Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' _publ_contact_author_name 'Prof Jean-Francois Carpentier' _publ_contact_author_address ; Prof Jean-Francois Carpentier Laboratoire Organométalliques et Catalyse UMR 6509 CNRS - Université de Rennes 1 Campus de Beaulieu - F35042 Rennes France ; _publ_contact_author_email 'JEAN-FRANCOIS.CARPENTIER@UNIV-RENNES1.FR' _publ_section_title ; Direct Zn-diamine promoted reduction of C==O and C==N bonds by polymethylhydrosiloxane in methanol ; loop_ _publ_author_name _publ_author_address 'Carpentier, Jean-Francois' ; Laboratoire Organométalliques et Catalyse UMR 6509 CNRS - Université de Rennes 1 Campus de Beaulieu - F35042 Rennes France ; 'Lehmann, Christian W.' ; Max-Planck-Institut f\"ur Kohlenforschung Kaiser-Wilhelm-Platz 1 D-45470 M\"ulheim an der Ruhr Germany ; 'Virginie Bette' . 'Andre Mortreux' . ############################################################################ data_3844 _database_code_CSD 195656 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_compound_source 'see paper' _chemical_formula_moiety ? _chemical_formula_sum 'C36 H48 N4 Zn2' _chemical_formula_weight 667.52 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' 'Zn' 'Zn' 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P b c a' _symmetry_Int_Tables_number 61 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' '-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 8.6479(4) _cell_length_b 19.4712(9) _cell_length_c 19.5345(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3289.3(3) _cell_formula_units_Z 4 _cell_measurement_temperature 100 _cell_measurement_reflns_used 6161 _cell_measurement_theta_min 2.09 _cell_measurement_theta_max 33.18 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.348 _exptl_crystal_density_method none _exptl_crystal_F_000 1408 _exptl_absorpt_coefficient_mu 1.489 _exptl_absorpt_correction_type gaussian _exptl_absorpt_process_details 'XPREP, Siemens (1995)' _exptl_absorpt_correction_T_min 0.68 _exptl_absorpt_correction_T_max 0.78 _diffrn_ambient_temperature 100 _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 'Siemens SMART' _diffrn_measurement_method 'CCD \w-scan' _diffrn_standards_number 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0.00 _diffrn_reflns_number 34336 _diffrn_reflns_av_R_equivalents 0.0901 _diffrn_reflns_av_sigmaI/netI 0.0962 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -29 _diffrn_reflns_limit_k_max 29 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 2.09 _diffrn_reflns_theta_max 33.18 _reflns_number_total 6259 _reflns_number_gt 3713 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'SMART software (Siemens, 1995)' _computing_cell_refinement 'SMART software (Siemens, 1995)' _computing_data_reduction 'SAINT software (Siemens, 