# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 1999 # CCDC Number: 186/1579 # Paper ref. 9/04176A # Journal: Dalton Transactions, Paper ref. 9/04176A # Title: Dramatic structural changes of donor-functionalized alkoxides # of aluminium upon replacement of the ester to ketone functionality # Authors: Janusz Lewinski, Iwona Justyniak, Zbigniew Ochal, Janusz Zachara # data_global #======================================================================= # 1. SUBMISSION DETAILS- publication No.: _publ_contact_author ; Dr. Janusz Lewinski, Department of Chemistry Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warszawa Poland ; _publ_contact_author_phone '048 22 6607315' _publ_contact_author_fax '048 22 6607279' _publ_contact_author_email lewin@ch.pw.edu.pl _publ_requested_journal 'Dalton Transactions' #======================================================================= # 2. PROCESSING SUMMARY _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_date_from_coeditor ? _journal_date_accepted ? _journal_date_printers_first ? _journal_date_printers_final ? _journal_date_proofs_out ? _journal_date_proofs_in ? _journal_coeditor_name ? _journal_coeditor_code ? _journal_coeditor_notes ? _journal_techeditor_code ? _journal_techeditor_notes ? _journal_coden_ASTM ? _journal_name_full ? _journal_year ? _journal_volume ? _journal_issue ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? #======================================================================= # 3. TITLE AND AUTHOR LIST _publ_section_title ; Dramatic structural changes of donor-functionalized alkoxides of aluminium upon replacement of the ester to ketone functionality ; loop_ _publ_author_name _publ_author_address 'dr Lewi\'nski, Janusz' ; Department of Chemistry Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warszawa Poland e-mail: lewin@ch.pw.edu.pl Phone: +48 22 6607315 Fax: +48 22 6607279 ; 'mgr Iwona Justyniak' ; Department of Chemistry Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warszawa Poland ; 'dr Zbigniew Ochal' ; Department of Chemistry Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warszawa Poland ; 'dr Janusz Zachara' ; Department of Chemistry Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warszawa Poland e-mail: janzac@ch.pw.edu.pl Fax: +48 22 6282741 Phone: +48 22 6225186 ; #======================================================================= # 4. COMPOUND (1b) data_acet _audit_creation_method SHELXL-97 _chemical_name_systematic ; bis[\m-(acetoinato)]tetraethyldialuminum ; _chemical_name_common ? _chemical_formula_moiety 'C16 H34 Al2 O4' _chemical_formula_structural '[Al(C2H5)2(C4H7O2)]2' _chemical_formula_sum 'C16 H34 Al2 O4' _chemical_formula_weight 344.39 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' 'Al' 'Al' 0.0645 0.0514 '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_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.3548(18) _cell_length_b 8.8850(17) _cell_length_c 16.790(3) _cell_angle_alpha 84.371(16) _cell_angle_beta 86.844(18) _cell_angle_gamma 78.253(17) _cell_volume 1068.3(4) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 24 _cell_measurement_theta_min 7.68 _cell_measurement_theta_max 15.80 _exptl_crystal_description 'prism' _exptl_crystal_colour 'white' _exptl_crystal_size_max 