# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 182/1803 data_global # 1. SUBMISSION DETAILS _publ_contact_autor ; Katharina M. Fromm University of Geneva Sciences II, 30 Quai Ernest-Ansermet CH-1211 Geneva 4 Switzerland ; _publ_contact_author_phone '041 22 702-6421' _publ_contact_author_fax '041 22 702-6069' _publ_contact_author_email Katharina.Fromm@chiam.unige.ch _publ_requested_journal 'Chem. Comm.' _publ_requested_coeditor_name ? _publ_contact_letter ; ? ; #============================================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; Synthesis and crystal structure of [IBa(OtBu)4{Li(thf)}4(OH)]: a mixed ligand heterometallic cluster with an unusual low coordination number for barium** ; loop_ _publ_author_name _publ_author_address 'Fromm, Katharina M.' ; University of Geneva Sciences II 30 Quai Ernest-Ansermet CH-1211 Geneva 4 Switzerland ; 'Gueneau, Estelle' ; University of Geneva Sciences II 30 Quai Ernest-Ansermet CH-1211 Geneva 4 Switzerland ; 'Goesmann, Helmut' ; University of Karlsruhe Institute of Inorganic Chemistry D-76128 Karlsruhe Germany ; #============================================================================== data_BaLi4-Cluster _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety [IBa(OtBu)4{Li(thf)}4(OH)] _chemical_formula_sum 'C32 H69 Ba1 I1 Li4 O9' _chemical_formula_weight 889.87 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' 'Li' 'Li' -0.0003 0.0001 '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' 'I' 'I' -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ba' 'Ba' -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M P4/nmm loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z' '-y+1/2, x, z' 'y, -x+1/2, z' '-x, y+1/2, -z' 'x+1/2, -y, -z' 'y+1/2, x+1/2, -z' '-y, -x, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z' 'y-1/2, -x, -z' '-y, x-1/2, -z' 'x, -y-1/2, z' '-x-1/2, y, z' '-y-1/2, -x-1/2, z' 'y, x, z' _cell_length_a 15.574(2) _cell_length_b 15.574(2) _cell_length_c 10.395(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2521.5(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needles _exptl_crystal_colour colorless _exptl_crystal_size_max .65 _exptl_crystal_size_mid .3 _exptl_crystal_size_min .3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.172 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 908 _exptl_absorpt_coefficient_mu 1.435 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 STADI-4' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 120 _diffrn_standards_decay_% ? _diffrn_reflns_number 4721 _diffrn_reflns_av_R_equivalents 0.1139 _diffrn_reflns_av_sigmaI/netI 0.0811 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 13.71 _diffrn_reflns_theta_max 27.01 _reflns_number_total 1313 _reflns_number_gt 932 _reflns_threshold_expression >2sigma(I) _computing_data_collection STOE _computing_cell_refinement STOE _computing_data_reduction STOE _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics SCHAKAL _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^)+(0.1295P)^2^+1.0636P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1313 _refine_ls_number_parameters 86 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1138 _refine_ls_R_factor_gt 0.0807 _refine_ls_wR_factor_ref 0.2343 _refine_ls_wR_factor_gt 0.2014 _refine_ls_goodness_of_fit_ref 1.033 _refine_ls_restrained_S_all 1.033 _refine_ls_shift/su_max 0.002 _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 Ba Ba 0.7500 0.7500 0.61486(8) 0.0775(6) Uani 1 8 d S . . I I 0.7500 0.7500 0.2931(2) 0.219(2) Uani 1 8 d S . . O3 O 0.7500 0.7500 0.9146(10) 0.066(2) Uani 1 8 d S . . O1 O 0.6487(2) 0.8513(2) 0.7427(5) 0.0757(14) Uani 1 2 d S A . C1 C 0.5913(5) 0.9087(5) 0.6791(12) 0.107(3) Uani 1 2 d S . . C2 C 0.5995(13) 0.9005(13) 0.537(3) 0.156(6) Uiso 1 2 d S A . C3 C 0.565(2) 0.9781(18) 0.760(3) 0.083(6) Uiso 0.25 1 d P A 1 C4 C 0.654(3) 1.012(3) 0.697(5) 0.105(8) Uiso 0.25 1 d P A 1 C3A C 0.599(3) 0.993(2) 0.718(4) 0.101(8) Uiso 0.25 1 d P A 2 C4A C 0.636(2) 0.994(2) 0.640(4) 0.090(6) Uiso 0.25 1 d P A 2 Li Li 0.6267(8) 0.7500 0.8499(13) 0.073(3) Uani 1 2 d S . . O2 O 0.5392(6) 0.7500 0.9905(9) 0.100(2) Uani 1 2 d S . . C5 C 0.545(3) 0.682(2) 1.089(3) 0.157(14) Uani 0.50 1 d P . 1 C6 C 0.484(3) 0.710(2) 1.190(2) 0.145(11) Uani 0.50 1 d P . 1 C5A C 0.467(3) 0.802(4) 1.024(5) 0.18(2) Uani 0.50 1 d P . 2 C6A C 0.421(4) 0.7500 1.121(6) 0.207(18) Uani 1 2 d S . 2 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 Ba 0.0871(7) 0.0871(7) 0.0583(7) 0.000 0.000 0.000 I 0.294(3) 0.294(3) 0.0699(11) 0.000 0.000 0.000 O3 0.072(3) 0.072(3) 0.054(4) 0.000 0.000 0.000 O1 0.077(2) 0.077(2) 0.073(3) 0.0080(15) -0.0080(15) 0.018(2) C1 0.114(5) 0.114(5) 0.093(6) 0.016(3) -0.016(3) 0.044(6) Li 0.071(6) 0.077(7) 0.072(6) 0.000 0.009(5) 0.000 O2 0.097(4) 0.102(5) 0.102(4) 0.000 0.034(4) 0.000 C5 0.21(4) 0.141(19) 0.125(16) 0.047(15) 0.08(2) 0.05(2) C6 0.16(2) 0.176(19) 0.103(12) 0.000(13) 0.062(16) -0.04(2) C5A 0.14(3) 0.21(3) 0.19(4) 0.06(3) 0.08(3) 0.07(3) C6A 0.17(3) 0.25(4) 0.20(3) 0.000 0.08(3) 0.000 _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 Ba O1 2.597(6) 4_565 ? Ba O1 2.597(6) 3_655 ? Ba O1 2.597(6) 2_665 ? Ba O1 2.597(6) . ? Ba Li 3.108(13) 4_565 ? Ba Li 3.108(13) 2_665 ? Ba Li 3.108(13) 3_655 ? Ba Li 3.108(13) . ? Ba O3 3.115(10) . ? Ba I 3.344(2) . ? Ba C2 3.41(3) 3_655 ? Ba C2 3.41(3) 4_565 ? O3 Li 2.035(14) 3_655 ? O3 Li 2.035(14) 4_565 ? O3 Li 2.035(14) 2_665 ? O3 Li 2.035(14) . ? O1 C1 1.427(11) . ? O1 Li 1.962(8) 4_565 ? O1 Li 1.962(8) . ? C1 C3A 1.37(4) . ? C1 C3A 1.37(4) 15_775 ? C1 C3 1.43(3) . ? C1 C3 1.43(3) 15_775 ? C1 C2 1.48(3) . ? C1 C4A 1.55(3) . ? C1 C4A 1.55(3) 15_775 ? C1 C4 1.89(5) . ? C1 C4 1.89(5) 15_775 ? C2 C4A 1.89(4) . ? C2 C4A 1.89(4) 15_775 ? C3 C3 0.94(6) 15_775 ? C3 C4 1.63(5) . ? C3A C4A 0.99(5) . ? C3A C3A 2.02(9) 15_775 ? Li O1 1.962(8) 3_655 ? Li O2 1.997(14) . ? Li Li 2.716(18) 4_565 ? Li Li 2.716(18) 3_655 ? O2 C5A 1.42(3) 13_575 ? O2 C5A 1.42(3) . ? O2 C5 1.47(3) 13_575 ? O2 C5 1.47(3) . ? C5 C6 1.48(4) . ? C6 C6 1.23(7) 13_575 ? C5A C6A 1.48(6) . ? C5A C5A 1.60(11) 13_575 ? C6A C5A 1.48(6) 13_575 ? 