Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2003 data_global _publ_contact_author_email R.LAMB@UNSW.EDU.AU _publ_contact_author_name 'Prof Robert Norman Lamb' _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_address ; School of Chemical Sciences University of New South Wales Sydney New South Wales 2052 AUSTRALIA ; _publ_section_title ; A facile route to hetero-bimetallic Ti(IV)-alkali metal calix[4]arene complexes involving alkali metal ; _publ_section_references ; Altomare, A., Burla, M.C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Polidori, G., J. Appl. Cryst., 1994, 27, 435. Ibers, J.A. and Hamilton, W.C., (Eds) International Tables for X-Ray Crystallography Vol. 4 , Kynoch Press, Birmingham, 1974. Johnson, C.K.,'ORTEP-II', Oak Ridge National Laboratory, Tennessee, U.S.A., 1976. Rae, A.D., RAELS. A comprehensive Constrained Least Squares Refinement Program, University of New South Wales, 1989. ; loop_ _publ_author_name 'Robert Norman Lamb' 'Donald C. Craig' 'Antonella J. Petrella' 'Colin L. Raston' 'Nicholas K. Roberts' data_tiacac _database_code_CSD 208112 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C57 H91 K O14 Ti' _chemical_formula_weight 1087.30 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' K K 0.2009 0.2494 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 14.2018(5) _cell_length_b 21.9002(9) _cell_length_c 21.1284(8) _cell_angle_alpha 90.00 _cell_angle_beta 106.461(2) _cell_angle_gamma 90.00 _cell_volume 6302.1(4) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.146 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2344 _exptl_absorpt_coefficient_mu 0.259 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9549 _exptl_absorpt_correction_T_max 0.9821 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 15 degree phi range. ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12718 _diffrn_reflns_av_R_equivalents 0.0385 _diffrn_reflns_av_sigmaI/netI 0.0398 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -23 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.74 _diffrn_reflns_theta_max 22.76 _reflns_number_total 4209 _reflns_number_gt 3614 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; ORTEP3 for Windows (Farrugia, 1997) XSeed (Barbour, 2001) ; _computing_publication_material 'WC (Thornton-Pett, 2000)' _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^)+(0.0503P)^2^+11.0106P] 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 SHELXL _refine_ls_extinction_coef 0.0026(5) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 4209 _refine_ls_number_parameters 381 _refine_ls_number_restraints 30 _refine_ls_R_factor_all 0.0591 _refine_ls_R_factor_gt 0.0503 _refine_ls_wR_factor_ref 0.1389 _refine_ls_wR_factor_gt 0.1324 _refine_ls_goodness_of_fit_ref 1.112 _refine_ls_restrained_S_all 1.114 _refine_ls_shift/su_max 0.007 _refine_ls_shift/su_mean 0.001 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 Ti1 Ti 0.0000 -0.10303(3) 0.2500 0.0384(3) Uani 1 2 d S . . K1 K 0.0000 0.06780(4) 0.2500 0.0515(3) Uani 1 2 d S . . O1 O 0.07327(13) -0.04614(9) 0.22152(9) 0.0413(5) Uani 1 1 d . . . C1 C 0.1446(2) -0.03022(13) 0.19393(14) 0.0390(7) Uani 1 1 d . . . C2 C 0.2393(2) -0.01925(14) 0.23453(14) 0.0433(7) Uani 1 1 d . . . C3 C 0.3088(2) 0.00023(15) 0.20437(15) 0.0482(8) Uani 1 1 d . . . H3 H 0.3737 0.0080 0.2311 0.058 Uiso 1 1 calc R . . C4 C 0.2873(2) 0.00894(15) 0.13598(15) 0.0476(8) Uani 1 1 d . . . C5 C 0.1925(2) -0.00496(14) 0.09753(15) 0.0454(7) Uani 1 1 d . . . H5 H 0.1769 -0.0008 0.0509 0.055 Uiso 1 1 calc R . . C6 C 0.1199(2) -0.02481(13) 0.12559(13) 0.0394(7) Uani 1 1 d . . . C7 C 0.2634(2) -0.03500(15) 0.30776(14) 0.0465(8) Uani 1 1 d . . . H7A H 0.2599 -0.0799 0.3118 0.056 Uiso 1 1 calc R . . H7B H 0.3323 -0.0228 0.3291 0.056 Uiso 1 1 calc R . . C8 C 0.3677(3) 0.03043(19) 0.10563(17) 0.0629(10) Uani 1 1 d . . . C9 C 0.4470(3) -0.0210(3) 0.1169(2) 0.0919(15) Uani 1 1 d . . . H9A H 0.4165 -0.0588 0.0958 0.138 Uiso 1 1 calc R . . H9B H 0.4749 -0.0280 0.1644 0.138 Uiso 1 1 calc R . . H9C H 0.4992 -0.0086 0.0977 0.138 Uiso 1 1 calc R . . C10 C 0.4166(4) 0.0877(2) 0.1391(2) 0.1024(17) Uani 1 1 d . . . H10A H 0.4708 0.0988 0.1212 0.154 Uiso 1 1 calc R . . H10B H 0.4421 0.0805 0.1867 0.154 Uiso 1 1 calc R . . H10C H 0.3686 0.1210 0.1311 0.154 Uiso 1 1 calc R . . C11 C 0.3292(3) 0.0399(2) 0.03103(18) 0.0850(13) Uani 1 1 d . . . H11A H 0.2817 0.0735 0.0217 0.128 Uiso 1 1 calc R . . H11B H 0.2971 0.0024 0.0103 0.128 Uiso 1 1 calc R . . H11C H 0.3841 0.0497 0.0133 0.128 Uiso 1 1 calc R . . O2 O -0.10036(14) -0.09749(9) 0.16263(9) 0.0400(5) Uani 1 1 d . . . C12 C -0.1229(2) -0.03959(13) 0.13896(13) 0.0401(7) Uani 1 1 d . . . C13 C -0.0662(2) -0.01164(13) 0.10261(13) 0.0389(7) Uani 1 1 d . . . C14 C -0.0872(2) 0.04845(14) 0.08112(14) 0.0450(7) Uani 1 1 d . . . H14 H -0.0474 0.0672 0.0572 0.054 Uiso 1 1 calc R . . C15 C -0.1631(2) 0.08214(15) 0.09292(14) 0.0501(8) Uani 1 1 d . A . C16 C -0.2177(2) 0.05294(15) 0.13017(14) 0.0488(8) Uani 1 1 d . . . H16 H -0.2697 0.0749 0.1399 0.059 Uiso 1 1 calc R . . C17 C -0.1994(2) -0.00656(14) 0.15357(13) 0.0425(7) Uani 1 1 d . . . C18 C 0.0180(2) -0.04472(14) 0.08590(13) 0.0404(7) Uani 1 1 d . . . H18A H 0.0113 -0.0890 0.0928 0.049 Uiso 1 1 calc R . . H18B H 0.0118 -0.0384 0.0385 0.049 Uiso 1 1 calc R . . C19 C -0.1878(3) 0.14680(15) 0.06572(16) 0.0595(9) Uani 1 1 d D . . C20A C -0.1636(5) 0.1928(2) 0.1204(3) 0.0645(17) Uani 0.776(13) 1 d PD A 1 H20A H -0.0928 0.1925 0.1418 0.097 Uiso 0.776(13) 1 calc PR A 1 H20B H -0.1987 0.1824 0.1528 0.097 Uiso 0.776(13) 1 calc PR A 1 H20C H -0.1837 0.2335 0.1023 0.097 Uiso 0.776(13) 1 calc PR A 1 C21A C -0.1290(8) 0.1636(3) 0.0163(4) 0.102(3) Uani 0.776(13) 1 d PD A 1 H21A H -0.1399 0.1324 -0.0183 0.152 Uiso 0.776(13) 1 calc PR A 1 H21B H -0.0588 0.1657 0.0398 0.152 Uiso 0.776(13) 1 calc PR A 1 H21C H -0.1512 0.2034 -0.0038 0.152 Uiso 0.776(13) 1 calc PR A 1 C22A C -0.2972(5) 0.1505(3) 0.0283(4) 0.102(3) Uani 0.776(13) 1 d PD A 1 H22A H -0.3128 0.1917 0.0103 0.153 Uiso 0.776(13) 1 calc PR A 1 H22B H -0.3364 0.1413 0.0586 0.153 Uiso 0.776(13) 1 calc PR A 1 H22C H -0.3123 0.1208 -0.0078 0.153 Uiso 0.776(13) 1 calc PR A 1 C20B C -0.210(2) 0.1458(10) -0.0076(6) 0.085(8) Uani 0.224(13) 1 d PD A 2 H20D H -0.2200 0.1877 -0.0246 0.127 Uiso 0.224(13) 1 calc PR A 2 H20E H -0.2702 0.1221 -0.0264 0.127 Uiso 0.224(13) 1 calc PR A 2 H20F H -0.1555 0.1271 -0.0202 0.127 Uiso 0.224(13) 1 calc PR A 2 C21B C -0.277(2) 0.1689(13) 0.0861(16) 0.21(3) Uani 0.224(13) 1 d PD A 2 H21D H -0.3175 0.1955 0.0517 0.309 Uiso 0.224(13) 1 calc PR A 2 H21E H -0.2554 0.1916 0.1277 0.309 Uiso 0.224(13) 1 calc PR A 2 H21F H -0.3164 0.1336 0.0921 0.309 Uiso 0.224(13) 1 calc PR A 2 C22B C -0.1017(18) 0.1889(10) 0.0968(14) 0.124(15) Uani 0.224(13) 1 d PD A 2 H22D H -0.0428 0.1740 0.0863 0.186 Uiso 0.224(13) 1 calc PR A 2 H22E H -0.0900 0.1894 0.1448 0.186 Uiso 0.224(13) 1 calc PR A 2 H22F H -0.1169 0.2303 0.0793 0.186 Uiso 0.224(13) 1 calc PR A 2 O1Ac O 0.06780(16) -0.17138(10) 0.21798(11) 0.0570(6) Uani 1 1 d . . . C1Ac C 0.0610(3) -0.22970(18) 0.2200(2) 0.0748(12) Uani 1 1 d . . . C2Ac C 0.0000 -0.2593(3) 0.2500 0.097(2) Uani 1 2 d S . . H24 H 0.0000 -0.3027 0.2500 0.117 