# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 # Surface enhanced stereoselectivity in Mukaiyama-aldol # reactions catalyzed by clay-supported bis(oxazoline)- # copper complexes # # by Jos M. Fraile, Clara I. Herrerer as, Fernando J. Lahoz, # Mar a J. Fabra, Ignacio P rez and Jos A. Mayoral # # Submitted to Chemistry - A European Journal # Manuscript number ........... # ----------------------------------------------------------- # # Person for contact _publ_contact_author_name 'Dr. Fernando J. Lahoz' _publ_contact_author_address ; Dr. Fernando J. Lahoz Departamento de Qu\'imica Inorg\'anica - I.C.M.A. Facultad de Ciencias Universidad de Zaragoza - C.S.I.C. 50009 Zaragoza, Spain ; _publ_contact_author_phone '+34 976 761147' _publ_contact_author_fax '+34 976 761187' _publ_contact_author_email lahoz@unizar.es _journal_volume ? _journal_page_first ? _journal_page_last ? _journal_year ? loop_ _publ_author_name J.M.Fraile M.J.Fabra C.I.Herreras F.J.Lahoz J.A.Mayoral I.Perez # ---------------------------------------------------------- # Data for compound_9_10 (local labelling as fjl40as) data_compound_9_10 _database_code_depnum_ccdc_archive 'CCDC 684313' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C13 H12 O5' _chemical_formula_sum 'C13 H12 O5' _chemical_formula_weight 248.23 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall '-P 2ybc' _chemical_absolute_configuration rmad 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 11.5169(15) _cell_length_b 7.9585(11) _cell_length_c 13.1517(17) _cell_angle_alpha 90.00 _cell_angle_beta 94.033(2) _cell_angle_gamma 90.00 _cell_volume 1202.5(3) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 2598 _cell_measurement_theta_min 2.99 _cell_measurement_theta_max 26.99 _exptl_crystal_description 'regular block' _exptl_crystal_colour colorless _exptl_crystal_size_max 0.164 _exptl_crystal_size_mid 0.163 _exptl_crystal_size_min 0.161 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.371 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 520 _exptl_absorpt_coefficient_mu 0.106 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.971 _exptl_absorpt_correction_T_max 0.989 _exptl_absorpt_process_details ; SADABS: Area-Detector Absorption Correction. (1996) Bruker-AXS within SAINT+ package, v. 6.45. ; _diffrn_ambient_temperature 100(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 'Bruker SMART APEX CCD system' _diffrn_measurement_method '\w rotations with narrow frames' _diffrn_detector_area_resol_mean 8.26 _diffrn_standards_decay_% 'no decay' _diffrn_reflns_number 7457 _diffrn_reflns_av_R_equivalents 0.0222 _diffrn_reflns_av_sigmaI/netI 0.0250 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.77 _diffrn_reflns_theta_max 27.00 _reflns_number_total 2602 _reflns_number_gt 2295 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART v. 5.611 (Bruker AXS, 2000)' _computing_cell_refinement 'SAINT+ v. 6.45 (Bruker AXS, 2003)' _computing_data_reduction 'SAINT+ v. 6.45 (Bruker AXS, 2003)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XP program, SHELXTL v6.12, Bruker2000' _computing_publication_material 'XCIF program, SHELXTLv6.12, BrukerAXS' _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. