# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _publ_section_title ;Lithium-Promoted Hydrogenation of Carbon Dioxide to Formates by Heterobimetallic Hydridozinc tert-Butoxide Clusters ; loop_ _publ_author_name M.Driess K.Fink L.Khodeir E.Loffler K.Merz M.Moreno M.Muhler ; A.Rittermeier ; _publ_contact_author_name 'Prof. Matthias Driess' _publ_contact_author_email MATTHIAS.DRIESS@TU-BERLIN.DE # Attachment 'md1404t.cif' data_md1404t _database_code_depnum_ccdc_archive 'CCDC 650772' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C2 H6 O6 Zn' _chemical_formula_weight 191.44 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' O O 0.0106 0.0060 '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 monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 8.6803(9) _cell_length_b 7.1241(10) _cell_length_c 9.3060(12) _cell_angle_alpha 90.00 _cell_angle_beta 97.664(3) _cell_angle_gamma 90.00 _cell_volume 570.34(12) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.229 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 384 _exptl_absorpt_coefficient_mu 4.265 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.4825 _exptl_absorpt_correction_T_max 0.6750 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 213(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2069 _diffrn_reflns_av_R_equivalents 0.0198 _diffrn_reflns_av_sigmaI/netI 0.0278 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 3 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.71 _diffrn_reflns_theta_max 25.02 _reflns_number_total 926 _reflns_number_gt 734 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0311P)^2^+0.1477P] 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 refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0217(18) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 926 _refine_ls_number_parameters 110 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0309 _refine_ls_R_factor_gt 0.0223 _refine_ls_wR_factor_ref 0.0623 _refine_ls_wR_factor_gt 0.0580 _refine_ls_goodness_of_fit_ref 1.059 _refine_ls_restrained_S_all 1.059 _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 Zn1 Zn 0.5000 0.0000 1.0000 0.0116(2) Uani 1 2 d S . . C1 C 0.1756(3) 0.1153(4) 1.0630(3) 0.0193(6) Uani 1 1 d . . . H1 H 0.176(4) -0.008(4) 1.101(3) 0.028(9) Uiso 1 1 d . . . O1 O 0.06338(18) 0.2212(3) 1.07847(18) 0.0230(5) Uani 1 1 d . . . Zn2 Zn 0.0000 0.5000 1.0000 0.0153(2) Uani 1 2 d S . . C2 C 0.5353(3) 0.2228(4) 1.2752(3) 0.0178(6) Uani 1 1 d . . . H2 H 0.436(4) 0.286(4) 1.231(3) 0.033(8) Uiso 1 1 d . . . O2 O 0.29037(18) 0.1587(2) 1.00069(17) 0.0169(5) Uani 1 1 d . . . O3 O 0.58913(18) 0.2720(3) 1.40197(17) 0.0166(4) Uani 1 1 d . . . O4 O 0.59695(19) 0.1040(3) 1.20264(17) 0.0158(4) Uani 1 1 d . . . O5 O 0.2184(2) 0.5236(4) 0.9283(2) 0.0182(5) Uani 