Uiso 1 2 calc SR . . C3Ac C 0.1255(4) -0.2640(2) 0.1865(3) 0.122(2) Uani 1 1 d . . . H25A H 0.1075 -0.2530 0.1397 0.182 Uiso 1 1 calc R . . H25B H 0.1164 -0.3081 0.1909 0.182 Uiso 1 1 calc R . . H25C H 0.1943 -0.2534 0.2072 0.182 Uiso 1 1 calc R . . O1Me1 O 0.1004(2) 0.15653(14) 0.21302(15) 0.0845(9) Uani 1 1 d . . . H26 H 0.096(3) 0.200(2) 0.226(2) 0.101(15) Uiso 1 1 d . . . C26 C 0.1617(4) 0.1468(2) 0.1723(3) 0.0931(14) Uani 1 1 d . . . H26A H 0.1603 0.1035 0.1604 0.140 Uiso 1 1 calc R . . H26B H 0.2291 0.1586 0.1959 0.140 Uiso 1 1 calc R . . H26C H 0.1387 0.1714 0.1321 0.140 Uiso 1 1 calc R . . O1S O 0.1278(3) 0.27958(13) 0.23114(19) 0.1054(11) Uani 1 1 d . . . H1S H 0.1412 0.2898 0.1963 0.158 Uiso 1 1 calc R . . C1S C 0.1375(5) 0.3308(2) 0.2732(3) 0.1117(18) Uani 1 1 d . . . H1S1 H 0.1152 0.3201 0.3117 0.168 Uiso 1 1 calc R . . H1S2 H 0.0975 0.3645 0.2493 0.168 Uiso 1 1 calc R . . H1S3 H 0.2065 0.3434 0.2880 0.168 Uiso 1 1 calc R . . O2S O 0.3052(2) 0.31693(17) 0.07939(19) 0.1103(12) Uani 1 1 d . . . H2S H 0.3379 0.3421 0.1069 0.165 Uiso 1 1 calc R . . C2S C 0.3652(5) 0.2878(4) 0.0499(4) 0.208(5) Uani 1 1 d . . . H2S1 H 0.3554 0.3043 0.0054 0.312 Uiso 1 1 calc R . . H2S2 H 0.3500 0.2440 0.0471 0.312 Uiso 1 1 calc R . . H2S3 H 0.4336 0.2939 0.0758 0.312 Uiso 1 1 calc R . . O3S O 0.1374(3) 0.3025(2) 0.10907(19) 0.1158(12) Uani 1 1 d . . . H3S H 0.1875 0.3060 0.0957 0.174 Uiso 1 1 calc R . . C3S C 0.0581(4) 0.3276(3) 0.0636(3) 0.127(2) Uani 1 1 d . . . H3S1 H -0.0007 0.3225 0.0787 0.191 Uiso 1 1 calc R . . H3S2 H 0.0483 0.3070 0.0211 0.191 Uiso 1 1 calc R . . H3S3 H 0.0700 0.3712 0.0587 0.191 Uiso 1 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 Ti1 0.0424(5) 0.0380(4) 0.0338(4) 0.000 0.0090(3) 0.000 K1 0.0595(6) 0.0437(6) 0.0491(6) 0.000 0.0117(5) 0.000 O1 0.0408(11) 0.0487(12) 0.0319(10) 0.0026(9) 0.0060(9) -0.0023(9) C1 0.0392(16) 0.0408(16) 0.0378(16) 0.0015(12) 0.0122(13) 0.0018(13) C2 0.0439(17) 0.0485(18) 0.0367(16) -0.0008(13) 0.0101(14) 0.0008(14) C3 0.0393(16) 0.060(2) 0.0440(18) -0.0025(15) 0.0104(14) -0.0004(14) C4 0.0466(18) 0.0568(19) 0.0408(17) -0.0021(14) 0.0146(14) -0.0035(15) C5 0.0516(18) 0.0515(18) 0.0342(16) -0.0022(13) 0.0137(14) 0.0004(15) C6 0.0419(16) 0.0415(16) 0.0349(16) -0.0012(12) 0.0109(13) 0.0030(13) C7 0.0373(16) 0.063(2) 0.0367(16) 0.0038(14) 0.0070(13) -0.0004(14) C8 0.052(2) 0.091(3) 0.0470(19) -0.0040(18) 0.0161(16) -0.0155(19) C9 0.053(2) 0.151(5) 0.076(3) -0.002(3) 0.024(2) -0.002(3) C10 0.116(4) 0.120(4) 0.083(3) -0.016(3) 0.047(3) -0.065(3) C11 0.072(3) 0.135(4) 0.053(2) 0.006(2) 0.025(2) -0.029(3) O2 0.0433(11) 0.0408(11) 0.0344(10) -0.0036(8) 0.0087(8) -0.0017(9) C12 0.0413(16) 0.0449(17) 0.0300(15) -0.0040(13) 0.0032(12) 0.0014(13) C13 0.0418(16) 0.0444(17) 0.0279(14) -0.0009(12) 0.0060(12) 0.0031(13) C14 0.0528(18) 0.0487(18) 0.0334(16) -0.0003(13) 0.0121(14) 0.0024(15) C15 0.062(2) 0.0518(19) 0.0324(16) 0.0007(14) 0.0067(15) 0.0100(16) C16 0.0478(18) 0.059(2) 0.0378(17) -0.0034(15) 0.0085(14) 0.0140(15) C17 0.0408(16) 0.0551(19) 0.0276(15) -0.0013(13) 0.0033(12) 0.0022(14) C18 0.0445(16) 0.0459(17) 0.0298(15) -0.0006(12) 0.0088(12) 0.0014(13) C19 0.079(2) 0.051(2) 0.0487(19) 0.0078(16) 0.0176(18) 0.0185(18) C20A 0.074(4) 0.051(3) 0.065(3) 0.001(2) 0.014(3) 0.014(3) C21A 0.174(9) 0.059(4) 0.098(6) 0.038(4) 0.080(6) 0.045(5) C22A 0.109(5) 0.062(3) 0.095(5) 0.016(3) -0.038(4) 0.017(3) C20B 0.11(2) 0.090(16) 0.058(12) 0.022(10) 0.026(12) 0.039(14) C21B 0.28(6) 0.18(4) 0.23(5) 0.16(4) 0.18(5) 0.20(4) C22B 0.16(3) 0.068(14) 0.10(2) 0.010(14) -0.03(2) -0.003(17) O1Ac 0.0579(14) 0.0511(15) 0.0571(14) -0.0092(11) 0.0084(11) 0.0108(11) C1Ac 0.060(2) 0.054(3) 0.096(3) -0.021(2) -0.001(2) 0.0126(19) C2Ac 0.082(4) 0.041(3) 0.150(7) 0.000 0.003(4) 0.000 C3Ac 0.095(3) 0.088(3) 0.167(5) -0.061(4) 0.015(3) 0.031(3) O1Me1 0.111(2) 0.0612(18) 0.089(2) -0.0046(15) 0.0418(18) -0.0179(16) C26 0.111(4) 0.072(3) 0.106(4) -0.014(3) 0.048(3) -0.004(3) O1S 0.149(3) 0.0600(18) 0.121(3) -0.0040(18) 0.061(2) -0.0085(19) C1S 0.150(5) 0.070(3) 0.130(4) -0.007(3) 0.062(4) -0.001(3) O2S 0.081(2) 0.112(3) 0.130(3) -0.068(2) 0.018(2) -0.0242(19) C2S 0.109(5) 0.256(10) 0.254(10) -0.203(9) 0.041(5) -0.027(5) O3S 0.101(3) 0.140(3) 0.108(3) 0.017(2) 0.031(2) -0.003(2) C3S 0.111(4) 0.138(5) 0.140(5) 0.030(4) 0.048(4) 0.031(4) _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 Ti1 O1 1.8307(19) . ? Ti1 O1 1.8307(19) 2 ? Ti1 O2 1.9907(18) . ? Ti1 O2 1.9907(18) 2 ? Ti1 O1Ac 1.999(2) 2 ? Ti1 O1Ac 1.999(2) . ? Ti1 K1 3.7411(12) . ? K1 O1Me1 2.655(3) . ? K1 O1Me1 2.655(3) 2 ? K1 O1 2.833(2) 2 ? K1 O1 2.833(2) . ? K1 C17 3.399(3) . ? K1 C17 3.399(3) 2 ? K1 C1 3.407(3) 2 ? K1 C1 3.407(3) . ? K1 C16 3.412(3) . ? K1 C16 3.412(3) 2 ? K1 C12 3.429(3) . ? K1 C12 3.429(3) 2 ? O1 C1 1.350(3) . ? C1 C6 1.391(4) . ? C1 C2 1.396(4) . ? C2 C3 1.384(4) . ? C2 C7 1.526(4) . ? C3 C4 1.403(4) . ? C3 H3 0.9500 . ? C4 C5 1.394(4) . ? C4 C8 1.533(5) . ? C5 C6 1.396(4) . ? C5 H5 0.9500 . ? C6 C18 1.516(4) . ? C7 C17 1.518(4) 2 ? C7 H7A 0.9900 . ? C7 H7B 0.9900 . ? C8 C10 1.509(6) . ? C8 C11 1.529(5) . ? C8 C9 1.563(6) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? O2 C12 1.367(3) . ? C12 C13 1.400(4) . ? C12 C17 1.410(4) . ? C13 C14 1.396(4) . ? C13 C18 1.523(4) . ? C14 C15 1.386(4) . ? C14 H14 0.9500 . ? C15 C16 1.406(5) . ? C15 C19 1.531(4) . ? C16 C17 1.392(4) . ? C16 H16 0.9500 . ? C17 C7 1.518(4) 2 ? C18 H18A 0.9900 . ? C18 H18B 0.9900 . ? C19 C20B 1.491(11) . ? C19 C20A 1.497(6) . ? C19 C22B 1.523(13) . ? C19 C22A 1.533(6) . ? C19 C21B 1.533(12) . ? C19 C21A 1.555(6) . ? C20A H20A 0.9800 . ? C20A H20B 0.9800 . ? C20A H20C 0.9800 . ? C21A H21A 0.9800 . ? C21A H21B 0.9800 . ? C21A H21C 0.9800 . ? C22A H22A 0.9800 . ? C22A H22B 0.9800 . ? C22A H22C 0.9800 . ? C20B H20D 0.9800 . ? C20B H20E 0.9800 . ? C20B H20F 0.9800 . ? C21B H21D 0.9800 . ? C21B H21E 0.9800 . ? C21B H21F 0.9800 . ? C22B H22D 0.9800 . ? C22B H22E 0.9800 . ? C22B H22F 0.9800 . ? O1Ac C1Ac 1.282(4) . ? C1Ac C2Ac 1.372(5) . ? C1Ac C3Ac 1.508(6) . ? C2Ac C1Ac 1.372(5) 2 ? C2Ac H24 0.9500 . ? C3Ac H25A 0.9800 . ? C3Ac H25B 0.9800 . ? C3Ac H25C 0.9800 . ? O1Me1 C26 1.404(5) . ? O1Me1 H26 1.00(5) . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? O1S C1S 1.415(6) . ? O1S H1S 0.8400 . ? C1S H1S1 0.9800 . ? C1S H1S2 0.9800 . ? C1S H1S3 0.9800 . ? O2S C2S 1.350(7) . ? O2S H2S 0.8400 . ? C2S H2S1 0.9800 . ? C2S H2S2 0.9800 . ? C2S H2S3 0.9800 . ? O3S C3S 1.371(6) . ? O3S H3S 0.8400 . ? C3S H3S1 0.9800 . ? C3S H3S2 0.9800 . ? C3S H3S3 0.9800 . ? 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 Ti1 O1 94.24(13) . 2 ? O1 Ti1 O2 88.75(8) . . ? O1 Ti1 O2 86.51(8) 2 . ? O1 Ti1 O2 86.51(8) . 2 ? O1 Ti1 O2 88.74(8) 2 2 ? O2 Ti1 O2 173.02(11) . 2 ? O1 Ti1 O1Ac 173.76(9) . 2 ? O1 Ti1 O1Ac 91.45(9) 2 2 ? O2 Ti1 O1Ac 94.16(8) . 2 ? O2 Ti1 O1Ac 91.07(8) 2 2 ? O1 Ti1 O1Ac 91.45(9) . . ? O1 Ti1 O1Ac 173.76(9) 2 . ? O2 Ti1 O1Ac 91.07(8) . . ? O2 Ti1 O1Ac 94.16(8) 2 . ? O1Ac Ti1 O1Ac 82.99(14) 2 . ? O1 Ti1 K1 47.12(6) . . ? O1 Ti1 K1 47.12(6) 2 . ? O2 Ti1 K1 86.51(6) . . ? O2 Ti1 K1 86.51(6) 2 . ? O1Ac Ti1 K1 138.50(7) 2 . ? O1Ac Ti1 K1 138.50(7) . . ? O1Me1 K1 O1Me1 85.91(15) . 2 ? O1Me1 K1 O1 165.29(8) . 