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were included from observed positions and refined as free isotropic atoms. No eletron density residual was observed above 0.48 e/\%A^3^. ; _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^)+(0.0552P)^2^+0.4273P] 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 2602 _refine_ls_number_parameters 211 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0485 _refine_ls_R_factor_gt 0.0425 _refine_ls_wR_factor_ref 0.1075 _refine_ls_wR_factor_gt 0.1034 _refine_ls_goodness_of_fit_ref 1.046 _refine_ls_restrained_S_all 1.046 _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 O1 O 0.81143(9) 0.24468(13) 0.74456(7) 0.0204(2) Uani 1 1 d . . . H1 H 0.8193(16) 0.345(3) 0.7219(15) 0.038(5) Uiso 1 1 d . . . O2 O 1.11962(8) 0.02601(13) 0.87111(7) 0.0225(2) Uani 1 1 d . . . O3 O 0.95255(8) 0.13782(12) 0.91573(7) 0.0190(2) Uani 1 1 d . . . O4 O 0.82120(10) 0.53322(13) 0.84987(8) 0.0288(3) Uani 1 1 d . . . O5 O 0.79638(9) 0.39821(13) 0.99624(7) 0.0257(3) Uani 1 1 d . . . C1 C 0.76844(12) 0.24152(17) 0.84184(10) 0.0180(3) Uani 1 1 d . . . C2 C 0.83000(11) 0.09724(17) 0.90163(10) 0.0179(3) Uani 1 1 d . . . H2 H 0.8008(12) 0.0895(19) 0.9682(12) 0.014(4) Uiso 1 1 d . . . C3 C 0.82721(13) -0.06688(18) 0.84670(11) 0.0213(3) Uani 1 1 d . . . H3 H 0.7550(15) -0.126(2) 0.8300(13) 0.026(4) Uiso 1 1 d . . . C4 C 0.93439(12) -0.11365(18) 0.83004(11) 0.0221(3) Uani 1 1 d . . . H4 H 0.9589(15) -0.212(2) 0.7952(13) 0.029(4) Uiso 1 1 d . . . C5 C 1.01499(12) 0.01596(17) 0.87134(10) 0.0187(3) Uani 1 1 d . . . C6 C 0.79868(11) 0.40857(17) 0.89576(10) 0.0188(3) Uani 1 1 d . . . C7 C 0.82773(18) 0.5504(2) 1.05259(13) 0.0328(4) Uani 1 1 d . . . H7A H 0.8232(18) 0.517(3) 1.1207(18) 0.055(6) Uiso 1 1 d . . . H7B H 0.9035(19) 0.588(3) 1.0363(15) 0.044(6) Uiso 1 1 d . . . H7C H 0.775(2) 0.642(3) 1.0308(18) 0.062(7) Uiso 1 1 d . . . C8 C 0.63618(12) 0.21175(17) 0.83603(11) 0.0195(3) Uani 1 1 d . . . C9 C 0.57670(13) 0.18550(19) 0.74162(11) 0.0247(3) Uani 1 1 d . . . H9 H 0.6195(15) 0.186(2) 0.6825(14) 0.031(5) Uiso 1 1 d . . . C10 C 0.45781(14) 0.1557(2) 0.73519(13) 0.0308(4) Uani 1 1 d . . . H10 H 0.4184(17) 0.139(3) 0.6682(16) 0.040(5) Uiso 1 1 d . . . C11 C 0.39683(14) 0.1518(2) 0.82162(14) 0.0311(4) Uani 1 1 d . . . H11 H 0.3160(16) 0.130(2) 0.8170(13) 0.030(5) Uiso 1 1 d . . . C12 C 0.45582(14) 0.1766(2) 0.91578(14) 0.0334(4) Uani 1 1 d . . . H12 H 0.4154(16) 0.172(3) 0.9768(15) 0.042(5) Uiso 1 1 d . . . C13 C 