1 1 d . . . H51 H 0.275(4) 0.595(5) 0.969(3) 0.036(11) Uiso 1 1 d . . . H52 H 0.255(4) 0.423(6) 0.945(4) 0.033(11) Uiso 1 1 d . . . O6 O 0.0872(3) 0.6100(4) 1.1972(2) 0.0303(6) Uani 1 1 d . . . H61 H 0.034(4) 0.651(5) 1.266(4) 0.041(10) Uiso 1 1 d . . . H62 H 0.170(4) 0.600(5) 1.228(3) 0.036(10) 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 0.0139(3) 0.0109(3) 0.0099(3) 0.00004(16) 0.00155(18) -0.00007(16) C1 0.0211(13) 0.0172(17) 0.0188(15) 0.0024(14) -0.0001(11) -0.0009(13) O1 0.0198(9) 0.0223(11) 0.0283(11) 0.0054(9) 0.0088(8) 0.0060(9) Zn2 0.0137(3) 0.0171(3) 0.0150(3) -0.00108(18) 0.00216(19) 0.00011(17) C2 0.0215(13) 0.0134(15) 0.0174(15) -0.0017(13) -0.0014(11) 0.0019(12) O2 0.0158(9) 0.0175(11) 0.0177(10) 0.0002(8) 0.0035(7) 0.0019(8) O3 0.0198(8) 0.0160(11) 0.0133(10) -0.0056(8) -0.0005(7) 0.0018(8) O4 0.0179(8) 0.0172(11) 0.0114(9) -0.0062(9) -0.0007(7) 0.0002(9) O5 0.0178(10) 0.0157(13) 0.0211(11) 0.0009(10) 0.0025(9) -0.0012(10) O6 0.0147(10) 0.0530(16) 0.0229(12) -0.0134(11) 0.0012(9) 0.0014(11) _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 O3 2.0636(17) 4_565 ? Zn1 O3 2.0636(17) 2_647 ? Zn1 O4 2.0953(16) 3_657 ? Zn1 O4 2.0953(17) . ? Zn1 O2 2.1429(16) . ? Zn1 O2 2.1429(16) 3_657 ? C1 O1 1.256(3) . ? C1 O2 1.256(3) . ? O1 Zn2 2.1618(18) . ? Zn2 O6 2.046(2) 3_567 ? Zn2 O6 2.046(2) . ? Zn2 O5 2.0990(19) . ? Zn2 O5 2.0990(19) 3_567 ? Zn2 O1 2.1618(19) 3_567 ? C2 O4 1.247(3) . ? C2 O3 1.259(3) . ? O3 Zn1 2.0636(17) 2_657 ? 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 O3 Zn1 O3 180.0 4_565 2_647 ? O3 Zn1 O4 90.57(7) 4_565 3_657 ? O3 Zn1 O4 89.43(7) 2_647 3_657 ? O3 Zn1 O4 89.43(7) 4_565 . ? O3 Zn1 O4 90.57(7) 2_647 . ? O4 Zn1 O4 180.0 3_657 . ? O3 Zn1 O2 87.40(7) 4_565 . ? O3 Zn1 O2 92.60(7) 2_647 . ? O4 Zn1 O2 87.14(6) 3_657 . ? O4 Zn1 O2 92.86(6) . . ? O3 Zn1 O2 92.60(7) 4_565 3_657 ? O3 Zn1 O2 87.40(7) 2_647 3_657 ? O4 Zn1 O2 92.86(6) 3_657 3_657 ? O4 Zn1 O2 87.14(6) . 3_657 ? O2 Zn1 O2 180.0 . 3_657 ? O1 C1 O2 125.5(3) . . ? C1 O1 Zn2 132.83(18) . . ? O6 Zn2 O6 180.000(1) 3_567 . ? O6 Zn2 O5 89.25(9) 3_567 . ? O6 Zn2 O5 90.75(9) . . ? O6 Zn2 O5 90.75(9) 3_567 3_567 ? O6 Zn2 O5 89.25(9) . 3_567 ? O5 Zn2 O5 180.000(1) . 3_567 ? O6 Zn2 O1 90.11(9) 3_567 3_567 ? O6 Zn2 O1 89.89(9) . 3_567 ? O5 Zn2 O1 91.09(8) . 3_567 ? O5 Zn2 O1 88.91(8) 3_567 3_567 ? O6 Zn2 O1 89.89(9) 3_567 . ? O6 Zn2 O1 90.11(9) . . ? O5 Zn2 O1 88.91(8) . . ? O5 Zn2 O1 91.09(8) 3_567 . ? O1 Zn2 O1 180.0 3_567 . ? O4 C2 O3 124.3(2) . . ? C1 O2 Zn1 126.69(18) . . ? C2 O3 Zn1 121.24(16) . 2_657 ? C2 O4 Zn1 125.26(17) . . ? _diffrn_measured_fraction_theta_max 0.919 _diffrn_reflns_theta_full 25.02 _diffrn_measured_fraction_theta_full 0.919 _refine_diff_density_max 0.401 _refine_diff_density_min -0.293 _refine_diff_density_rms 0.074