2 ? O1Me1 K1 O1 108.78(8) 2 2 ? O1Me1 K1 O1 108.78(8) . . ? O1Me1 K1 O1 165.29(8) 2 . ? O1 K1 O1 56.53(8) 2 . ? O1Me1 K1 C17 126.85(8) . . ? O1Me1 K1 C17 95.83(9) 2 . ? O1 K1 C17 53.95(6) 2 . ? O1 K1 C17 75.19(7) . . ? O1Me1 K1 C17 95.83(9) . 2 ? O1Me1 K1 C17 126.85(8) 2 2 ? O1 K1 C17 75.19(7) 2 2 ? O1 K1 C17 53.95(6) . 2 ? C17 K1 C17 122.74(11) . 2 ? O1Me1 K1 C1 171.98(9) . 2 ? O1Me1 K1 C1 86.10(9) 2 2 ? O1 K1 C1 22.68(6) 2 2 ? O1 K1 C1 79.21(6) . 2 ? C17 K1 C1 54.88(7) . 2 ? C17 K1 C1 88.37(7) 2 2 ? O1Me1 K1 C1 86.10(9) . . ? O1Me1 K1 C1 171.98(9) 2 . ? O1 K1 C1 79.21(6) 2 . ? O1 K1 C1 22.68(6) . . ? C17 K1 C1 88.37(7) . . ? C17 K1 C1 54.88(7) 2 . ? C1 K1 C1 101.90(10) 2 . ? O1Me1 K1 C16 107.49(9) . . ? O1Me1 K1 C16 80.73(9) 2 . ? O1 K1 C16 76.32(7) 2 . ? O1 K1 C16 93.93(7) . . ? C17 K1 C16 23.59(7) . . ? C17 K1 C16 145.60(8) 2 . ? C1 K1 C16 71.89(7) 2 . ? C1 K1 C16 100.99(7) . . ? O1Me1 K1 C16 80.73(9) . 2 ? O1Me1 K1 C16 107.49(9) 2 2 ? O1 K1 C16 93.93(7) 2 2 ? O1 K1 C16 76.32(7) . 2 ? C17 K1 C16 145.60(8) . 2 ? C17 K1 C16 23.59(7) 2 2 ? C1 K1 C16 101.00(7) 2 2 ? C1 K1 C16 71.89(7) . 2 ? C16 K1 C16 169.06(11) . 2 ? O1Me1 K1 C12 120.80(8) . . ? O1Me1 K1 C12 119.45(9) 2 . ? O1 K1 C12 52.77(6) 2 . ? O1 K1 C12 52.91(6) . . ? C17 K1 C12 23.84(7) . . ? C17 K1 C12 104.92(7) 2 . ? C1 K1 C12 64.27(7) 2 . ? C1 K1 C12 64.53(7) . . ? C16 K1 C12 41.28(7) . . ? C16 K1 C12 128.37(8) 2 . ? O1Me1 K1 C12 119.45(9) . 2 ? O1Me1 K1 C12 120.80(8) 2 2 ? O1 K1 C12 52.91(6) 2 2 ? O1 K1 C12 52.77(6) . 2 ? C17 K1 C12 104.92(7) . 2 ? C17 K1 C12 23.84(7) 2 2 ? C1 K1 C12 64.53(7) 2 2 ? C1 K1 C12 64.27(7) . 2 ? C16 K1 C12 128.37(8) . 2 ? C16 K1 C12 41.28(7) 2 2 ? C12 K1 C12 93.40(10) . 2 ? C1 O1 Ti1 152.09(19) . . ? C1 O1 K1 103.30(16) . . ? Ti1 O1 K1 104.62(8) . . ? O1 C1 C6 118.1(2) . . ? O1 C1 C2 119.3(2) . . ? C6 C1 C2 122.6(3) . . ? O1 C1 K1 54.02(13) . . ? C6 C1 K1 107.91(18) . . ? C2 C1 K1 104.40(18) . . ? C3 C2 C1 117.3(3) . . ? C3 C2 C7 123.5(3) . . ? C1 C2 C7 119.0(3) . . ? C2 C3 C4 122.7(3) . . ? C2 C3 H3 118.6 . . ? C4 C3 H3 118.6 . . ? C5 C4 C3 117.6(3) . . ? C5 C4 C8 122.2(3) . . ? C3 C4 C8 120.1(3) . . ? C4 C5 C6 121.8(3) . . ? C4 C5 H5 119.1 . . ? C6 C5 H5 119.1 . . ? C1 C6 C5 117.9(3) . . ? C1 C6 C18 118.0(3) . . ? C5 C6 C18 123.9(2) . . ? C17 C7 C2 117.2(2) 2 . ? C17 C7 H7A 108.0 2 . ? C2 C7 H7A 108.0 . . ? C17 C7 H7B 108.0 2 . ? C2 C7 H7B 108.0 . . ? H7A C7 H7B 107.3 . . ? C10 C8 C11 110.7(4) . . ? C10 C8 C4 110.9(3) . . ? C11 C8 C4 112.4(3) . . ? C10 C8 C9 108.2(4) . . ? C11 C8 C9 106.6(3) . . ? C4 C8 C9 107.7(3) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C8 C10 H10A 109.5 . . ? C8 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C8 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? C8 C11 H11A 109.5 . . ? C8 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C8 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C12 O2 Ti1 115.30(16) . . ? O2 C12 C13 119.7(3) . . ? O2 C12 C17 120.7(3) . . ? C13 C12 C17 119.6(3) . . ? O2 C12 K1 111.40(15) . . ? C13 C12 K1 79.36(16) . . ? C17 C12 K1 76.86(16) . . ? C14 C13 C12 119.2(3) . . ? C14 C13 C18 118.8(3) . . ? C12 C13 C18 122.0(3) . . ? C14 C13 K1 78.30(16) . . ? C12 C13 K1 77.17(16) . . ? C18 C13 K1 114.65(16) . . ? C15 C14 C13 123.2(3) . . ? C15 C14 K1 79.53(17) . . ? C13 C14 K1 78.39(16) . . ? C15 C14 H14 118.4 . . ? C13 C14 H14 118.4 . . ? K1 C14 H14 113.8 . . ? C14 C15 C16 116.1(3) . . ? C14 C15 C19 122.1(3) . . ? C16 C15 C19 121.8(3) . . ? C14 C15 K1 77.42(17) . . ? C16 C15 K1 75.45(17) . . ? C19 C15 K1 117.5(2) . . ? C17 C16 C15 123.2(3) . . ? C17 C16 K1 77.69(17) . . ? C15 C16 K1 81.04(18) . . ? C17 C16 H16 118.4 . . ? C15 C16 H16 118.4 . . ? K1 C16 H16 112.8 . . ? C16 C17 C12 118.7(3) . . ? C16 C17 C7 119.7(3) . 2 ? C12 C17 C7 121.6(3) . 2 ? C16 C17 K1 78.73(17) . . ? C12 C17 K1 79.30(16) . . ? C7 C17 K1 113.48(16) 2 . ? C6 C18 C13 115.1(2) . . ? C6 C18 H18A 108.5 . . ? C13 C18 H18A 108.5 . . ? C6 C18 H18B 108.5 . . ? C13 C18 H18B 108.5 . . ? H18A C18 H18B 107.5 . . ? C20B C19 C20A 138.3(10) . . ? C20B C19 C22B 111.5(10) . . ? C20A C19 C22B 44.0(13) . . ? C20B C19 C15 109.6(9) . . ? C20A C19 C15 110.8(3) . . ? C22B C19 C15 109.1(9) . . ? C20B C19 C22A 65.0(10) . . ? C20A C19 C22A 109.8(4) . . ? C22B C19 C22A 139.7(11) . . ? C15 C19 C22A 109.5(4) . . ? C20B C19 C21B 110.3(10) . . ? C20A C19 C21B 66.2(15) . . ? C22B C19 C21B 108.4(10) . . ? C15 C19 C21B 107.8(9) . . ? C22A C19 C21B 47.7(13) . . ? C20B C19 C21A 45.8(9) . . ? C20A C19 C21A 108.0(4) . . ? C22B C19 C21A 68.2(12) . . ? C15 C19 C21A 111.2(3) . . ? C22A C19 C21A 107.5(4) . . ? C21B C19 C21A 139.5(8) . . ? C19 C20A H20A 109.5 . . ? C19 C20A H20B 109.5 . . ? C19 C20A H20C 109.5 . . ? C19 C21A H21A 109.5 . . ? C19 C21A H21B 109.5 . . ? C19 C21A H21C 109.5 . . ? C19 C22A H22A 109.5 . . ? C19 C22A H22B 109.5 . . ? C19 C22A H22C 109.5 . . ? C19 C20B H20D 109.5 . . ? C19 C20B H20E 109.5 . . ? H20D C20B H20E 109.5 . . ? C19 C20B H20F 109.5 . . ? H20D C20B H20F 109.5 . . ? H20E C20B H20F 109.5 . . ? C19 C21B H21D 109.5 . . ? C19 C21B H21E 109.5 . . ? H21D C21B H21E 109.5 . . ? C19 C21B H21F 109.5 . . ? H21D C21B H21F 109.5 . . ? H21E C21B H21F 109.5 . . ? C19 C22B H22D 109.5 . . ? C19 C22B H22E 109.5 . . ? H22D C22B H22E 109.5 . . ? C19 C22B H22F 109.5 . . ? H22D C22B H22F 109.5 . . ? H22E C22B H22F 109.5 . . ? C1Ac O1Ac Ti1 133.3(3) . . ? O1Ac C1Ac C2Ac 123.3(4) . . ? O1Ac C1Ac C3Ac 114.8(4) . . ? C2Ac C1Ac C3Ac 121.9(4) . . ? C1Ac C2Ac C1Ac 123.6(5) . 2 ? C1Ac C2Ac H24 118.2 . . ? C1Ac C2Ac H24 118.2 2 . ? C1Ac C3Ac H25A 109.5 . . ? C1Ac C3Ac H25B 109.5 . . ? H25A C3Ac H25B 109.5 . . ? C1Ac C3Ac H25C 109.5 . . ? H25A C3Ac H25C 109.5 . . ? H25B C3Ac H25C 109.5 . . ? C26 O1Me1 K1 123.2(3) . . ? C26 O1Me1 H26 114(3) . . ? K1 O1Me1 H26 122(3) . . ? O1Me1 C26 H26A 109.5 . . ? O1Me1 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? O1Me1 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C1S O1S H1S 109.5 . . ? O1S C1S H1S1 109.5 . . ? O1S C1S H1S2 109.5 . . ? H1S1 C1S H1S2 109.5 . . ? O1S C1S H1S3 109.5 . . ? H1S1 C1S H1S3 109.5 . . ? H1S2 C1S H1S3 109.5 . . ? C2S O2S H2S 109.5 . . ? O2S C2S H2S1 109.5 . . ? O2S C2S H2S2 109.5 . . ? H2S1 C2S H2S2 109.5 . . ? O2S C2S H2S3 109.5 . . ? H2S1 C2S H2S3 109.5 . . ? H2S2 C2S H2S3 109.5 . . ? C3S O3S H3S 109.5 . . ? O3S C3S H3S1 109.5 . . ? O3S C3S H3S2 109.5 . . ? H3S1 C3S H3S2 109.5 . . ? O3S C3S H3S3 109.5 . . ? H3S1 C3S H3S3 109.5 . . ? H3S2 C3S H3S3 109.5 . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 22.76 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.260 _refine_diff_density_min -0.260 _refine_diff_density_rms 0.043 data_ktithf _database_code_CSD 208113 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C61 H83 K O9 Ti' _chemical_formula_weight 1047.27 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' K K 0.2009 0.2494 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monclinic _symmetry_space_group_name_H-M P21/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 13.8800(2) _cell_length_b 20.3074(3) _cell_length_c 21.3492(3) _cell_angle_alpha 90.00 _cell_angle_beta 96.309(2) _cell_angle_gamma 90.00 _cell_volume 5981.18(15) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.163 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2248 _exptl_absorpt_coefficient_mu 0.265 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9392 _exptl_absorpt_correction_T_max 0.9843 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 15 degree phi range. ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 66468 _diffrn_reflns_av_R_equivalents 0.0820 _diffrn_reflns_av_sigmaI/netI 0.0649 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 1.67 _diffrn_reflns_theta_max 26.00 _reflns_number_total 11731 _reflns_number_gt 8338 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; ORTEP3 for Windows (Farrugia, 1997) XSeed (Barbour, 2001) ; _computing_publication_material 'WC (Thornton-Pett, 2000)' _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^)+(0.0884P)^2^+1.4351P] 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 SHELXL _refine_ls_extinction_coef 0.0009(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 11731 _refine_ls_number_parameters 700 _refine_ls_number_restraints 51 _refine_ls_R_factor_all 0.0882 _refine_ls_R_factor_gt 0.0562 _refine_ls_wR_factor_ref 0.1576 _refine_ls_wR_factor_gt 0.1455 _refine_ls_goodness_of_fit_ref 1.058 _refine_ls_restrained_S_all 1.071 _refine_ls_shift/su_max 0.167 _refine_ls_shift/su_mean 0.008 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 K1 K 0.16787(4) 0.27141(3) 0.23574(3) 0.03221(17) Uani 1 1 d . . . Ti1 Ti 0.07719(3) 0.42382(2) 0.15330(2) 0.01835(13) Uani 1 1 d . . . O1 O 0.19152(11) 0.37560(8) 0.15676(7) 0.0196(4) Uani 1 1 d . . . C1 C 0.28008(16) 0.37191(12) 0.13810(11) 0.0193(5) Uani 1 1 d . . . C2 C 0.35815(16) 0.40121(12) 0.17510(11) 0.0197(5) Uani 1 1 d . . . C3 C 0.44983(17) 0.39404(13) 0.15593(12) 0.0245(6) Uani 1 1 d . . . H3 H 0.5036 0.4124 0.1813 0.029 Uiso 1 1 calc R . . C4 C 0.46621(17) 0.36102(13) 0.10104(12) 0.0266(6) Uani 1 1 d . . . C5 C 0.38542(18) 0.33442(13) 0.06422(12) 0.0263(6) Uani 1 1 d . . . H5 H 0.3948 0.3122 0.0262 0.032 Uiso 1 1 calc R . . C6 C 0.29198(16) 0.33958(12) 0.08165(11) 0.0209(5) Uani 1 1 d . . . C7 C 0.56746(19) 0.35361(16) 0.07932(14) 0.0371(7) Uani 1 1 d . . . C8 C 0.64492(19) 0.39165(17) 0.12162(15) 0.0432(8) Uani 1 1 d . . . H8A H 0.6277 0.4384 0.1216 0.065 Uiso 1 1 calc R . . H8B H 0.7079 0.3864 0.1056 0.065 Uiso 1 1 calc R . . H8C H 0.6486 0.3744 0.1647 0.065 Uiso 1 1 calc R . . C9 C 0.5670(2) 0.3810(2) 0.01228(16) 0.0635(11) Uani 1 1 d . . . H9A H 0.5234 0.3545 -0.0169 0.095 Uiso 1 1 calc R . . H9B H 0.6328 0.3791 -0.0003 0.095 Uiso 1 1 calc R . . H9C H 0.5447 0.4268 0.0112 0.095 Uiso 1 1 calc R . . C10 C 0.5963(2) 0.28042(18) 0.0803(2) 0.0589(10) Uani 1 1 d . . . H10A H 0.6015 0.2641 0.1238 0.088 Uiso 1 1 calc R . . H10B H 0.6588 0.2755 0.0636 0.088 Uiso 1 1 calc R . . H10C H 0.5468 0.2551 0.0543 0.088 Uiso 1 1 calc R . . C11 C 0.33829(18) 0.44484(12) 0.23028(12) 0.0238(6) Uani 1 1 d . . . H11A H 0.4016 0.4575 0.2531 0.029 Uiso 1 1 calc R . . H11B H 0.3072 0.4857 0.2128 0.029 Uiso 1 1 calc R . . O2 O 0.13334(11) 0.47091(8) 0.22818(8) 0.0217(4) Uani 1 1 d . . . C12 C 0.17668(17) 0.43424(11) 0.27626(11) 0.0190(5) Uani 1 1 d . . . C13 C 0.12191(16) 0.40955(12) 0.32310(11) 0.0192(5) Uani 1 1 d . . . C14 C 0.16749(17) 0.37116(12) 0.37120(11) 0.0230(5) Uani 1 1 d . . . H14 H 0.1301 0.3553 0.4027 0.028 Uiso 1 1 calc R . . C15 C 0.26604(17) 0.35459(12) 0.37564(11) 0.0212(5) Uani 1 1 d . . . C16 C 0.31772(17) 0.37827(12) 0.32783(11) 0.0209(5) Uani 1 1 d . . . H16 H 0.3844 0.3673 0.3290 0.025 Uiso 1 1 calc R . . C17 C 0.27567(16) 0.41732(12) 0.27837(11) 0.0192(5) Uani 1 1 d . . . C18 C 0.31314(18) 0.31570(14) 0.43233(12) 0.0287(6) Uani 1 1 d . . . C19 C 0.2575(2) 0.25137(16) 0.43921(17) 0.0494(8) Uani 1 1 d . . . H19A H 0.2621 0.2236 0.4021 0.074 Uiso 1 1 calc R . . H19B H 0.1892 0.2613 0.4429 0.074 Uiso 1 1 calc R . . H19C H 0.2855 0.2280 0.4771 0.074 Uiso 1 1 calc R . . C20 C 0.3047(2) 0.35683(17) 0.49271(14) 0.0459(8) Uani 1 1 d . . . H20A H 0.3350 0.3328 0.5295 0.069 Uiso 1 1 calc R . . H20B H 0.2361 0.3645 0.4974 0.069 Uiso 1 1 calc R . . H20C H 0.3375 0.3992 0.4894 0.069 Uiso 1 1 calc R . . C21 C 0.4183(2) 0.30024(19) 0.42829(16) 0.0533(9) Uani 1 1 d . . . H21A H 0.4244 0.2739 0.3905 0.080 Uiso 1 1 calc R . . H21B H 0.4443 0.2754 0.4657 0.080 Uiso 1 1 calc R . . H21C H 0.4547 0.3414 0.4261 0.080 Uiso 1 1 calc R . . C22 C 0.01488(16) 0.42619(12) 0.32259(12) 0.0225(5) Uani 1 1 d . . . H22A H 0.0024 0.4363 0.3663 0.027 Uiso 1 1 calc R . . H22B H 0.0017 0.4668 0.2975 0.027 Uiso 1 1 calc R . . O3 O 0.02604(11) 0.36430(8) 0.20664(7) 0.0204(4) Uani 1 1 d . . . C23 C -0.05009(16) 0.34755(12) 0.23692(11) 0.0194(5) Uani 1 1 d . . . C24 C -0.11917(17) 0.30387(12) 0.20761(11) 0.0227(5) Uani 1 1 d . . . C25 C -0.19567(18) 0.28649(13) 0.24123(12) 0.0270(6) Uani 1 1 d . . . H25 H -0.2431 0.2567 0.2225 0.032 Uiso 1 1 calc R . . C26 C -0.20599(17) 0.31104(13) 0.30173(12) 0.0266(6) Uani 1 1 d . . . C27 C -0.13518(17) 0.35458(13) 0.32802(12) 0.0239(6) Uani 1 1 d . . . H27 H -0.1405 0.3718 0.3689 0.029 Uiso 1 1 calc R . . C28 C -0.05689(16) 0.37387(12) 0.29676(11) 0.0209(5) Uani 1 1 d . . . C29 C -0.29359(19) 0.29156(14) 0.33571(13) 0.0315(6) Uani 1 1 d . . . C30 C -0.3871(2) 0.3101(2) 0.29555(16) 0.0556(10) Uani 1 1 d . . . H30A H -0.3924 0.3582 0.2928 0.083 Uiso 1 1 calc R . . H30B H -0.4426 0.2925 0.3149 0.083 Uiso 1 1 calc R . . H30C H -0.3867 0.2916 0.2532 0.083 Uiso 1 1 calc R . . C31 C -0.2919(2) 0.21654(16) 0.34743(17) 0.0506(9) Uani 1 1 d . . . H31A H -0.2927 0.1934 0.3071 0.076 Uiso 1 1 calc R . . H31B H -0.3490 0.2038 0.3679 0.076 Uiso 1 1 calc R . . H31C H -0.2330 0.2048 0.3748 0.076 Uiso 1 1 calc R . . C32 C -0.2928(2) 0.32422(17) 0.40054(14) 0.0433(8) Uani 1 1 d . . . H32A H -0.2323 0.3132 0.4265 0.065 Uiso 1 1 calc R . . H32B H -0.3480 0.3082 0.4212 0.065 Uiso 1 1 calc R . . H32C H -0.2976 0.3721 0.3954 0.065 Uiso 1 1 calc R . . C33 C -0.11447(17) 0.28470(14) 0.13920(12) 0.0262(6) Uani 1 1 d . . . H33A H -0.1340 0.3237 0.1131 0.031 Uiso 1 1 calc R . . H33B H -0.1644 0.2505 0.1285 0.031 Uiso 1 1 calc R . . O4 O 0.02569(11) 0.36640(8) 0.08362(7) 0.0203(4) Uani 1 1 d . . . C34 C 0.04385(16) 0.30126(12) 0.08953(11) 0.0200(5) Uani 1 1 d . . . C35 C 0.12997(17) 0.27455(12) 0.06920(11) 0.0208(5) Uani 1 1 d . . . C36 C 0.14746(18) 0.20776(13) 0.07561(11) 0.0245(6) Uani 1 1 d . . . H36 H 0.2050 0.1906 0.0616 0.029 Uiso 1 1 calc R . . C37 C 0.08501(18) 0.16426(13) 0.10156(12) 0.0260(6) Uani 1 1 d . . . C38 C 0.00276(19) 0.19205(13) 0.12328(12) 0.0263(6) Uani 1 1 d . . . H38 H -0.0403 0.1640 0.1424 0.032 Uiso 1 1 calc R . . C39 C -0.01924(16) 0.25909(13) 0.11821(11) 0.0222(5) Uani 1 1 d . . . C40 C 0.1058(2) 0.09005(14) 0.10260(14) 0.0352(7) Uani 1 1 d . . . C41 C 0.2042(3) 0.07598(18) 0.1389(2) 0.0694(12) Uani 1 1 d . . . H41A H 0.2541 0.1016 0.1207 0.104 Uiso 1 1 calc R . . H41B H 0.2189 0.0289 0.1361 0.104 Uiso 1 1 calc R . . H41C H 0.2030 0.0883 0.1831 0.104 Uiso 1 1 calc R . . C42 C 0.1055(3) 0.06570(16) 0.03451(18) 0.0576(10) Uani 1 1 d . . . H42A H 0.0411 0.0724 0.0117 0.086 Uiso 1 1 calc R . . H42B H 0.1217 0.0187 0.0347 0.086 Uiso 1 1 calc R . . H42C H 0.1537 0.0904 0.0137 0.086 Uiso 1 1 calc R . . C43 C 0.0289(3) 0.05024(17) 0.13239(19) 0.0595(10) Uani 1 1 d . . . H43A H 0.0291 0.0629 0.1767 