0.57466(13) 0.2062(2) 0.92323(12) 0.0274(3) Uani 1 1 d . . . H13 H 0.6135(15) 0.223(2) 0.9892(14) 0.028(4) 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 O1 0.0253(5) 0.0186(5) 0.0177(5) 0.0005(4) 0.0044(4) -0.0017(4) O2 0.0199(5) 0.0259(6) 0.0218(5) 0.0003(4) 0.0025(4) 0.0004(4) O3 0.0175(5) 0.0183(5) 0.0209(5) -0.0019(4) -0.0003(4) -0.0003(4) O4 0.0430(7) 0.0184(5) 0.0247(5) 0.0010(4) 0.0013(5) -0.0054(5) O5 0.0371(6) 0.0209(5) 0.0191(5) -0.0029(4) 0.0031(4) -0.0041(4) C1 0.0194(7) 0.0172(7) 0.0174(6) 0.0001(5) 0.0019(5) 0.0000(5) C2 0.0165(6) 0.0181(7) 0.0191(7) 0.0013(5) 0.0003(5) -0.0019(5) C3 0.0241(7) 0.0165(7) 0.0228(7) 0.0030(5) -0.0019(5) -0.0027(6) C4 0.0266(7) 0.0164(7) 0.0230(7) -0.0002(5) 0.0004(5) 0.0003(6) C5 0.0234(7) 0.0178(7) 0.0150(6) 0.0027(5) 0.0014(5) 0.0018(5) C6 0.0163(6) 0.0187(7) 0.0214(7) -0.0002(5) 0.0006(5) 0.0010(5) C7 0.0482(11) 0.0251(9) 0.0248(8) -0.0074(7) 0.0010(7) -0.0051(8) C8 0.0195(7) 0.0145(6) 0.0243(7) 0.0016(5) 0.0005(5) -0.0006(5) C9 0.0241(7) 0.0241(8) 0.0255(7) 0.0002(6) -0.0010(6) -0.0012(6) C10 0.0262(8) 0.0294(9) 0.0357(8) -0.0008(7) -0.0070(6) -0.0037(6) C11 0.0176(7) 0.0261(8) 0.0493(10) 0.0019(7) -0.0008(6) -0.0024(6) C12 0.0256(8) 0.0376(10) 0.0380(9) 0.0026(7) 0.0100(7) -0.0004(7) C13 0.0245(8) 0.0330(9) 0.0247(7) 0.0007(6) 0.0024(6) 0.0004(6) _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 O1 C1 1.4042(16) . ? O1 H1 0.86(2) . ? O2 C5 1.2079(16) . ? O3 C5 1.3629(16) . ? O3 C2 1.4471(16) . ? O4 C6 1.1990(17) . ? O5 C6 1.3263(17) . ? O5 C7 1.4521(19) . ? C1 C6 1.5352(19) . ? C1 C2 1.5366(19) . ? C1 C8 1.5381(19) . ? C2 C3 1.492(2) . ? C2 H2 0.962(15) . ? C3 C4 1.322(2) . ? C3 H3 0.967(17) . ? C4 C5 1.4662(19) . ? C4 H4 0.959(19) . ? C7 H7A 0.94(2) . ? C7 H7B 0.96(2) . ? C7 H7C 0.98(3) . ? C8 C13 1.390(2) . ? C8 C9 1.3910(19) . ? C9 C10 1.386(2) . ? C9 H9 0.950(19) . ? C10 C11 1.378(2) . ? C10 H10 0.97(2) . ? C11 C12 1.384(2) . ? C11 H11 0.945(18) . ? C12 C13 1.385(2) . ? C12 H12 0.96(2) . ? C13 H13 0.958(18) . ? 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 C1 O1 H1 112.7(13) . . ? C5 O3 C2 109.00(10) . . ? C6 O5 C7 115.78(12) . . ? O1 C1 C6 108.80(11) . . ? O1 C1 C2 107.46(11) . . ? C6 C1 C2 109.22(11) . . ? O1 C1 C8 111.65(11) . . ? C6 C1 C8 110.37(11) . . ? C2 C1 C8 109.27(11) . . ? O3 C2 C3 104.19(11) . . ? O3 C2 C1 108.03(11) . . ? C3 C2 C1 114.40(11) . . ? O3 C2 H2 107.4(9) . . ? C3 C2 H2 112.8(9) . . ? C1 C2 H2 109.6(9) . . ? C4 C3 C2 109.76(13) . . ? C4 C3 H3 128.6(10) . . ? C2 C3 H3 121.6(10) . . ? C3 C4 C5 108.34(13) . . ? C3 C4 H4 128.2(11) . . ? C5 C4 H4 123.4(11) . . ? O2 C5 O3 120.69(12) . . ? O2 C5 C4 130.65(13) . . ? O3 C5 C4 108.66(11) . . ? O4 C6 O5 124.98(13) . . ? O4 C6 C1 122.28(12) . . ? O5 C6 C1 112.74(11) . . ? O5 C7 H7A 102.9(14) . . ? O5 C7 H7B 110.0(12) . . ? H7A C7 H7B 114.4(17) . . ? O5 C7 H7C 