.17(13) . . . . ? C11 N2 Zn1 C14 6.8(2) . . . . ? C7 N2 Zn1 N1 -3.32(12) . . . . ? C11 N2 Zn1 N1 172.65(15) . . . . ? _diffrn_measured_fraction_theta_max 0.987 _diffrn_reflns_theta_full 25.02 _diffrn_measured_fraction_theta_full 0.987 _refine_diff_density_max 0.297 _refine_diff_density_min -0.227 _refine_diff_density_rms 0.043