0.089 Uiso 1 1 calc R . . H43B H 0.0435 0.0032 0.1298 0.089 Uiso 1 1 calc R . . H43C H -0.0351 0.0591 0.1098 0.089 Uiso 1 1 calc R . . C44 C 0.20213(17) 0.31810(13) 0.03947(11) 0.0226(5) Uani 1 1 d . . . H44A H 0.2235 0.2942 0.0030 0.027 Uiso 1 1 calc R . . H44B H 0.1675 0.3582 0.0229 0.027 Uiso 1 1 calc R . . O6 O 0.08791(17) 0.18433(10) 0.30993(10) 0.0492(6) Uani 1 1 d . . . C46 C 0.0042(3) 0.19768(17) 0.34022(18) 0.0531(9) Uani 1 1 d . . . H46A H -0.0346 0.2331 0.3179 0.064 Uiso 1 1 calc R . . H46B H 0.0226 0.2116 0.3843 0.064 Uiso 1 1 calc R . . C47 C -0.0522(3) 0.13505(18) 0.3383(2) 0.0613(10) Uani 1 1 d . . . H47A H -0.1016 0.1339 0.3011 0.074 Uiso 1 1 calc R . . H47B H -0.0849 0.1297 0.3769 0.074 Uiso 1 1 calc R . . C48 C 0.0241(3) 0.08148(17) 0.33387(19) 0.0558(9) Uani 1 1 d . . . H48A H 0.0320 0.0544 0.3727 0.067 Uiso 1 1 calc R . . H48B H 0.0061 0.0524 0.2972 0.067 Uiso 1 1 calc R . . C49 C 0.1147(3) 0.11864(16) 0.3261(2) 0.0600(10) Uani 1 1 d . . . H49A H 0.1588 0.1178 0.3658 0.072 Uiso 1 1 calc R . . H49B H 0.1486 0.0985 0.2924 0.072 Uiso 1 1 calc R . . O5 O 0.32845(16) 0.19495(11) 0.24945(12) 0.0567(6) Uani 1 1 d . . . C51 C 0.3905(3) 0.2108(2) 0.2023(2) 0.0683(12) Uani 1 1 d . . . H51A H 0.4263 0.2522 0.2131 0.082 Uiso 1 1 calc R . . H51B H 0.3524 0.2161 0.1606 0.082 Uiso 1 1 calc R . . C52 C 0.4603(3) 0.1530(2) 0.2017(2) 0.0806(13) Uani 1 1 d . . . H52A H 0.4349 0.1192 0.1708 0.097 Uiso 1 1 calc R . . H52B H 0.5247 0.1678 0.1914 0.097 Uiso 1 1 calc R . . C53 C 0.4659(3) 0.1272(2) 0.2676(2) 0.0747(13) Uani 1 1 d . . . H53A H 0.4788 0.0792 0.2686 0.090 Uiso 1 1 calc R . . H53B H 0.5178 0.1497 0.2952 0.090 Uiso 1 1 calc R . . O8 O 0.12882(12) 0.49036(8) 0.09557(8) 0.0252(4) Uani 1 1 d . . . C54 C 0.3699(3) 0.14161(18) 0.28782(19) 0.0618(10) Uani 1 1 d . . . H54A H 0.3277 0.1022 0.2823 0.074 Uiso 1 1 calc R . . H54B H 0.3765 0.1543 0.3329 0.074 Uiso 1 1 calc R . . C56 C 0.08936(18) 0.53802(13) 0.06328(11) 0.0253(6) Uani 1 1 d . . . C57 C -0.00710(19) 0.55637(13) 0.06432(13) 0.0315(6) Uani 1 1 d . . . H57 H -0.0319 0.5912 0.0375 0.038 Uiso 1 1 calc R . . C58 C -0.06866(18) 0.52635(12) 0.10251(13) 0.0271(6) Uani 1 1 d . . . O7 O -0.04230(12) 0.47933(8) 0.14084(8) 0.0259(4) Uani 1 1 d . . . C60 C 0.1539(2) 0.57493(14) 0.02371(14) 0.0355(7) Uani 1 1 d . . . H60A H 0.1900 0.6086 0.0495 0.053 Uiso 1 1 calc R . . H60B H 0.1143 0.5961 -0.0115 0.053 Uiso 1 1 calc R . . H60C H 0.1995 0.5443 0.0073 0.053 Uiso 1 1 calc R . . C61 C -0.1718(2) 0.54862(16) 0.10250(17) 0.0459(8) Uani 1 1 d . . . H61A H -0.2145 0.5101 0.1013 0.069 Uiso 1 1 calc R . . H61B H -0.1900 0.5762 0.0654 0.069 Uiso 1 1 calc R . . H61C H -0.1782 0.5741 0.1408 0.069 Uiso 1 1 calc R . . O1S O -0.2439(6) 0.5256(4) 0.3601(3) 0.216(3) Uani 1 1 d DU . . C2S C -0.3121(12) 0.5018(8) 0.3033(6) 0.109(6) Uani 0.50 1 d PDU A 1 H2S1 H -0.3214 0.4535 0.3045 0.131 Uiso 0.50 1 calc PR A 1 H2S2 H -0.3761 0.5237 0.3015 0.131 Uiso 0.50 1 calc PR A 1 C3S C -0.2642(14) 0.5197(10) 0.2542(7) 0.166(9) Uani 0.50 1 d PDU A 1 H3S1 H -0.3105 0.5266 0.2161 0.200 Uiso 0.50 1 calc PR A 1 H3S2 H -0.2177 0.4849 0.2452 0.200 Uiso 0.50 1 calc PR A 1 C4S C -0.2138(11) 0.5797(7) 0.2716(7) 0.106(5) Uani 0.50 1 d PDU A 1 H4S1 H -0.1455 0.5759 0.2628 0.127 Uiso 0.50 1 calc PR A 1 H4S2 H -0.2440 0.6166 0.2463 0.127 Uiso 0.50 1 calc PR A 1 C5S C -0.2168(15) 0.5918(6) 0.3318(7) 0.132(6) Uani 0.50 1 d PDU A 1 H5S1 H -0.2662 0.6257 0.3379 0.158 Uiso 0.50 1 calc PR A 1 H5S2 H -0.1530 0.6072 0.3517 0.158 Uiso 0.50 1 calc PR A 1 C6S C -0.2360(17) 0.5987(6) 0.3501(7) 0.120(5) Uani 0.50 1 d PDU A 2 H6S1 H -0.2941 0.6214 0.3624 0.144 Uiso 0.50 1 calc PR A 2 H6S2 H -0.1781 0.6165 0.3758 0.144 Uiso 0.50 1 calc PR A 2 C7S C -0.2287(14) 0.6077(7) 0.2891(7) 0.132(7) Uani 0.50 1 d PDU A 2 H7S1 H -0.1736 0.6373 0.2834 0.158 Uiso 0.50 1 calc PR A 2 H7S2 H -0.2888 0.6278 0.2682 0.158 Uiso 0.50 1 calc PR A 2 C8S C -0.2133(19) 0.5443(10) 0.2627(9) 0.183(11) Uani 0.50 1 d PDU A 2 H8S1 H -0.2290 0.5450 0.2163 0.219 Uiso 0.50 1 calc PR A 2 H8S2 H -0.1453 0.5300 0.2729 0.219 Uiso 0.50 1 calc PR A 2 C9S C -0.2748(12) 0.5039(8) 0.2899(7) 0.142(7) Uani 0.50 1 d PDU A 2 H9S1 H -0.2614 0.4567 0.2828 0.170 Uiso 0.50 1 calc PR A 2 H9S2 H -0.3437 0.5137 0.2761 0.170 Uiso 0.50 1 calc PR A 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 K1 0.0375(3) 0.0225(3) 0.0355(4) 0.0096(3) -0.0011(3) 0.0035(2) Ti1 0.0207(2) 0.0154(2) 0.0189(2) 0.00425(18) 0.00194(17) 0.00253(17) O1 0.0215(8) 0.0185(9) 0.0186(9) 0.0008(7) 0.0011(7) -0.0007(7) C1 0.0217(12) 0.0162(13) 0.0198(13) 0.0054(10) 0.0020(10) 0.0000(10) C2 0.0242(13) 0.0180(13) 0.0171(12) 0.0026(10) 0.0023(10) -0.0027(10) C3 0.0223(13) 0.0278(15) 0.0233(14) 0.0022(11) 0.0020(10) -0.0042(11) C4 0.0228(13) 0.0335(16) 0.0243(14) 0.0014(12) 0.0057(10) -0.0021(11) C5 0.0287(14) 0.0303(15) 0.0205(13) -0.0002(11) 0.0060(11) 0.0004(11) C6 0.0222(12) 0.0208(14) 0.0197(13) 0.0021(10) 0.0022(10) 0.0018(10) C7 0.0240(14) 0.054(2) 0.0344(16) -0.0063(14) 0.0098(12) -0.0069(13) C8 0.0254(14) 0.058(2) 0.0479(19) -0.0058(16) 0.0103(13) -0.0049(14) C9 0.0382(18) 0.120(4) 0.0350(19) 0.003(2) 0.0152(15) -0.015(2) C10 0.0321(17) 0.065(3) 0.082(3) -0.027(2) 0.0165(17) 0.0042(16) C11 0.0265(13) 0.0193(14) 0.0255(14) -0.0024(11) 0.0028(11) -0.0068(10) O2 0.0279(9) 0.0143(9) 0.0227(9) 0.0000(7) 0.0023(7) 0.0000(7) C12 0.0257(12) 0.0106(12) 0.0201(13) -0.0031(10) 0.0004(10) -0.0026(9) C13 0.0228(12) 0.0157(13) 0.0190(13) -0.0055(10) 0.0019(10) -0.0035(10) C14 0.0271(13) 0.0236(14) 0.0187(13) -0.0037(11) 0.0043(10) -0.0060(10) C15 0.0237(12) 0.0197(13) 0.0196(13) -0.0028(10) 0.0000(10) -0.0026(10) C16 0.0195(12) 0.0211(14) 0.0216(13) -0.0042(10) -0.0003(10) -0.0022(10) C17 0.0246(12) 0.0146(13) 0.0186(12) -0.0051(10) 0.0027(10) -0.0063(10) C18 0.0306(14) 0.0304(16) 0.0240(14) 0.0053(12) -0.0019(11) -0.0014(11) C19 0.057(2) 0.039(2) 0.050(2) 0.0181(16) -0.0020(16) -0.0013(15) C20 0.059(2) 0.050(2) 0.0258(16) 0.0007(14) -0.0065(14) 0.0074(16) C21 0.0409(18) 0.076(3) 0.0427(19) 0.0212(18) 0.0026(15) 0.0177(17) C22 0.0233(12) 0.0219(14) 0.0226(13) -0.0021(11) 0.0044(10) 0.0015(10) O3 0.0223(8) 0.0207(9) 0.0185(9) 0.0016(7) 0.0039(7) -0.0025(7) C23 0.0191(12) 0.0184(13) 0.0208(13) 0.0057(10) 0.0027(10) 0.0014(10) C24 0.0219(12) 0.0249(14) 0.0205(13) 0.0023(11) -0.0013(10) -0.0007(10) C25 0.0241(13) 0.0292(15) 0.0276(14) 0.0018(12) 0.0024(11) -0.0089(11) C26 0.0239(13) 0.0305(16) 0.0256(14) 0.0039(12) 0.0034(11) -0.0006(11) C27 0.0241(13) 0.0277(15) 0.0203(13) 0.0006(11) 0.0048(10) 0.0027(11) C28 0.0213(12) 0.0197(13) 0.0216(13) 0.0016(10) 0.0016(10) 0.0029(10) C29 0.0275(14) 0.0391(17) 0.0292(15) 0.0021(13) 0.0089(11) -0.0081(12) C30 0.0302(16) 0.094(3) 0.043(2) 0.0112(19) 0.0092(14) -0.0032(17) C31 0.054(2) 0.045(2) 0.056(2) 0.0036(16) 0.0242(17) -0.0134(16) C32 0.0417(17) 0.054(2) 0.0374(18) 0.0002(15) 0.0179(14) -0.0107(15) C33 0.0223(13) 0.0318(16) 0.0240(14) -0.0012(11) -0.0001(10) -0.0068(11) O4 0.0227(8) 0.0204(9) 0.0168(9) 0.0038(7) -0.0020(7) 0.0031(7) C34 0.0238(12) 0.0220(14) 0.0123(12) -0.0006(10) -0.0066(9) 0.0004(10) C35 0.0233(12) 0.0236(14) 0.0138(12) -0.0002(10) -0.0050(10) -0.0006(10) C36 0.0281(13) 0.0244(14) 0.0195(13) -0.0028(11) -0.0049(10) 