0.47 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.071 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 376 _exptl_absorpt_coefficient_mu 0.149 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed X-ray tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Siemens P3 four-circle diffractometer' _diffrn_measurement_method '\q/2\q' _diffrn_standards_number 3 _diffrn_standards_interval_count 100 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 8.6 _diffrn_reflns_number 7403 _diffrn_reflns_av_R_equivalents 0.0219 _diffrn_reflns_av_sigmaI/netI 0.0268 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.35 _diffrn_reflns_theta_max 25.05 _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.05 _diffrn_measured_fraction_theta_full 0.997 _diffrn_special_details ; 2\q scan width: 2.0\% plus K\a1-K\a2 separation; variable scan speed: 4.19 to 29.30\%(2\q)/min, background/peak time ratio 0.60 ; _reflns_number_total 3785 _reflns_number_gt 2947 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens P3 software' _computing_cell_refinement 'Siemens P3 software' _computing_data_reduction 'XDISK, Siemens P3 software' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP III (Burnett, Johnson, 1996)' _computing_publication_material ; SHELXL-93 (Sheldrick, 1993) & PARST 96 (Nardelli, 1996)' ; _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. Positional parameters of all hydrogen atoms were calculated. Methyl group (C11) was refined as a disordered group over two positions with adjusted occupancy factors, restraining chemically equivalent C-C distances to be equal. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.1032P)^2^+0.2931P] 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 3785 _refine_ls_number_parameters 231 _refine_ls_number_restraints 7 _refine_ls_R_factor_all 0.0761 _refine_ls_R_factor_gt 0.0592 _refine_ls_wR_factor_ref 0.1769 _refine_ls_wR_factor_gt 0.1628 _refine_ls_goodness_of_fit_ref 1.068 _refine_ls_restrained_S_all 1.068 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 _refine_diff_density_max 0.358 _refine_diff_density_min -0.329 _refine_diff_density_rms 0.052 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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Al1 Al 0.60574(12) -0.11100(9) 0.06150(5) 0.0536(3) Uani 1 d . . . Al2 Al 0.12490(12) 0.40689(9) 0.44233(4) 0.0547(3) Uani 1 d . . . O1 O 0.5416(2) 0.09788(19) 0.03169(10) 0.0518(5) Uani 1 d . . . O2 O 0.7324(3) -0.0094(2) 0.15077(12) 0.0722(6) Uani 1 d . . . O3 O 0.0791(2) 0.4190(2) 0.55073(10) 0.0527(5) Uani 1 d . . . O4 O 0.3278(3) 0.2180(3) 0.49488(13) 0.0773(6) Uani 1 d . . . C1 C 0.4710(6) 0.3425(4) 0.0896(3) 0.1012(14) Uani 1 d . . . H1A H 0.4016 0.3895 0.0437 0.126(9) Uiso 1 calc R . . H1B H 0.5293 0.4171 0.1103 0.126(9) Uiso 1 calc R . . H1C H 0.3888 0.3064 0.1301 0.126(9) Uiso 1 calc R . . C2 C 0.6173(4) 0.2089(3) 0.06558(18) 0.0620(7) Uani 1 d . . . H2 H 0.7027 0.2483 0.0258 0.071(9) Uiso 1 calc R . . C3 C 0.7272(4) 0.1279(4) 0.13551(17) 0.0636(7) Uani 1 d . . . C4 C 0.8293(6) 0.2146(5) 0.1837(2) 0.0900(11) Uani 1 d . . . H4A H 0.9241 0.1432 0.2127 0.155(12) Uiso 1 calc R . . H4B H 0.7439 0.2707 0.2208 0.155(12) Uiso 1 calc R . . H4C H 0.8855 0.2855 0.1486 0.155(12) Uiso 1 calc R . . C5 C 