1995)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP (Johnson, 1976)' _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^)+(0.0423P)^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 none _refine_ls_number_reflns 6259 _refine_ls_number_parameters 195 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1177 _refine_ls_R_factor_gt 0.0535 _refine_ls_wR_factor_ref 0.1037 _refine_ls_wR_factor_gt 0.0899 _refine_ls_goodness_of_fit_ref 0.996 _refine_ls_restrained_S_all 0.996 _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 Zn1 Zn 0.01539(3) 0.005910(11) 0.427794(12) 0.01525(8) Uani 1 1 d . . . C1 C 0.1687(2) -0.11347(10) 0.35241(10) 0.0193(4) Uani 1 1 d . . . H1A H 0.1745 -0.0764 0.3193 0.023 Uiso 1 1 calc R . . H1B H 0.0723 -0.1377 0.3448 0.023 Uiso 1 1 calc R . . N2 N 0.1666(2) -0.08341(9) 0.42251(9) 0.0174(4) Uani 1 1 d . . . C3 C 0.1094(2) -0.13067(11) 0.47621(11) 0.0195(4) Uani 1 1 d . . . H3A H 0.1540 -0.1181 0.5200 0.023 Uiso 1 1 calc R . . H3B H 0.1414 -0.1772 0.4657 0.023 Uiso 1 1 calc R . . C4 C 0.0662(2) 0.12749(10) 0.51927(11) 0.0182(4) Uani 1 1 d . . . H4A H 0.1015 0.1561 0.4817 0.022 Uiso 1 1 calc R . . H4B H 0.1109 0.1451 0.5613 0.022 Uiso 1 1 calc R . . N5 N 0.1176(2) 0.05668(9) 0.50834(8) 0.0157(4) Uani 1 1 d . . . C6 C 0.2858(2) 0.05260(11) 0.51758(11) 0.0181(4) Uani 1 1 d . . . H6A H 0.3163 0.0047 0.5160 0.022 Uiso 1 1 calc R . . H6B H 0.3111 0.0698 0.5628 0.022 Uiso 1 1 calc R . . C7 C -0.0591(2) 0.04190(11) 0.33828(10) 0.0202(5) Uani 1 1 d . . . H7A H -0.0982 0.0881 0.3452 0.024 Uiso 1 1 calc R . . H7B H 0.0283 0.0449 0.3073 0.024 Uiso 1 1 calc R . . C8 C -0.1856(3) -0.00089(11) 0.30394(11) 0.0261(5) Uani 1 1 d . . . H8A H -0.1499 -0.0472 0.2981 0.039 Uiso 1 1 calc R . . H8B H -0.2098 0.0185 0.2600 0.039 Uiso 1 1 calc R . . H8C H -0.2766 -0.0008 0.3321 0.039 Uiso 1 1 calc R . . C11 C 0.3011(2) -0.16225(10) 0.33993(10) 0.0170(4) Uani 1 1 d . . . C12 C 0.4473(2) -0.13682(11) 0.32464(10) 0.0212(5) Uani 1 1 d . . . H12 H 0.4632 -0.0897 0.3221 0.025 Uiso 1 1 calc R . . C13 C 0.5696(3) -0.18160(13) 0.31319(11) 0.0266(5) Uani 1 1 d . . . H13 H 0.6671 -0.1643 0.3030 0.032 Uiso 1 1 calc R . . C14 C 0.5471(3) -0.25159(13) 0.31682(11) 0.0306(6) Uani 1 1 d . . . H14 H 0.6293 -0.2813 0.3087 0.037 Uiso 1 1 calc R . . C15 C 0.4034(3) -0.27767(12) 0.33249(12) 0.0296(5) Uani 1 1 d . . . H15 H 0.3886 -0.3249 0.3354 0.036 Uiso 1 1 calc R . . C16 C 0.2804(3) -0.23299(11) 0.34397(12) 0.0248(5) Uani 1 1 d . . . H16 H 0.1833 -0.2506 0.3544 0.030 Uiso 1 1 calc R . . C21 C 0.3808(2) 0.09207(11) 0.46506(10) 0.0187(4) Uani 1 1 d . . . C22 C 0.4728(2) 0.14728(12) 0.48417(12) 0.0232(5) Uani 1 1 d . . . H22 H 0.4749 0.1611 0.5297 0.028 Uiso 1 1 calc R . . C23 C 0.5621(2) 0.18240(12) 0.43595(12) 0.0272(5) Uani 1 1 d . . . H23 H 0.6244 0.2188 0.4497 