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 O1 Ba O1 118.5(2) 4_565 3_655 ? O1 Ba O1 74.83(11) 4_565 2_665 ? O1 Ba O1 74.83(11) 3_655 2_665 ? O1 Ba O1 74.83(11) 4_565 . ? O1 Ba O1 74.83(11) 3_655 . ? O1 Ba O1 118.5(2) 2_665 . ? O1 Ba Li 38.95(11) 4_565 4_565 ? O1 Ba Li 88.5(2) 3_655 4_565 ? O1 Ba Li 88.5(2) 2_665 4_565 ? O1 Ba Li 38.95(11) . 4_565 ? O1 Ba Li 38.95(11) 4_565 2_665 ? O1 Ba Li 88.5(2) 3_655 2_665 ? O1 Ba Li 38.95(11) 2_665 2_665 ? O1 Ba Li 88.5(2) . 2_665 ? Li Ba Li 51.8(3) 4_565 2_665 ? O1 Ba Li 88.5(2) 4_565 3_655 ? O1 Ba Li 38.95(11) 3_655 3_655 ? O1 Ba Li 38.95(11) 2_665 3_655 ? O1 Ba Li 88.5(2) . 3_655 ? Li Ba Li 76.3(5) 4_565 3_655 ? Li Ba Li 51.8(3) 2_665 3_655 ? O1 Ba Li 88.5(2) 4_565 . ? O1 Ba Li 38.95(11) 3_655 . ? O1 Ba Li 88.5(2) 2_665 . ? O1 Ba Li 38.95(11) . . ? Li Ba Li 51.8(3) 4_565 . ? Li Ba Li 76.3(5) 2_665 . ? Li Ba Li 51.8(3) 3_655 . ? O1 Ba O3 59.23(12) 4_565 . ? O1 Ba O3 59.23(12) 3_655 . ? O1 Ba O3 59.23(12) 2_665 . ? O1 Ba O3 59.23(12) . . ? Li Ba O3 38.2(3) 4_565 . ? Li Ba O3 38.2(3) 2_665 . ? Li Ba O3 38.2(3) 3_655 . ? Li Ba O3 38.2(3) . . ? O1 Ba I 120.77(12) 4_565 . ? O1 Ba I 120.77(12) 3_655 . ? O1 Ba I 120.77(12) 2_665 . ? O1 Ba I 120.77(12) . . ? Li Ba I 141.8(3) 4_565 . ? Li Ba I 141.8(3) 2_665 . ? Li Ba I 141.8(3) 3_655 . ? Li Ba I 141.8(3) . . ? O3 Ba I 180.000(1) . . ? O1 Ba C2 162.9(5) 4_565 3_655 ? O1 Ba C2 44.4(4) 3_655 3_655 ? O1 Ba C2 96.9(2) 2_665 3_655 ? O1 Ba C2 96.9(2) . 3_655 ? Li Ba C2 127.6(4) 4_565 3_655 ? Li Ba C2 127.6(4) 2_665 3_655 ? Li Ba C2 76.2(4) 3_655 3_655 ? Li Ba C2 76.2(4) . 3_655 ? O3 Ba C2 103.6(4) . 3_655 ? I Ba C2 76.4(4) . 3_655 ? O1 Ba C2 44.4(4) 4_565 4_565 ? O1 Ba C2 162.9(5) 3_655 4_565 ? O1 Ba C2 96.9(2) 2_665 4_565 ? O1 Ba C2 96.9(2) . 4_565 ? Li Ba C2 76.2(4) 4_565 4_565 ? Li Ba C2 76.2(4) 2_665 4_565 ? Li Ba C2 127.6(4) 3_655 4_565 ? Li Ba C2 127.6(4) . 4_565 ? O3 Ba C2 103.6(4) . 4_565 ? I Ba C2 76.4(4) . 4_565 ? C2 Ba C2 152.7(9) 3_655 4_565 ? Li O3 Li 141.4(9) 3_655 4_565 ? Li O3 Li 83.7(3) 3_655 2_665 ? Li O3 Li 83.7(3) 4_565 2_665 ? Li O3 Li 83.7(3) 3_655 . ? Li O3 Li 83.7(3) 4_565 . ? Li O3 Li 141.4(9) 2_665 . ? Li O3 Ba 70.7(5) 3_655 . ? Li O3 Ba 70.7(5) 4_565 . ? Li O3 Ba 70.7(5) 2_665 . ? Li O3 Ba 70.7(5) . . ? C1 O1 Li 131.1(5) . 4_565 ? C1 O1 Li 131.1(5) . . ? Li O1 Li 87.6(8) 4_565 . ? C1 O1 Ba 121.6(6) . . ? Li O1 Ba 84.8(4) 4_565 . ? Li O1 Ba 84.8(4) . . ? C3A C1 C3A 94(4) . 