0.4510(5) -0.2053(4) 0.14355(19) 0.0763(9) Uani 1 d . . . H5A H 0.4080 -0.2878 0.1212 0.097(8) Uiso 1 calc R . . H5B H 0.5276 -0.2510 0.1883 0.097(8) Uiso 1 calc R . . C6 C 0.2852(6) -0.0947(6) 0.1743(3) 0.1069(14) Uani 1 d . . . H6A H 0.2227 -0.1468 0.2168 0.135(10) Uiso 1 calc R . . H6B H 0.2015 -0.0571 0.1316 0.135(10) Uiso 1 calc R . . H6C H 0.3254 -0.0095 0.1940 0.135(10) Uiso 1 calc R . . C7 C 0.8578(5) -0.2190(4) 0.0276(2) 0.0753(9) Uani 1 d . . . H7A H 0.8499 -0.2577 -0.0239 0.097(9) Uiso 1 calc R . . H7B H 0.9382 -0.1443 0.0202 0.097(9) Uiso 1 calc R . . C8 C 0.9468(6) -0.3509(5) 0.0845(3) 0.1117(15) Uani 1 d . . . H8A H 1.0665 -0.3969 0.0629 0.144(11) Uiso 1 calc R . . H8B H 0.8697 -0.4266 0.0920 0.144(11) Uiso 1 calc R . . H8C H 0.9612 -0.3136 0.1351 0.144(11) Uiso 1 calc R . . C11 C 0.0914(7) 0.2539(7) 0.6740(3) 0.107(3) Uani 0.853(11) d PDU A 1 H11A H 0.0049 0.3310 0.7004 0.129(12) Uiso 0.853(11) calc PR A 1 H11B H 0.1774 0.1954 0.7120 0.129(12) Uiso 0.853(11) calc PR A 1 H11C H 0.0251 0.1861 0.6519 0.129(12) Uiso 0.853(11) calc PR A 1 C12 C 0.1942(5) 0.3294(4) 0.60910(17) 0.0679(8) Uani 0.853(11) d PD A 1 H12 H 0.2609 0.3976 0.6331 0.064(10) Uiso 0.853(11) calc PR A 1 C11A C 0.200(5) 0.377(4) 0.6894(11) 0.112(14) Uani 0.147(11) d PDU A 2 H11D H 0.0906 0.4530 0.7000 0.167 Uiso 0.147(11) calc PR A 2 H11E H 0.3083 0.4197 0.6933 0.167 Uiso 0.147(11) calc PR A 2 H11F H 0.2041 0.2888 0.7278 0.167 Uiso 0.147(11) calc PR A 2 C12A C 0.1942(5) 0.3294(4) 0.60910(17) 0.0679(8) Uani 0.147(11) d PD A 2 H12A H 0.1096 0.2585 0.6244 0.081 Uiso 0.147(11) calc PR A 2 C13 C 0.3346(4) 0.2139(3) 0.56698(19) 0.0659(8) Uani 1 d . . . C14 C 0.4801(6) 0.1031(4) 0.6134(3) 0.0982(13) Uani 1 d . . . H14A H 0.5887 0.0750 0.5794 0.170(13) Uiso 1 calc R . . H14B H 0.4333 0.0124 0.6324 0.170(13) Uiso 1 calc R . . H14C H 0.5119 0.1509 0.6582 0.170(13) Uiso 1 calc R . . C15 C 0.0098(6) 0.2697(5) 0.3858(2) 0.0907(11) Uani 1 d . . . H15A H -0.0456 0.3275 0.3381 0.121(11) Uiso 1 calc R . . H15B H 0.1068 0.1868 0.3685 0.121(11) Uiso 1 calc R . . C16 C -0.1342(9) 0.2009(6) 0.4324(4) 0.147(2) Uani 1 d . . . H16A H -0.1857 0.1392 0.3992 0.25(2) Uiso 1 calc R . . H16B H -0.2309 0.2815 0.4504 0.25(2) Uiso 1 calc R . . H16C H -0.0795 0.1371 0.4779 0.25(2) Uiso 1 calc R . . C17 C 0.3298(5) 0.4993(4) 0.3898(2) 0.0772(9) Uani 1 d . . . H17A H 0.2838 0.6089 0.3772 0.110(10) Uiso 1 calc R . . H17B H 0.4281 0.4879 0.4275 0.110(10) Uiso 1 calc R . . C18 C 0.4110(7) 0.4296(6) 0.3142(3) 0.1233(18) Uani 1 d . . . H18A H 0.4978 0.4883 0.2889 0.164(13) Uiso 1 calc R . . H18B H 0.3131 0.4312 0.2784 0.164(13) Uiso 1 calc R . . H18C H 0.4738 0.3249 0.3271 0.164(13) Uiso 1 calc R . . 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 Al1 0.0685(5) 0.0416(4) 0.0458(4) -0.0019(3) -0.0041(4) -0.0002(4) Al2 0.0669(5) 0.0556(5) 0.0399(4) -0.0090(3) 0.0022(3) -0.0073(4) O1 0.0677(12) 0.0402(9) 0.0465(9) -0.0072(7) -0.0065(8) -0.0054(8) O2 0.0903(15) 0.0631(13) 0.0616(12) -0.0035(10) -0.0184(11) -0.0084(11) O3 0.0622(11) 0.0530(10) 0.0392(9) -0.0019(7) 0.0007(8) -0.0042(8) O4 0.0916(16) 0.0666(13) 0.0645(14) -0.0129(10) -0.0026(11) 0.0089(11) C1 0.128(3) 0.0568(19) 0.116(3) -0.035(2) -0.030(3) 0.009(2) C2 0.0771(19) 0.0519(15) 0.0587(16) -0.0101(12) -0.0024(14) -0.0142(14) C3 