0.0025(11) C37 0.0324(14) 0.0222(14) 0.0211(13) 0.0008(11) -0.0077(11) -0.0015(11) C38 0.0343(14) 0.0251(15) 0.0173(13) 0.0026(11) -0.0067(10) -0.0093(11) C39 0.0220(12) 0.0280(15) 0.0155(12) -0.0021(10) -0.0027(10) -0.0039(10) C40 0.0426(16) 0.0201(15) 0.0400(17) 0.0051(12) -0.0092(13) -0.0005(12) C41 0.067(2) 0.035(2) 0.097(3) 0.023(2) -0.030(2) 0.0014(17) C42 0.081(3) 0.0266(19) 0.064(2) -0.0054(16) 0.003(2) 0.0023(17) C43 0.077(3) 0.0297(19) 0.069(3) 0.0143(17) -0.001(2) -0.0065(17) C44 0.0257(13) 0.0263(14) 0.0157(12) 0.0008(10) 0.0011(10) 0.0009(10) O6 0.0699(15) 0.0352(13) 0.0448(13) 0.0102(10) 0.0168(11) 0.0066(11) C46 0.067(2) 0.038(2) 0.056(2) 0.0104(16) 0.0157(18) 0.0142(17) C47 0.052(2) 0.054(2) 0.076(3) -0.005(2) -0.0002(19) 0.0034(17) C48 0.066(2) 0.036(2) 0.067(2) -0.0026(17) 0.0159(19) -0.0033(17) C49 0.062(2) 0.0294(19) 0.089(3) -0.0036(18) 0.007(2) 0.0029(16) O5 0.0497(13) 0.0412(14) 0.0759(18) 0.0113(12) -0.0076(12) 0.0144(11) C51 0.053(2) 0.062(3) 0.086(3) 0.034(2) -0.008(2) -0.0021(18) C52 0.052(2) 0.100(4) 0.090(3) 0.018(3) 0.007(2) 0.021(2) C53 0.043(2) 0.053(2) 0.125(4) 0.037(2) -0.003(2) 0.0019(17) O8 0.0270(9) 0.0225(10) 0.0260(10) 0.0078(8) 0.0030(7) 0.0025(7) C54 0.076(3) 0.044(2) 0.061(2) 0.0101(18) -0.009(2) 0.0195(19) C56 0.0353(14) 0.0202(14) 0.0188(13) 0.0017(11) -0.0045(11) -0.0068(11) C57 0.0340(15) 0.0219(15) 0.0359(16) 0.0119(12) -0.0086(12) 0.0036(11) C58 0.0299(14) 0.0166(14) 0.0328(15) -0.0016(12) -0.0057(11) 0.0054(11) O7 0.0267(9) 0.0211(10) 0.0298(10) 0.0030(8) 0.0030(7) 0.0041(7) C60 0.0412(16) 0.0279(16) 0.0354(16) 0.0129(13) -0.0046(13) -0.0114(12) C61 0.0341(16) 0.0407(19) 0.062(2) 0.0103(16) 0.0005(15) 0.0108(14) O1S 0.300(8) 0.198(6) 0.141(4) 0.035(4) -0.017(5) -0.024(6) C2S 0.151(15) 0.071(8) 0.106(8) -0.001(7) 0.022(7) -0.020(9) C3S 0.168(17) 0.23(2) 0.092(7) -0.015(11) -0.003(9) -0.102(16) C4S 0.078(8) 0.087(11) 0.165(12) 0.029(9) 0.064(10) 0.022(8) C5S 0.129(14) 0.061(7) 0.202(15) -0.065(8) 0.011(14) 0.013(8) C6S 0.151(11) 0.100(7) 0.120(9) -0.017(7) 0.060(9) 0.067(8) C7S 0.172(15) 0.105(11) 0.117(10) 0.083(10) 0.014(11) 0.065(9) C8S 0.18(2) 0.26(3) 0.125(11) -0.046(13) 0.080(14) 0.093(17) C9S 0.100(11) 0.093(9) 0.211(14) -0.027(11) -0.078(12) 0.068(8) _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 K1 O6 2.693(2) . ? K1 O5 2.706(2) . ? K1 O1 2.7476(17) . ? K1 O3 2.7479(17) . ? K1 C17 3.398(2) . ? K1 C23 3.400(2) . ? K1 C1 3.413(2) . ? K1 C39 3.416(2) . ? K1 C12 3.417(2) . ? K1 C34 3.449(2) . ? K1 C16 3.464(2) . ? K1 C13 3.467(2) . ? Ti1 O3 1.8547(16) . ? Ti1 O1 1.8593(16) . ? Ti1 O2 1.9503(17) . ? Ti1 O4 1.9622(17) . ? Ti1 O7 1.9989(17) . ? Ti1 O8 2.0130(17) . ? O1 C1 1.335(3) . ? C1 C6 1.398(3) . ? C1 C2 1.401(3) . ? C2 C3 1.386(3) . ? C2 C11 1.523(3) . ? C3 C4 1.390(4) . ? C4 C5 1.405(4) . ? C4 C7 1.535(4) . ? C5 C6 1.392(3) . ? C6 C44 1.520(3) . ? C7 C8 1.535(4) . ? C7 C9 1.535(4) . ? C7 C10 1.539(5) . ? C11 C17 1.523(3) . ? O2 C12 1.354(3) . ? C12 C17 1.412(3) . ? C12 C13 1.413(3) . ? C13 C14 1.386(4) . ? C13 C22 1.522(3) . ? C14 C15 1.402(3) . ? C15 C16 1.396(3) . ? C15 C18 1.530(4) . ? C16 C17 1.396(3) . ? C18 C21 1.505(4) . ? C18 C19 1.533(4) . ? C18 C20 1.551(4) . ? C22 C28 1.518(3) . ? O3 C23 1.342(3) . ? C23 C28 1.398(3) . ? C23 C24 1.402(3) . ? C24 C25 1.391(3) . ? C24 C33 1.520(3) . ? C25 C26 1.406(4) . ? C26 C27 1.393(4) . ? C26 C29 1.535(3) . ? C27 C28 1.392(3) . ? C29 C30 1.522(4) . ? C29 C32 1.534(4) . ? C29 C31 1.544(4) . ? C33 C39 1.533(3) . ? O4 C34 1.350(3) . ? C34 C39 1.412(3) . ? C34 C35 1.423(3) . ? C35 C36 1.382(4) . ? C35 C44 1.526(3) . ? C36 C37 1.394(4) . ? C37 C38 1.398(4) . ? C37 C40 1.534(4) . ? C38 C39 1.397(4) . ? C40 C41 1.522(4) . ? C40 C43 1.531(4) . ? C40 C42 1.535(5) . ? O6 C46 1.417(4) . ? O6 C49 1.417(4) . ? C46 C47 1.492(5) . ? C47 C48 1.529(5) . ? C48 C49 1.492(5) . ? O5 C51 1.432(4) . ? O5 C54 1.439(4) . ? C51 C52 1.523(6) . ? C52 C53 1.496(6) . ? C53 C54 1.475(5) . ? O8 C56 1.276(3) . ? C56 C57 1.392(4) . ? C56 C60 1.498(4) . ? C57 C58 1.385(4) . ? C58 O7 1.284(3) . ? C58 C61 1.501(4) . ? O1S C6S 1.506(12) . ? O1S C2S 1.533(12) . ? O1S C5S 1.538(13) . ? O1S C9S 1.576(13) . ? C2S C3S 1.352(14) . ? C3S C4S 1.433(17) . ? C4S C5S 1.314(14) . ? C6S C7S 1.329(13) . ? C7S C8S 1.430(18) . ? C8S C9S 1.361(16) . ? 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 O6 K1 O5 86.98(7) . . ? O6 K1 O1 162.04(6) . . ? O5 K1 O1 110.84(6) . . ? O6 K1 O3 104.62(6) . . ? O5 K1 O3 168.40(7) . . ? O1 K1 O3 57.56(5) . . ? O6 K1 C17 127.79(7) . . ? O5 K1 C17 97.94(7) . . ? O1 K1 C17 54.13(5) . . ? O3 K1 C17 75.25(5) . . ? O6 K1 C23 82.51(6) . . ? O5 K1 C23 169.49(7) . . ? O1 K1 C23 79.67(5) . . ? O3 K1 C23 22.12(5) . . ? C17 K1 C23 88.13(6) . . ? O6 K1 C1 175.52(7) . . ? O5 K1 C1 89.05(7) . . ? O1 K1 C1 21.79(5) . . ? O3 K1 C1 79.35(5) . . ? C17 K1 C1 54.91(6) . . ? C23 K1 C1 101.46(6) . . ? O6 K1 C39 93.14(7) . . ? O5 K1 C39 126.03(7) . . ? O1 K1 C39 74.82(5) . . ? O3 K1 C39 54.29(6) . . ? C17 K1 C39 122.51(6) . . ? C23 K1 C39 55.50(6) . . ? C1 K1 C39 87.50(6) . . ? O6 K1 C12 119.48(6) . . ? O5 K1 C12 121.45(7) . . ? O1 K1 C12 53.61(5) . . ? O3 K1 C12 52.96(5) . . ? C17 K1 C12 23.92(6) . . ? C23 K1 C12 64.22(6) . . ? C1 K1 C12 64.52(6) . . ? C39 K1 C12 105.07(6) . . ? O6 K1 C34 116.79(7) . . ? O5 K1 C34 121.48(7) . . ? O1 K1 C34 52.45(5) . . ? O3 K1 C34 53.19(5) . . ? C17 K1 C34 104.50(6) . . ? C23 K1 C34 64.58(6) . . ? C1 K1 C34 63.77(6) . . ? C39 K1 C34 23.73(6) . . ? C12 K1 C34 93.41(6) . . ? O6 K1 C16 109.75(7) . . ? O5 K1 C16 82.07(7) . . ? O1 K1 C16 76.18(5) . . ? O3 K1 C16 93.94(5) . . ? C17 K1 C16 23.45(6) . . ? C23 K1 C16 100.96(6) . . ? C1 K1 C16 71.71(6) . . ? C39 K1 C16 145.41(6) . . ? C12 K1 C16 41.20(6) . . ? C34 K1 C16 127.76(6) . . ? O6 K1 C13 95.90(6) . . ? O5 K1 C13 127.17(7) . . ? O1 K1 C13 75.43(5) . . ? O3 K1 C13 52.88(5) . . ? C17 K1 C13 41.57(5) . . ? C23 K1 C13 53.95(6) . . ? C1 K1 C13 88.17(6) . . ? C39 K1 C13 106.53(6) . . ? C12 K1 C13 23.68(6) . . ? C34 K1 C13 103.98(6) . . ? C16 K1 C13 47.33(6) . . ? O3 Ti1 O1 90.86(7) . . ? O3 Ti1 O2 87.81(7) . . ? O1 Ti1 O2 87.89(7) . . ? O3 Ti1 O4 86.91(7) . . ? O1 Ti1 O4 87.44(7) . . ? O2 Ti1 O4 172.90(7) . . ? O3 Ti1 O7 94.66(7) . . ? O1 Ti1 O7 173.94(7) . . ? O2 Ti1 O7 94.79(7) . . ? O4 Ti1 O7 90.37(7) . . ? O3 Ti1 O8 178.09(7) . . ? O1 Ti1 O8 91.04(7) . . ? O2 Ti1 O8 92.04(7) . . ? O4 Ti1 O8 93.40(7) . . ? O7 Ti1 O8 83.45(7) . . ? O3 Ti1 K1 45.42(5) . . ? O1 Ti1 K1 45.45(5) . . ? O2 Ti1 K1 86.34(5) . . ? O4 Ti1 K1 86.57(5) . . ? O7 Ti1 K1 140.05(5) . . ? O8 Ti1 K1 136.48(5) . . ? C1 O1 Ti1 145.83(15) . . ? C1 O1 K1 108.41(13) . . ? Ti1 O1 K1 105.72(7) . . ? O1 C1 C6 118.9(2) . . ? O1 C1 C2 119.2(2) . . ? C6 C1 C2 121.9(2) . . ? O1 C1 K1 49.80(10) . . ? C6 C1 K1 110.53(16) . . ? C2 C1 K1 106.63(15) . . ? C3 C2 C1 117.8(2) . . ? C3 C2 C11 122.6(2) . . ? C1 C2 C11 119.2(2) . . ? C2 C3 C4 122.7(2) . . ? C3 C4 C5 117.6(2) . . ? C3 C4 C7 122.8(2) . . ? C5 C4 C7 119.6(2) . . ? C6 C5 C4 122.1(2) . . ? C5 C6 C1 117.9(2) . . ? C5 C6 C44 123.2(2) . . ? C1 C6 C44 118.6(2) . . ? C8 C7 C9 107.3(3) . . ? C8 C7 C4 112.2(2) . . ? C9 C7 C4 109.7(2) . . ? C8 C7 C10 108.3(3) . . ? C9 C7 C10 109.7(3) . . ? C4 C7 C10 109.6(2) . . ? C17 