110.1(14) . . ? H7A C7 H7C 114.4(19) . . ? H7B C7 H7C 105.1(18) . . ? C13 C8 C9 118.94(13) . . ? C13 C8 C1 121.61(12) . . ? C9 C8 C1 119.42(13) . . ? C10 C9 C8 120.16(14) . . ? C10 C9 H9 121.2(11) . . ? C8 C9 H9 118.6(11) . . ? C11 C10 C9 120.80(15) . . ? C11 C10 H10 120.8(12) . . ? C9 C10 H10 118.4(12) . . ? C10 C11 C12 119.23(15) . . ? C10 C11 H11 120.5(11) . . ? C12 C11 H11 120.2(11) . . ? C11 C12 C13 120.52(15) . . ? C11 C12 H12 120.5(12) . . ? C13 C12 H12 119.0(12) . . ? C12 C13 C8 120.35(14) . . ? C12 C13 H13 119.0(11) . . ? C8 C13 H13 120.7(11) . . ? 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 C5 O3 C2 C3 1.98(13) . . . . ? C5 O3 C2 C1 -120.05(11) . . . . ? O1 C1 C2 O3 65.00(13) . . . . ? C6 C1 C2 O3 -52.87(14) . . . . ? C8 C1 C2 O3 -173.70(10) . . . . ? O1 C1 C2 C3 -50.51(15) . . . . ? C6 C1 C2 C3 -168.38(11) . . . . ? C8 C1 C2 C3 70.80(15) . . . . ? O3 C2 C3 C4 -0.77(15) . . . . ? C1 C2 C3 C4 116.95(13) . . . . ? C2 C3 C4 C5 -0.64(16) . . . . ? C2 O3 C5 O2 177.90(12) . . . . ? C2 O3 C5 C4 -2.42(14) . . . . ? C3 C4 C5 O2 -178.43(14) . . . . ? C3 C4 C5 O3 1.94(15) . . . . ? C7 O5 C6 O4 -2.1(2) . . . . ? C7 O5 C6 C1 178.14(13) . . . . ? O1 C1 C6 O4 20.81(18) . . . . ? C2 C1 C6 O4 137.83(14) . . . . ? C8 C1 C6 O4 -102.02(15) . . . . ? O1 C1 C6 O5 -159.45(11) . . . . ? C2 C1 C6 O5 -42.42(15) . . . . ? C8 C1 C6 O5 77.73(14) . . . . ? O1 C1 C8 C13 -179.09(13) . . . . ? C6 C1 C8 C13 -57.94(17) . . . . ? C2 C1 C8 C13 62.18(17) . . . . ? O1 C1 C8 C9 2.53(18) . . . . ? C6 C1 C8 C9 123.68(14) . . . . ? C2 C1 C8 C9 -116.20(14) . . . . ? C13 C8 C9 C10 0.5(2) . . . . ? C1 C8 C9 C10 178.93(14) . . . . ? C8 C9 C10 C11 0.1(2) . . . . ? C9 C10 C11 C12 -0.6(2) . . . . ? C10 C11 C12 C13 0.5(3) . . . . ? C11 C12 C13 C8 0.1(3) . . . . ? C9 C8 C13 C12 -0.6(2) . . . . ? C1 C8 C13 C12 -178.99(14) . . . . ? _diffrn_measured_fraction_theta_max 0.986 _diffrn_reflns_theta_full 27.00 _diffrn_measured_fraction_theta_full 0.986 _refine_diff_density_max 0.475 _refine_diff_density_min -0.155 _refine_diff_density_rms 0.047 # Data for compound_11 (local labelling as fjl42b) data_compound_11 _database_code_depnum_ccdc_archive 'CCDC 684314' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C13 H12 O5' _chemical_formula_sum 'C13 H12 O5' _chemical_formula_weight 248.23 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21 _symmetry_space_group_name_Hall 'P 2yb' _chemical_absolute_configuration ad loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 7.5836(15) _cell_length_b 5.7612(12) _cell_length_c 13.331(3) _cell_angle_alpha 90.00 _cell_angle_beta 102.73(3) _cell_angle_gamma 90.00 _cell_volume 568.1(2) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4998 _cell_measurement_theta_min 3.3908 _cell_measurement_theta_max 73.4687 _exptl_crystal_description 'irregular block' _exptl_crystal_colour colorless _exptl_crystal_size_max 