0.033 Uiso 1 1 calc R . . C24 C 0.5583(2) 0.16321(12) 0.36807(12) 0.0277(5) Uani 1 1 d . . . H24 H 0.6178 0.1866 0.3360 0.033 Uiso 1 1 calc R . . C25 C 0.4659(3) 0.10913(12) 0.34789(12) 0.0285(5) Uani 1 1 d . . . H25 H 0.4621 0.0963 0.3021 0.034 Uiso 1 1 calc R . . C26 C 0.3786(3) 0.07403(11) 0.39598(11) 0.0245(5) Uani 1 1 d . . . H26 H 0.3171 0.0375 0.3818 0.029 Uiso 1 1 calc R . . H2 H 0.255(3) -0.0736(11) 0.4315(10) 0.014(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 Zn1 0.01556(12) 0.01628(13) 0.01392(12 -0.00145(9) -0.00029(9) 0.00082(9) C1 0.0209(11) 0.0211(11) 0.0159(11) -0.0011(9) 0.0006(8) 0.0034(8) N2 0.0153(9) 0.0205(9) 0.0165(9) -0.0025(7) 0.0008(7) 0.0012(7) C3 0.0234(11) 0.0173(11) 0.0178(11) -0.0002(9) 0.0004(9) 0.0043(8) C4 0.0208(11) 0.0170(10) 0.0170(10) -0.0017(8) 0.0015(9) 0.0010(8) N5 0.0155(8) 0.0151(8) 0.0164(9) -0.0028(7) -0.0011(6) 0.0008(7) C6 0.0162(10) 0.0205(10) 0.0177(10) -0.0026(9) -0.0016(8) -0.0013(8) C7 0.0199(11) 0.0204(11) 0.0203(11) 0.0004(9) -0.0008(8) -0.0005(8) C8 0.0284(12) 0.0279(12) 0.0220(11) 0.0019(10) -0.0067(9) -0.0030(10) C11 0.0188(10) 0.0225(11) 0.0097(10) -0.0029(8) 0.0006(8) 0.0045(8) C12 0.0235(12) 0.0227(11) 0.0173(11) -0.0014(9) 0.0019(9) -0.0030(9) C13 0.0167(11) 0.0415(15) 0.0217(12) -0.0026(10) 0.0039(9) 0.0002(10) C14 0.0266(13) 0.0360(14) 0.0292(13) -0.0021(11) 0.0028(10) 0.0158(11) C15 0.0346(14) 0.0217(12) 0.0325(14) -0.0006(10) 0.0040(11) 0.0077(10) C16 0.0208(12) 0.0242(12) 0.0296(12) -0.0015(10) 0.0061(9) -0.0005(9) C21 0.0145(10) 0.0213(11) 0.0203(12) -0.0014(9) -0.0003(8) 0.0026(8) C22 0.0187(11) 0.0246(12) 0.0263(12) -0.0006(9) -0.0047(9) 0.0017(9) C23 0.0164(11) 0.0254(12) 0.0399(15) 0.0045(11) -0.0051(10) -0.0023(8) C24 0.0171(11) 0.0320(13) 0.0342(14) 0.0073(11) 0.0068(10) 0.0002(9) C25 0.0276(12) 0.0338(13) 0.0242(12) -0.0023(10) 0.0083(10) 0.0010(10) C26 0.0231(12) 0.0247(12) 0.0257(12) -0.0049(10) 0.0037(9) -0.0035(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 Zn1 C7 1.991(2) . ? Zn1 N5 2.0580(16) . ? Zn1 N5 2.0893(17) 5_556 ? Zn1 N2 2.1784(17) . ? Zn1 Zn1 2.8428(5) 5_556 ? C1 N2 1.489(3) . ? C1 C11 1.508(3) . ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? N2 C3 1.480(3) . ? N2 H2 0.80(2) . ? C3 C4 1.522(3) 5_556 ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 N5 1.464(2) . ? C4 C3 1.522(3) 5_556 ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? N5 C6 1.468(3) . ? N5 Zn1 2.0893(17) 5_556 ? C6 C21 1.522(3) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C8 1.530(3) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 H8A 0.9600 . ? C8 H8B 0.9600 . ? C8 H8C 0.9600 . ? C11 C12 1.390(3) . ? C11 C16 1.391(3) . ? C12 C13 1.389(3) . ? C12 H12 0.9300 . ? C13 C14 1.378(3) . ? C13 H13 0.9300 . ? C14 C15 1.377(3) . ? C14 H14 0.9300 . ? C15 C16 1.393(3) . ? C15 H15 0.9300 . ? C16 H16 0.9300 . ? C21 C22 1.388(3) . ? C21 C26 1.395(3) . ? C22 C23 1.397(3) . ? C22 H22 0.9300 . ? C23 C24 1.378(3) . ? C23 H23 0.9300 . ? C24 C25 1.379(3) . ? C24 H24 0.9300 . ? C25 C26 1.385(3) . ? C25 H25 0.9300 . ? C26 H26 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 C7 Zn1 N5 129.91(8) . . ? C7 Zn1 N5 123.47(7) . 