C11 C2 118.2(2) . . ? C12 O2 Ti1 117.11(14) . . ? O2 C12 C17 120.5(2) . . ? O2 C12 C13 120.2(2) . . ? C17 C12 C13 119.2(2) . . ? O2 C12 K1 109.86(13) . . ? C17 C12 K1 77.31(13) . . ? C13 C12 K1 80.13(13) . . ? C14 C13 C12 119.1(2) . . ? C14 C13 C22 119.7(2) . . ? C12 C13 C22 121.1(2) . . ? C14 C13 K1 81.23(14) . . ? C12 C13 K1 76.19(13) . . ? C22 C13 K1 114.39(14) . . ? C13 C14 C15 123.2(2) . . ? C13 C14 K1 75.96(14) . . ? C15 C14 K1 80.12(14) . . ? C16 C15 C14 116.4(2) . . ? C16 C15 C18 123.1(2) . . ? C14 C15 C18 120.4(2) . . ? C15 C16 C17 122.9(2) . . ? C15 C16 K1 82.79(14) . . ? C17 C16 K1 75.62(13) . . ? C16 C17 C12 119.1(2) . . ? C16 C17 C11 119.8(2) . . ? C12 C17 C11 121.0(2) . . ? C16 C17 K1 80.93(14) . . ? C12 C17 K1 78.78(13) . . ? C11 C17 K1 113.99(14) . . ? C21 C18 C15 113.3(2) . . ? C21 C18 C19 109.3(3) . . ? C15 C18 C19 109.9(2) . . ? C21 C18 C20 108.8(2) . . ? C15 C18 C20 108.3(2) . . ? C19 C18 C20 107.1(2) . . ? C28 C22 C13 116.6(2) . . ? C23 O3 Ti1 146.71(15) . . ? C23 O3 K1 107.44(13) . . ? Ti1 O3 K1 105.85(7) . . ? O3 C23 C28 118.6(2) . . ? O3 C23 C24 118.8(2) . . ? C28 C23 C24 122.6(2) . . ? O3 C23 K1 50.45(11) . . ? C28 C23 K1 109.28(15) . . ? C24 C23 K1 105.93(15) . . ? C25 C24 C23 117.0(2) . . ? C25 C24 C33 123.1(2) . . ? C23 C24 C33 119.4(2) . . ? C24 C25 C26 123.0(2) . . ? C27 C26 C25 117.1(2) . . ? C27 C26 C29 122.3(2) . . ? C25 C26 C29 120.6(2) . . ? C28 C27 C26 122.6(2) . . ? C27 C28 C23 117.7(2) . . ? C27 C28 C22 122.6(2) . . ? C23 C28 C22 119.5(2) . . ? C30 C29 C32 108.8(3) . . ? C30 C29 C26 110.0(2) . . ? C32 C29 C26 112.8(2) . . ? C30 C29 C31 109.4(3) . . ? C32 C29 C31 106.4(2) . . ? C26 C29 C31 109.4(2) . . ? C24 C33 C39 119.8(2) . . ? C34 O4 Ti1 117.56(13) . . ? O4 C34 C39 121.1(2) . . ? O4 C34 C35 120.0(2) . . ? C39 C34 C35 118.9(2) . . ? O4 C34 K1 109.05(13) . . ? C39 C34 K1 76.85(13) . . ? C35 C34 K1 81.76(13) . . ? C36 C35 C34 119.2(2) . . ? C36 C35 C44 119.6(2) . . ? C34 C35 C44 121.2(2) . . ? C36 C35 K1 82.97(14) . . ? C34 C35 K1 74.77(13) . . ? C44 C35 K1 113.37(14) . . ? C35 C36 C37 123.4(2) . . ? C36 C37 C38 116.2(2) . . ? C36 C37 C40 120.3(2) . . ? C38 C37 C40 123.4(2) . . ? C39 C38 C37 123.2(2) . . ? C39 C38 K1 74.17(13) . . ? C37 C38 K1 85.23(15) . . ? C38 C39 C34 119.0(2) . . ? C38 C39 C33 119.8(2) . . ? C34 C39 C33 121.1(2) . . ? C38 C39 K1 82.67(14) . . ? C34 C39 K1 79.42(13) . . ? C33 C39 K1 111.77(14) . . ? C41 C40 C43 108.5(3) . . ? C41 C40 C37 110.4(2) . . ? C43 C40 C37 112.7(3) . . ? C41 C40 C42 109.2(3) . . ? C43 C40 C42 107.1(3) . . ? C37 C40 C42 108.8(2) . . ? C6 C44 C35 117.0(2) . . ? C46 O6 C49 106.0(2) . . ? C46 O6 K1 123.67(18) . . ? C49 O6 K1 130.3(2) . . ? O6 C46 C47 106.2(3) . . ? C46 C47 C48 104.1(3) . . ? C49 C48 C47 104.2(3) . . ? O6 C49 C48 107.5(3) . . ? C51 O5 C54 109.6(3) . . ? C51 O5 K1 110.29(18) . . ? C54 O5 K1 140.0(2) . . ? O5 C51 C52 105.4(3) . . ? O5 C51 K1 46.96(14) . . ? C52 C51 K1 148.9(3) . . ? C53 C52 C51 103.3(4) . . ? C54 C53 C52 104.5(3) . . ? C56 O8 Ti1 132.78(16) . . ? O5 C54 C53 107.5(3) . . ? O8 C56 C57 123.4(2) . . ? O8 C56 C60 115.9(2) . . ? C57 C56 C60 120.7(2) . . ? C58 C57 C56 123.2(2) . . ? O7 C58 C57 123.4(2) . . ? O7 C58 C61 115.4(2) . . ? C57 C58 C61 121.1(2) . . ? C58 O7 Ti1 132.71(16) . . ? C6S O1S C2S 104.3(11) . . ? C6S O1S C5S 19.4(9) . . ? C2S O1S C5S 97.0(9) . . ? C6S O1S C9S 99.0(9) . . ? C2S O1S C9S 23.0(9) . . ? C5S O1S C9S 85.6(10) . . ? C3S C2S O1S 102.4(10) . . ? C2S C3S C4S 107.2(10) . . ? C5S C4S C3S 110.2(9) . . ? C4S C5S O1S 104.8(9) . . ? C7S C6S O1S 106.8(10) . . ? C6S C7S C8S 107.1(12) . . ? C9S C8S C7S 104.3(13) . . ? C8S C9S O1S 96.9(12) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.649 _refine_diff_density_min -0.541 _refine_diff_density_rms 0.120 data_4 _database_code_CSD 218774 _audit_creation_method 'RAELSPUB and manual entry' # TEXT _publ_section_abstract ? _publ_section_comment ? _publ_section_acknowledgements ? _publ_section_references ; Altomare, A., Burla, M.C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Polidori, G., J. Appl. Cryst., 1994, 27, 435. Ibers, J.A. and Hamilton, W.C., (Eds) International Tables for X-Ray Crystallography Vol. 4 , Kynoch Press, Birmingham, 1974. Johnson, C.K.,'ORTEP-II', Oak Ridge National Laboratory, Tennessee, U.S.A., 1976. Rae, A.D., RAELS. A comprehensive Constrained Least Squares Refinement Program, University of New South Wales, 1989. ; _publ_section_figure_captions ? _publ_section_exptl_prep ? _publ_section_exptl_refinement ? _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR92 (Altomare et al, 1994)' _computing_structure_refinement 'RAELS, (Rae, 1989)' _computing_molecular_graphics 'ORTEP-II, (Johnson, 1976)' _computing_publication_material 'Local programs' # CHEMICAL DATA _chemical_name_systematic ? _chemical_formula_moiety 'C51 H67 Cs O8 Ti,4(C H4 O)' _chemical_formula_sum 'C55 H83 Cs O12 Ti' _chemical_formula_iupac ? _chemical_formula_weight 1117.1 # CRYSTAL DATA _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 2/c' loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 x,-y,1/2+z 3 -x,-y,-z 4 -x,y,1/2-z 5 1/2+x,1/2+y,z 6 1/2+x,1/2-y,1/2+z 7 1/2-x,1/2-y,-z 8 1/2-x,1/2+y,1/2-z _cell_length_a 13.622(5) _cell_length_b 22.248(7) _cell_length_c 21.168(7) _cell_angle_alpha 90 _cell_angle_beta 105.12(1) _cell_angle_gamma 90 _cell_volume 6193(6) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 983 _cell_measurement_theta_min 2.97 _cell_measurement_theta_max 27.38 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_size_rad ? _exptl_crystal_density_diffrn 1.20 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2344.0 _exptl_absorpt_coefficient_mu 0.761 _exptl_absorpt_correction_type none _exptl_absorpt_process_details ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_ambient_temperature 273(2) _diffrn_reflns_number 29958 _diffrn_reflns_av_R_equivalents 0.030 _diffrn_reflns_theta_max 27 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 29 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 28 _diffrn_standards_number ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 # REFINEMENT DATA _refine_special_details ? _reflns_number_total 7399 _reflns_number_gt 6178 _reflns_threshold_expression I>2\s(I) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.061 _refine_ls_wR_factor_ref 0.093 _refine_ls_hydrogen_treatment noref _refine_ls_number_reflns 6178 _refine_ls_number_parameters 171 _refine_ls_goodness_of_fit_ref 1.94 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[\s^2^(F) + 0.0004F^2^]' _refine_ls_shift/su_max 0.004 _refine_diff_density_max 1.14 _refine_diff_density_min -0.97 _refine_ls_extinction_method none _refine_ls_extinction_coef ? _atom_type_scat_source 'International Tables for X-ray Crystallography, Vol. IV' # ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_type_symbol _atom_site_occupancy Cs1 0.00000 0.08120(2) 0.25000 0.0425(2) Uani Cs 1.0 Ti1 0.00000 -0.10089(4) 0.25000 0.0263(2) Uani Ti 1.0 O1 0.0757(2) -0.0460(1) 0.2193(1) 0.0277(3) Uani O 1.0 O2 -0.1038(2) -0.0956(1) 0.1645(1) 0.0293(3) Uani O 1.0 C1 0.1461(2) -0.0292(1) 0.1911(1) 0.0297(3) Uani C 1.0 C2 0.2452(2) -0.0164(1) 0.2289(1) 0.0339(3) Uani C 1.0 C3 0.3153(2) 0.0063(1) 0.1975(1) 0.0392(5) Uani