0.124 _exptl_crystal_size_mid 0.120 _exptl_crystal_size_min 0.074 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.451 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 260 _exptl_absorpt_coefficient_mu 0.949 _exptl_absorpt_correction_T_min 0.812 _exptl_absorpt_correction_T_max 0.940 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.5 (release 08-05-2007 CrysAlis171 .NET) (compiled May 8 2007,13:10:02) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'Nova micro-focus (Cu) X-ray source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford diffraction Xcalibur Nova' _diffrn_measurement_method '\w rotations with narrow frames' _diffrn_detector_area_resol_mean 8.2640 _diffrn_standards_decay_% 'no decay' _diffrn_reflns_number 5624 _diffrn_reflns_av_R_equivalents 0.0214 _diffrn_reflns_av_sigmaI/netI 0.0184 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.40 _diffrn_reflns_theta_max 73.78 _reflns_number_total 2199 _reflns_number_gt 2088 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.32.5 (release 08-05-2007 CrysAlis171 .NET) (compiled May 8 2007,13:10:02) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.5 (release 08-05-2007 CrysAlis171 .NET) (compiled May 8 2007,13:10:02) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.5 (release 08-05-2007 CrysAlis171 .NET) (compiled May 8 2007,13:10:02) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XP program, SHELXTL v6.12, Bruker2000' _computing_publication_material 'XCIF program, SHELXTLv6.12, BrukerAXS' _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^)+(0.0384P)^2^+0.2259P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.1(2) _refine_ls_number_reflns 2199 _refine_ls_number_parameters 211 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0355 _refine_ls_R_factor_gt 0.0316 _refine_ls_wR_factor_ref 0.0841 _refine_ls_wR_factor_gt 0.0815 _refine_ls_goodness_of_fit_ref 1.127 _refine_ls_restrained_S_all 1.127 _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 C1 C 0.9224(2) 0.3169(3) 0.71185(14) 0.0195(4) Uani 1 1 d . . . C2 C 0.8490(2) 0.5160(3) 0.63675(14) 0.0199(4) Uani 1 1 d . . . C3 C 0.9014(3) 0.5063(3) 0.53483(14) 0.0243(4) Uani 1 1 d . . . C4 C 0.7543(3) 0.4944(4) 0.46060(15) 0.0289(4) Uani 1 1 d . . . C5 C 0.5962(3) 0.4910(4) 0.50655(15) 0.0271(4) Uani 1 1 d . . . C6 C 1.1302(2) 0.3302(4) 0.74532(13) 0.0205(4) Uani 1 1 d . . . C7 C 1.3812(3) 0.5843(4) 0.77496(17) 0.0280(4) Uani 1 1 d . . . C8 C 0.8503(2) 0.3403(3) 0.81035(14) 0.0203(4) Uani 1 1 d . . . C9 C 0.8860(2) 0.5406(3) 0.87055(14) 0.0219(4) Uani 1 1 d . . . C10 C 0.8294(2) 0.5578(4) 0.96249(15) 0.0254(4) Uani 1 1 d . . . C11 C 0.7347(3) 0.3767(4) 0.99495(15) 0.0263(4) Uani 1 1 d . . . C12 C 0.6960(3) 0.1803(4) 0.93428(16) 0.0270(4) Uani 1 1 d . . . C13 C 0.7542(2) 0.1603(3) 0.84278(14) 0.0229(4) Uani 1 1 d . . . O1 O 0.88505(18) 