0.0715(19) 0.0646(18) 0.0541(16) -0.0162(14) -0.0002(13) -0.0075(14) C4 0.100(3) 0.094(3) 0.083(2) -0.035(2) -0.017(2) -0.020(2) C5 0.103(3) 0.0665(19) 0.0578(18) 0.0083(14) -0.0010(17) -0.0197(18) C6 0.106(3) 0.124(4) 0.089(3) 0.000(2) 0.024(2) -0.032(3) C7 0.073(2) 0.0656(19) 0.080(2) -0.0119(16) -0.0044(16) 0.0045(16) C8 0.104(3) 0.084(3) 0.127(4) 0.003(2) -0.013(3) 0.024(2) C11 0.103(4) 0.130(5) 0.062(3) 0.035(3) 0.009(2) 0.014(3) C12 0.083(2) 0.0675(18) 0.0467(15) -0.0036(13) -0.0091(14) 0.0016(16) C11A 0.14(3) 0.09(2) 0.081(18) -0.001(15) -0.036(18) 0.02(2) C12A 0.083(2) 0.0675(18) 0.0467(15) -0.0036(13) -0.0091(14) 0.0016(16) C13 0.0741(19) 0.0555(16) 0.0657(19) -0.0061(13) -0.0087(15) -0.0053(14) C14 0.111(3) 0.072(2) 0.098(3) -0.001(2) -0.027(2) 0.017(2) C15 0.110(3) 0.078(2) 0.090(3) -0.034(2) -0.016(2) -0.018(2) C16 0.167(5) 0.111(4) 0.185(6) -0.015(4) -0.040(5) -0.072(4) C17 0.071(2) 0.090(2) 0.0640(19) -0.0017(16) 0.0128(16) -0.0072(17) C18 0.132(4) 0.149(4) 0.087(3) -0.020(3) 0.054(3) -0.032(3) _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 Al1 O1 1.8452(18) . ? Al1 O1 1.9328(19) 2_655 ? Al1 C5 1.971(3) . ? Al1 C7 1.987(3) . ? Al1 O2 2.166(2) . ? Al1 Al1 2.9799(17) 2_655 ? Al2 O3 1.8423(18) . ? Al2 O3 1.9311(19) 2_566 ? Al2 C15 1.959(4) . ? Al2 C17 1.984(3) . ? Al2 O4 2.158(2) . ? Al2 Al2 2.9770(17) 2_566 ? O1 C2 1.406(3) . ? O1 Al1 1.9328(19) 2_655 ? O2 C3 1.215(4) . ? O3 C12 1.405(3) . ? O3 Al2 1.9311(19) 2_566 ? O4 C13 1.211(4) . ? C1 C2 1.502(4) . ? C2 C3 1.501(4) . ? C3 C4 1.495(4) . ? C5 C6 1.504(5) . ? C7 C8 1.501(5) . ? C11 C12 1.477(5) . ? C12 C13 1.500(4) . ? C13 C14 1.495(5) . ? C15 C16 1.479(7) . ? C17 C18 1.508(5) . ? 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 Al1 O1 75.88(8) . 2_655 ? O1 Al1 C5 119.11(12) . . ? O1 Al1 C5 100.62(13) 2_655 . ? O1 Al1 C7 117.12(13) . . ? O1 Al1 C7 104.49(12) 2_655 . ? C5 Al1 C7 122.26(15) . . ? O1 Al1 O2 76.75(8) . . ? O1 Al1 O2 152.63(9) 2_655 . ? C5 Al1 O2 91.93(13) . . ? C7 Al1 O2 88.68(13) . . ? O1 Al1 Al1 38.98(6) . 2_655 ? O1 Al1 Al1 36.91(5) 2_655 2_655 ? C5 Al1 Al1 114.88(12) . 2_655 ? C7 Al1 Al1 116.39(11) . 2_655 ? O2 Al1 Al1 115.73(7) . 2_655 ? O3 Al2 O3 75.85(9) . 2_566 ? O3 Al2 C15 119.96(15) . . ? O3 Al2 C15 100.75(14) 2_566 . ? O3 Al2 C17 118.49(13) . . ? O3 Al2 C17 103.76(13) 2_566 . ? C15 Al2 C17 120.33(17) . . ? O3 Al2 O4 76.72(8) . . ? O3 Al2 O4 152.56(9) 2_566 . ? C15 Al2 O4 92.78(14) . . ? C17 Al2 O4 89.40(13) . . ? O3 Al2 Al2 38.98(6) . 2_566 ? O3 Al2 Al2 36.87(5) 2_566 2_566 ? C15 Al2 Al2 115.47(14) . 2_566 ? C17 Al2 Al2 116.71(12) . 2_566 ? O4 Al2 Al2 115.69(7) . 2_566 ? C2 O1 Al1 123.32(17) . . ? C2 O1 Al1 131.76(17) . 2_655 ? Al1 O1 Al1 104.12(8) . 2_655 ? C3 O2 Al1 113.44(19) . . ? C12 O3 Al2 123.28(17) . . ? C12 O3 Al2 131.94(16) . 2_566 ? Al2 O3 Al2 104.15(9) . 2_566 ? C13 O4 Al2 114.3(2) . . ? O1 C2 C3 107.2(2) . . ? O1 C2 C1 112.4(3) . . ? C3 C2 C1 111.9(3) . . ? O2 C3 C4 121.5(3) . . ? O2 C3 C2 118.1(3) . . ? C4 C3 C2 120.4(3) . . ? C6 C5 Al1 114.3(2) . . ? C8 C7 Al1 115.4(3) . . ? O3 C12 C11 113.5(3) . . ? O3 C12 C13 107.5(2) . . ? C11 C12 C13 111.7(3) . . ? O4 C13 C14 122.4(3) . . ? O4 C13 C12 117.5(3) . . ? C14 C13 C12 120.1(3) . . ? C16 C15 Al2 115.6(3) . . ? C18 C17 Al2 114.5(3) . . ? #===END