5_556 ? N5 Zn1 N5 93.46(6) . 5_556 ? C7 Zn1 N2 115.70(8) . . ? N5 Zn1 N2 99.31(7) . . ? N5 Zn1 N2 83.87(7) 5_556 . ? C7 Zn1 Zn1 150.42(6) . 5_556 ? N5 Zn1 Zn1 47.19(5) . 5_556 ? N5 Zn1 Zn1 46.27(4) 5_556 5_556 ? N2 Zn1 Zn1 92.21(5) . 5_556 ? N2 C1 C11 113.94(16) . . ? N2 C1 H1A 108.8 . . ? C11 C1 H1A 108.8 . . ? N2 C1 H1B 108.8 . . ? C11 C1 H1B 108.8 . . ? H1A C1 H1B 107.7 . . ? C3 N2 C1 114.29(16) . . ? C3 N2 Zn1 105.20(12) . . ? C1 N2 Zn1 111.39(12) . . ? C3 N2 H2 108.1(15) . . ? C1 N2 H2 106.4(15) . . ? Zn1 N2 H2 111.6(15) . . ? N2 C3 C4 110.42(17) . 5_556 ? N2 C3 H3A 109.6 . . ? C4 C3 H3A 109.6 5_556 . ? N2 C3 H3B 109.6 . . ? C4 C3 H3B 109.6 5_556 . ? H3A C3 H3B 108.1 . . ? N5 C4 C3 110.49(17) . 5_556 ? N5 C4 H4A 109.6 . . ? C3 C4 H4A 109.6 5_556 . ? N5 C4 H4B 109.6 . . ? C3 C4 H4B 109.6 5_556 . ? H4A C4 H4B 108.1 . . ? C4 N5 C6 109.53(16) . . ? C4 N5 Zn1 115.66(13) . . ? C6 N5 Zn1 119.59(13) . . ? C4 N5 Zn1 107.14(12) . 5_556 ? C6 N5 Zn1 116.15(13) . 5_556 ? Zn1 N5 Zn1 86.54(6) . 5_556 ? N5 C6 C21 115.13(17) . . ? N5 C6 H6A 108.5 . . ? C21 C6 H6A 108.5 . . ? N5 C6 H6B 108.5 . . ? C21 C6 H6B 108.5 . . ? H6A C6 H6B 107.5 . . ? C8 C7 Zn1 115.14(14) . . ? C8 C7 H7A 108.5 . . ? Zn1 C7 H7A 108.5 . . ? C8 C7 H7B 108.5 . . ? Zn1 C7 H7B 108.5 . . ? H7A C7 H7B 107.5 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C12 C11 C16 118.84(19) . . ? C12 C11 C1 120.06(19) . . ? C16 C11 C1 121.10(19) . . ? C13 C12 C11 120.2(2) . . ? C13 C12 H12 119.9 . . ? C11 C12 H12 119.9 . . ? C14 C13 C12 120.3(2) . . ? C14 C13 H13 119.8 . . ? C12 C13 H13 119.8 . . ? C15 C14 C13 120.2(2) . . ? C15 C14 H14 119.9 . . ? C13 C14 H14 119.9 . . ? C14 C15 C16 119.7(2) . . ? C14 C15 H15 120.2 . . ? C16 C15 H15 120.2 . . ? C11 C16 C15 120.7(2) . . ? C11 C16 H16 119.6 . . ? C15 C16 H16 119.6 . . ? C22 C21 C26 117.6(2) . . ? C22 C21 C6 121.25(19) . . ? C26 C21 C6 121.17(19) . . ? C21 C22 C23 121.0(2) . . ? C21 C22 H22 119.5 . . ? C23 C22 H22 119.5 . . ? C24 C23 C22 120.2(2) . . ? C24 C23 H23 119.9 . . ? C22 C23 H23 119.9 . . ? C23 C24 C25 119.7(2) . . ? C23 C24 H24 120.1 . . ? C25 C24 H24 120.1 . . ? C24 C25 C26 119.9(2) . . ? C24 C25 H25 120.1 . . ? C26 C25 H25 120.1 . . ? C25 C26 C21 121.6(2) . . ? C25 C26 H26 119.2 . . ? C21 C26 H26 119.2 . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 33.18 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.609 _refine_diff_density_min -0.991 _refine_diff_density_rms 0.104