0.0996(2) 0.66426(10) 0.0224(3) Uani 1 1 d . . . O2 O 0.43650(19) 0.4854(3) 0.46746(12) 0.0355(4) Uani 1 1 d . . . O3 O 0.65417(16) 0.4947(2) 0.61037(9) 0.0229(3) Uani 1 1 d . . . O4 O 1.22555(17) 0.1665(2) 0.77340(10) 0.0264(3) Uani 1 1 d . . . O5 O 1.18713(16) 0.5487(2) 0.74095(10) 0.0241(3) Uani 1 1 d . . . H9 H 0.955(3) 0.668(5) 0.8483(18) 0.031(6) Uiso 1 1 d . . . H13 H 0.733(3) 0.019(4) 0.8010(17) 0.021(5) Uiso 1 1 d . . . H12 H 0.633(3) 0.054(5) 0.9548(19) 0.034(6) Uiso 1 1 d . . . H4 H 0.749(3) 0.489(5) 0.390(2) 0.041(7) Uiso 1 1 d . . . H7A H 1.440(3) 0.503(5) 0.7252(19) 0.035(6) Uiso 1 1 d . . . H10 H 0.859(3) 0.697(5) 1.0055(19) 0.033(6) Uiso 1 1 d . . . H2 H 0.883(3) 0.668(4) 0.6686(15) 0.014(5) Uiso 1 1 d . . . H7B H 1.424(3) 0.520(5) 0.8443(19) 0.029(6) Uiso 1 1 d . . . H11 H 0.697(3) 0.392(4) 1.0627(18) 0.023(5) Uiso 1 1 d . . . H3 H 1.026(3) 0.514(5) 0.5284(17) 0.028(6) Uiso 1 1 d . . . H7C H 1.395(3) 0.759(5) 0.7749(18) 0.031(6) Uiso 1 1 d . . . H1 H 0.775(4) 0.091(5) 0.633(2) 0.048(8) 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 C1 0.0224(9) 0.0167(8) 0.0178(9) -0.0009(7) 0.0010(7) 0.0003(7) C2 0.0192(8) 0.0203(9) 0.0194(9) 0.0004(8) 0.0024(6) 0.0000(7) C3 0.0319(10) 0.0185(9) 0.0234(10) 0.0021(8) 0.0082(7) 0.0005(8) C4 0.0457(11) 0.0229(9) 0.0167(9) 0.0027(8) 0.0036(8) 0.0003(9) C5 0.0336(10) 0.0169(9) 0.0251(10) 0.0030(8) -0.0061(8) 0.0000(8) C6 0.0213(8) 0.0245(9) 0.0146(9) -0.0010(7) 0.0014(7) 0.0024(7) C7 0.0192(8) 0.0317(11) 0.0313(11) -0.0001(9) 0.0016(8) -0.0013(8) C8 0.0190(8) 0.0203(9) 0.0196(9) 0.0030(7) -0.0001(6) 0.0038(7) C9 0.0220(8) 0.0219(10) 0.0208(9) -0.0006(7) 0.0023(7) 0.0002(7) C10 0.0244(9) 0.0267(10) 0.0223(10) -0.0024(8) -0.0007(7) 0.0040(8) C11 0.0245(9) 0.0347(12) 0.0194(10) 0.0032(8) 0.0041(7) 0.0064(8) C12 0.0244(9) 0.0275(10) 0.0287(10) 0.0060(9) 0.0048(7) 0.0013(8) C13 0.0239(9) 0.0224(9) 0.0215(9) 0.0004(8) 0.0027(7) 0.0012(7) O1 0.0239(6) 0.0193(7) 0.0220(7) -0.0034(5) 0.0005(5) 0.0015(5) O2 0.0322(7) 0.0231(7) 0.0409(8) 0.0054(7) -0.0141(6) -0.0014(6) O3 0.0207(6) 0.0233(6) 0.0224(7) 0.0023(6) -0.0001(5) 0.0025(5) O4 0.0250(6) 0.0267(7) 0.0252(7) 0.0001(6) 0.0007(5) 0.0050(6) O5 0.0189(6) 0.0227(7) 0.0286(7) 0.0031(6) 0.0012(5) -0.0004(5) _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 O1 1.404(2) . ? C1 C8 1.535(3) . ? C1 C6 1.542(2) . ? C1 C2 1.543(3) . ? C2 O3 1.447(2) . ? C2 C3 1.498(3) . ? C2 H2 0.98(2) . ? C3 C4 1.320(3) . ? C3 H3 0.97(2) . ? C4 C5 1.462(3) . ? C4 H4 0.94(3) . ? C5 O2 1.209(2) . ? C5 O3 1.357(2) . ? C6 O4 1.197(2) . ? C6 O5 1.336(2) . ? C7 O5 1.456(2) . ? C7 H7A 1.00(3) . ? C7 H7B 0.98(2) . ? C7 H7C 1.01(3) . ? C8 C13 1.390(3) . ? C8 C9 1.397(3) . ? C9 C10 1.389(3) . ? C9 H9 0.98(3) . ? C10 C11 1.388(3) . ? C10 H10 0.98(3) . ? C11 C12 1.384(3) . ? C11 H11 1.01(2) . ? C12 C13 1.390(3) . ? C12 H12 0.94(3) . ? C13 H13 0.98(2) . ? O1 H1 0.85(3) . ? 