15_775 ? C3A C1 O1 113.8(16) . . ? C3A C1 O1 113.8(16) 15_775 . ? C3A C1 C3 29.9(17) . . ? C3A C1 C3 67(3) 15_775 . ? O1 C1 C3 112.6(14) . . ? C3A C1 C3 67(3) . 15_775 ? C3A C1 C3 29.9(17) 15_775 15_775 ? O1 C1 C3 112.6(14) . 15_775 ? C3 C1 C3 38(3) . 15_775 ? C3A C1 C2 112(2) . . ? C3A C1 C2 112(2) 15_775 . ? O1 C1 C2 110.6(13) . . ? C3 C1 C2 132.3(16) . . ? C3 C1 C2 132.3(16) 15_775 . ? C3A C1 C4A 39(2) . . ? C3A C1 C4A 125(2) 15_775 . ? O1 C1 C4A 112.2(14) . . ? C3 C1 C4A 68.8(18) . . ? C3 C1 C4A 104.0(19) 15_775 . ? C2 C1 C4A 77.0(16) . . ? C3A C1 C4A 125(2) . 15_775 ? C3A C1 C4A 39(2) 15_775 15_775 ? O1 C1 C4A 112.2(13) . 15_775 ? C3 C1 C4A 104.0(19) . 15_775 ? C3 C1 C4A 68.8(18) 15_775 15_775 ? C2 C1 C4A 77.0(16) . 15_775 ? C4A C1 C4A 134(3) . 15_775 ? C3A C1 C4 28(2) . . ? C3A C1 C4 122(3) 15_775 . ? O1 C1 C4 99.4(14) . . ? C3 C1 C4 56.7(16) . . ? C3 C1 C4 95(2) 15_775 . ? C2 C1 C4 97.3(15) . . ? C4A C1 C4 21.2(14) . . ? C4A C1 C4 148.0(19) 15_775 . ? C3A C1 C4 122(3) . 15_775 ? C3A C1 C4 28(2) 15_775 15_775 ? O1 C1 C4 99.4(13) . 15_775 ? C3 C1 C4 95(2) . 15_775 ? C3 C1 C4 56.7(16) 15_775 15_775 ? C2 C1 C4 97.3(15) . 15_775 ? C4A C1 C4 148.0(19) . 15_775 ? C4A C1 C4 21.2(14) 15_775 15_775 ? C4 C1 C4 150(3) . 15_775 ? C1 C2 C4A 53.0(12) . . ? C1 C2 C4A 53.0(12) . 15_775 ? C4A C2 C4A 98(2) . 15_775 ? C1 C2 Ba 83.4(11) . . ? C4A C2 Ba 100.9(13) . . ? C4A C2 Ba 100.9(13) 15_775 . ? C3 C3 C1 70.9(13) 15_775 . ? C3 C3 C4 146(2) 15_775 . ? C1 C3 C4 76(2) . . ? C3 C4 C1 47.4(17) . . ? C4A C3A C1 80(3) . . ? C4A C3A C3A 115(3) . 15_775 ? C1 C3A C3A 43(2) . 15_775 ? C3A C4A C1 61(3) . . ? C3A C4A C2 106(3) . . ? C1 C4A C2 50.0(15) . . ? O1 Li O1 107.0(7) 3_655 . ? O1 Li O2 122.3(4) 3_655 . ? O1 Li O2 122.3(4) . . ? O1 Li O3 91.3(5) 3_655 . ? O1 Li O3 91.3(5) . . ? O2 Li O3 113.7(8) . . ? O1 Li Li 116.4(4) 3_655 4_565 ? O1 Li Li 46.2(4) . 4_565 ? O2 Li Li 118.8(3) . 4_565 ? O3 Li Li 48.13(14) . 4_565 ? O1 Li Li 46.2(4) 3_655 3_655 ? O1 Li Li 116.4(4) . 3_655 ? O2 Li Li 118.8(3) . 3_655 ? O3 Li Li 48.13(14) . 3_655 ? Li Li Li 90.000(5) 4_565 3_655 ? O1 Li Ba 56.3(3) 3_655 . ? O1 Li Ba 56.3(3) . . ? O2 Li Ba 175.2(7) . . ? O3 Li Ba 71.1(4) . . ? Li Li Ba 64.09(15) 4_565 . ? Li Li Ba 64.09(15) 3_655 . ? C5A O2 C5A 69(5) 13_575 . ? C5A O2 C5 106.2(19) 13_575 13_575 ? C5A O2 C5 58(3) . 13_575 ? C5A O2 C5 58(3) 13_575 . ? C5A O2 C5 106.2(19) . . ? C5 O2 C5 92(3) 13_575 . ? C5A O2 Li 135.7(16) 13_575 . ? C5A O2 Li 135.7(16) . . ? C5 O2 Li 118.0(12) 13_575 . ? C5 O2 Li 118.0(12) . . ? O2 C5 C6 104(2) . . ? C6 C6 C5 107.2(18) 13_575 . ? O2 C5A C6A 104(3) . . ? O2 C5A C5A 56(3) . 13_575 ? C6A C5A C5A 57(2) . 13_575 ? C5A C6A C5A 66(4) . 13_575 ? _diffrn_measured_fraction_theta_max 0.841 _diffrn_reflns_theta_full 27.01 _diffrn_measured_fraction_theta_full 0.841 _refine_diff_density_max 1.003 _refine_diff_density_min -0.479 _refine_diff_density_rms 0.058