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 C1 C8 112.96(15) . . ? O1 C1 C6 105.44(15) . . ? C8 C1 C6 106.39(14) . . ? O1 C1 C2 111.20(14) . . ? C8 C1 C2 110.14(14) . . ? C6 C1 C2 110.50(15) . . ? O3 C2 C3 103.71(14) . . ? O3 C2 C1 107.32(14) . . ? C3 C2 C1 115.52(16) . . ? O3 C2 H2 109.9(12) . . ? C3 C2 H2 109.1(12) . . ? C1 C2 H2 111.0(12) . . ? C4 C3 C2 109.43(17) . . ? C4 C3 H3 128.1(13) . . ? C2 C3 H3 122.5(13) . . ? C3 C4 C5 108.80(18) . . ? C3 C4 H4 127.0(16) . . ? C5 C4 H4 124.2(16) . . ? O2 C5 O3 120.6(2) . . ? O2 C5 C4 131.01(19) . . ? O3 C5 C4 108.43(16) . . ? O4 C6 O5 125.24(16) . . ? O4 C6 C1 124.05(18) . . ? O5 C6 C1 110.69(15) . . ? O5 C7 H7A 107.3(14) . . ? O5 C7 H7B 110.0(14) . . ? H7A C7 H7B 110(2) . . ? O5 C7 H7C 103.6(14) . . ? H7A C7 H7C 114(2) . . ? H7B C7 H7C 111(2) . . ? C13 C8 C9 119.05(18) . . ? C13 C8 C1 120.72(17) . . ? C9 C8 C1 120.19(17) . . ? C10 C9 C8 120.49(18) . . ? C10 C9 H9 120.1(15) . . ? C8 C9 H9 119.4(14) . . ? C11 C10 C9 120.21(19) . . ? C11 C10 H10 119.8(15) . . ? C9 C10 H10 120.0(15) . . ? C12 C11 C10 119.3(2) . . ? C12 C11 H11 122.0(14) . . ? C10 C11 H11 118.7(14) . . ? C11 C12 C13 120.8(2) . . ? C11 C12 H12 121.1(15) . . ? C13 C12 H12 118.0(16) . . ? C8 C13 C12 120.07(18) . . ? C8 C13 H13 118.3(13) . . ? C12 C13 H13 121.6(13) . . ? C1 O1 H1 111(2) . . ? C5 O3 C2 109.45(14) . . ? C6 O5 C7 115.68(15) . . ? 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 O1 C1 C2 O3 64.26(18) . . . . ? C8 C1 C2 O3 -61.74(18) . . . . ? C6 C1 C2 O3 -178.99(14) . . . . ? O1 C1 C2 C3 -50.8(2) . . . . ? C8 C1 C2 C3 -176.83(15) . . . . ? C6 C1 C2 C3 65.9(2) . . . . ? O3 C2 C3 C4 3.1(2) . . . . ? C1 C2 C3 C4 120.26(18) . . . . ? C2 C3 C4 C5 -1.0(2) . . . . ? C3 C4 C5 O2 178.5(2) . . . . ? C3 C4 C5 O3 -1.7(2) . . . . ? O1 C1 C6 O4 -33.9(2) . . . . ? C8 C1 C6 O4 86.2(2) . . . . ? C2 C1 C6 O4 -154.21(17) . . . . ? O1 C1 C6 O5 147.60(15) . . . . ? C8 C1 C6 O5 -92.20(17) . . . . ? C2 C1 C6 O5 27.3(2) . . . . ? O1 C1 C8 C13 -1.9(2) . . . . ? C6 C1 C8 C13 -117.08(18) . . . . ? C2 C1 C8 C13 123.14(18) . . . . ? O1 C1 C8 C9 175.97(15) . . . . ? C6 C1 C8 C9 60.8(2) . . . . ? C2 C1 C8 C9 -59.0(2) . . . . ? C13 C8 C9 C10 1.3(2) . . . . ? C1 C8 C9 C10 -176.59(16) . . . . ? C8 C9 C10 C11 -0.8(3) . . . . ? C9 C10 C11 C12 -0.6(3) . . . . ? C10 C11 C12 C13 1.5(3) . . . . ? C9 C8 C13 C12 -0.4(3) . . . . ? C1 C8 C13 C12 177.42(16) . . . . ? C11 C12 C13 C8 -0.9(3) . . . . ? O2 C5 O3 C2 -176.39(18) . . . . ? C4 C5 O3 C2 3.7(2) . . . . ? C3 C2 O3 C5 -4.15(19) . . . . ? C1 C2 O3 C5 -126.87(16) . . . . ? O4 C6 O5 C7 -0.9(3) . . . . ? C1 C6 O5 C7 177.57(15) . . . . ? _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 72 _diffrn_measured_fraction_theta_full 0.986 _refine_diff_density_max 0.143 _refine_diff_density_min -0.208 _refine_diff_density_rms 0.045