C 1.0 C4 0.2911(2) 0.0170(1) 0.1302(1) 0.0389(6) Uani C 1.0 C5 0.1920(2) 0.0037(1) 0.0944(1) 0.0333(5) Uani C 1.0 C6 0.1188(2) -0.0191(1) 0.1231(1) 0.0296(3) Uani C 1.0 C7 0.2730(3) -0.0370(2) 0.3008(2) 0.0350(4) Uani C 1.0 C8 0.3728(6) 0.0365(5) 0.0969(5) 0.062(1) Uani C 0.5 C9 0.4361(11) -0.0177(10) 0.0869(13) 0.107(5) Uani C 0.5 C10 0.4436(14) 0.0828(9) 0.1389(11) 0.076(3) Uani C 0.5 C11 0.3241(17) 0.0645(14) 0.0302(8) 0.130(2) Uani C 0.5 C8' 0.3733(6) 0.0402(5) 0.0993(5) 0.061(1) Uani C 0.5 C9' 0.4520(10) -0.0089(10) 0.0999(13) 0.097(4) Uani C 0.5 C10' 0.4274(15) 0.0944(8) 0.1373(13) 0.085(3) Uani C 0.5 C11' 0.3267(17) 0.0592(14) 0.0285(7) 0.129(2) Uani C 0.5 C12 -0.1298(2) -0.0387(1) 0.1413(1) 0.0287(3) Uani C 1.0 C13 -0.0739(2) -0.0108(1) 0.1021(1) 0.0279(3) Uani C 1.0 C14 -0.1019(2) 0.0468(1) 0.0785(1) 0.0299(4) Uani C 1.0 C15 -0.1830(2) 0.0779(1) 0.0921(1) 0.0335(6) Uani C 1.0 C16 -0.2366(2) 0.0488(1) 0.1312(1) 0.0342(6) Uani C 1.0 C17 -0.2120(2) -0.0088(1) 0.1561(1) 0.0316(3) Uani C 1.0 C18 0.0150(3) -0.0417(2) 0.0853(2) 0.0281(3) Uani C 1.0 C19 -0.2129(3) 0.1414(2) 0.0632(2) 0.048(1) Uani C 1.0 C20 -0.1542(4) 0.1883(2) 0.1112(3) 0.090(2) Uani C 1.0 C21 -0.3267(3) 0.1529(3) 0.0527(3) 0.096(3) Uani C 1.0 C22 -0.1865(6) 0.1490(3) -0.0021(3) 0.137(5) Uani C 1.0 O1Ac 0.0754(4) -0.1664(3) 0.2208(2) 0.107(7) Uani O 1.0 C1Ac 0.0785(9) -0.2194(4) 0.2216(5) 0.191(9) Uani C 1.0 C2Ac 0.0000 -0.2481(5) 0.2500 0.222(9) Uani C 1.0 C3Ac 0.1563(11) -0.2526(6) 0.1967(7) 0.340(9) Uani C 1.0 O1Me1 0.1158(4) 0.1796(3) 0.2031(3) 0.103(2) Uani O 1.0 C1Me1 0.1696(8) 0.1524(5) 0.1616(5) 0.130(4) Uani C 1.0 O1Me2 0.2986(7) 0.3101(4) 0.1083(6) 0.199(5) Uani O 1.0 C1Me2 0.3610(10) 0.2866(7) 0.0699(6) 0.308(9) Uani C 1.0 O1Me3 0.1131(8) 0.2934(5) 0.1484(8) 0.192(7) Uani O 0.67 C1Me3 0.0522(15) 0.3207(8) 0.0913(8) 0.149(6) Uani C 0.67 O1Me3' 0.1088(19) 0.3011(6) 0.2520(14) 0.192(7) Uani O 0.33 C1Me3' 0.0741(26) 0.3598(9) 0.2593(19) 0.149(6) Uani C 0.33 HC3 0.3857 0.0155 0.2243 0.045 Uani H 1.0 HC5 0.1728 0.0109 0.0461 0.034 Uani H 1.0 H1C7 0.3463 -0.0272 0.3203 0.040 Uani H 1.0 H2C7 0.2631 -0.0815 0.3013 0.035 Uani H 1.0 H1C9 0.4893 -0.0044 0.0651 0.133 Uani H 0.5 H2C9 0.4696 -0.0360 0.1303 0.125 Uani H 0.5 H3C9 0.3909 -0.0481 0.0588 0.150 Uani H 0.5 H1C10 0.4966 0.0951 0.1165 0.092 Uani H 0.5 H2C10 0.4034 0.1188 0.1453 0.115 Uani H 0.5 H3C10 0.4773 0.0647 0.1824 0.086 Uani H 0.5 H1C11 0.3786 0.0770 0.0091 0.170 Uani H 0.5 H2C11 0.2786 0.0344 0.0018 0.160 Uani H 0.5 H3C11 0.2834 0.1005 0.0360 0.164 Uani H 0.5 H1C9' 0.5054 0.0068 0.0796 0.117 Uani H 0.5 H2C9' 0.4843 -0.0212 0.1461 0.112 Uani H 0.5 H3C9' 0.4179 -0.0444 0.0745 0.141 Uani H 0.5 H1C10' 0.4810 0.1091 0.1165 0.102 Uani H 0.5 H2C10' 0.3770 0.1272 0.1367 0.130 Uani H 0.5 H3C10' 0.4598 0.0823 0.1836 0.093 Uani H 0.5 H1C11' 0.3815 0.0743 0.0090 0.168 Uani H 0.5 H2C11' 0.2922 0.0240 0.0027 0.157 Uani H 0.5 H3C11' 0.2758 0.0919 0.0273 0.165 Uani H 0.5 HC14 -0.0623 0.0667 0.0507 0.031 Uani H 1.0 HC16 -0.2950 0.0702 0.1416 0.038 Uani H 1.0 H1C18 0.0086 -0.0356 0.0376 0.029 Uani H 1.0 H2C18 0.0111 -0.0856 0.0945 0.029 Uani H 1.0 H1C20 -0.1730 0.2294 0.0930 0.097 Uani H 1.0 H2C20 -0.1717 0.1842 0.1540 0.128 Uani H 1.0 H3C20 -0.0796 0.1818 0.1178 0.161 Uani H 1.0 H1C21 -0.3437 0.1940 0.0340 0.103 Uani H 1.0 H2C21 -0.3662 0.1223 0.0216 0.169 Uani H 1.0 H3C21 -0.3446 0.1498 0.0954 0.135 Uani H 1.0 H1C22 -0.2065 0.1902 -0.0197 0.164 Uani H 1.0 H2C22 -0.1116 0.1436 0.0044 0.197 Uani H 1.0 H3C22 -0.2239 0.1184 -0.0339 0.196 Uani H 1.0 HC2Ac 0.0000 -0.2924 0.2500 0.335 Uani H 1.0 H1C3Ac 0.1470 -0.2968 0.2012 0.439 Uani H 1.0 H2C3Ac 0.1479 -0.2425 0.1495 0.365 Uani H 1.0 H3C3Ac 0.2259 -0.2407 0.2226 0.364 Uani H 1.0 H1O1Me1 0.1149 0.2205 0.1834 0.103 Uani H 1.0 H1C1Me1 0.2444 0.1567 0.1814 0.130 Uani H 1.0 H2C1Me1 0.1517 0.1088 0.1563 0.130 Uani H 1.0 H3C1Me1 0.1507 0.1725 0.1178 0.130 Uani H 1.0 H1O1Me2 0.3362 0.3464 0.1299 0.199 Uani H 1.0 H1C1Me2 0.4290 0.3067 0.0825 0.308 Uani H 1.0 H2C1Me2 0.3697 0.2424 0.0775 0.308 Uani H 1.0 H3C1Me2 0.3281 0.2943 0.0225 0.308 Uani H 1.0 H1O1Me3 0.1773 0.2992 0.1346 0.192 Uani H 1.0 H1C1Me3 0.0548 0.3653 0.0967 0.149 Uani H 1.0 H2C1Me3 0.0783 0.3094 0.0529 0.149 Uani H 1.0 H3C1Me3 -0.0197 0.3066 0.0838 0.149 Uani H 1.0 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 _atom_site_aniso_type_symbol Cs1 0.0564(3) 0.0320(2) 0.0302(2) 0.0000 -0.0045(1) 0.0000 Cs Ti1 0.0317(5) 0.0246(4) 0.0226(4) 0.0000 0.0069(3) 0.0000 Ti O1 0.0259(5) 0.0365(6) 0.0196(4) 0.0008(2) 0.0042(3) 0.0002(1) O O2 0.0300(5) 0.0372(6) 0.0196(4) -0.0032(3) 0.0042(4) -0.0006(1) O C1 0.0262(5) 0.0416(6) 0.0206(4) 0.0003(3) 0.0049(3) 0.0001(1) C C2 0.0259(5) 0.0528(8) 0.0223(5) -0.0010(4) 0.0050(4) -0.0002(1) C C3 0.0275(5) 0.065(1) 0.0247(8) -0.0049(6) 0.0066(5) -0.0009(2) C C4 0.0301(6) 0.062(1) 0.0248(8) -0.0063(6) 0.0084(7) -0.0012(2) C C5 0.0301(7) 0.048(1) 0.0224(5) -0.0030(4) 0.0075(6) -0.0006(1) C C6 0.0279(5) 0.0400(7) 0.0206(4) -0.0004(2) 0.0057(4) -0.0001(1) C C7 0.0255(6) 0.0557(9) 0.0223(5) 0.0016(5) 0.0038(4) 0.0003(1) C C8 0.041(2) 0.119(4) 0.028(2) -0.032(2) 0.013(1) -0.005(2) C C9 0.056(5) 0.156(7) 0.124(9) -0.037(5) 0.053(6) -0.065(5) C C10 0.058(5) 0.123(8) 0.056(3) -0.046(6) 0.028(3) -0.018(4) C C11 0.066(4) 0.266(9) 0.050(2) -0.070(4) 0.001(2) 0.059(4) C C8' 0.041(2) 0.116(4) 0.029(2) -0.031(2) 0.013(1) -0.003(2) C C9' 0.049(3) 0.146(8) 0.108(9) -0.028(4) 0.042(5) -0.046(5) C C10' 0.067(6) 0.115(6) 0.082(4) -0.047(6) 0.036(4) -0.017(5) C C11' 0.065(4) 0.273(9) 0.043(2) -0.075(4) 0.002(2) 0.048(4) C C12 0.0264(5) 0.0386(6) 0.0196(4) -0.0008(2) 0.0033(4) -0.0001(1) C C13 0.0277(5) 0.0355(6) 0.0193(5) 0.0004(1) 0.0037(4) 0.0001(1) C C14 0.0323(5) 0.0366(6) 0.0195(5) 0.0029(3) 0.0042(4) 0.0005(1) C C15 0.0359(6) 0.0426(8) 0.0202(4) 0.0083(6) 0.0043(5) 0.0015(3) C C16 0.0305(5) 0.0492(9) 0.0211(4) 0.0081(5) 0.0035(4) 0.0015(3) C C17 0.0260(5) 0.0465(7) 0.0207(4) 0.0016(3) 0.0031(4) 0.0003(1) C C18 0.0288(6) 0.0350(6) 0.0196(4) 0.0003(1) 0.0049(3) 0.0001(1) C C19 0.060(2) 0.046(2) 0.037(2) 0.017(2) 0.011(2) 0.013(1) C C20 0.094(4) 0.045(2) 0.104(4) 0.009(2) -0.027(4) 0.006(2) C C21 0.056(2) 0.062(3) 0.151(6) 0.026(2) -0.005(3) 0.023(3) C C22 0.286(9) 0.072(3) 0.095(3) 0.091(4) 0.125(5) 0.051(3) C O1Ac 0.128(9) 0.110(3) 0.055(4) 0.083(3) -0.027(6) -0.041(2) O C1Ac 0.281(9) 0.112(3) 0.100(6) 0.130(4) -0.092(8) -0.063(3) C C2Ac 0.382(9) 0.048(3) 0.116(9) 0.0000 -0.149(9) 0.0000 C C3Ac 0.431(9) 0.295(9) 0.184(9) 0.309(9) -0.113(9) -0.149(7) C O1Me1 0.088(4) 0.088(4) 0.141(5) -0.005(3) 0.047(4) 0.018(4) O C1Me1 0.127(8) 0.110(8) 0.159(9) -0.005(7) 0.048(8) -0.016(8) C O1Me2 0.216(9) 0.077(5) 0.227(9) -0.054(6) -0.081(8) -0.043(6) O C1Me2 0.479(9) 0.088(9) 0.189(9) -0.033(9) -0.216(9) -0.009(9) C O1Me3 0.147(9) 0.083(6) 0.290(9) -0.006(6) -0.044(9) 0.053(9) O C1Me3 0.169(9) 0.115(9) 0.142(9) -0.026(9) 0.001(9) 0.012(9) C O1Me3' 0.147(9) 0.083(6) 0.290(9) -0.006(6) -0.044(9) 0.053(9) O C1Me3' 0.169(9) 0.115(9) 0.142(9) -0.026(9) 0.001(9) 0.012(9) C # MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cs1 O1 3.137(3) 1_555 1_555 no Cs1 O1 3.137(3) 1_555 4_555 no Cs1 O1Me1 3.014(5) 1_555 1_555 no Cs1 O1Me1 3.014(5) 1_555 4_555 no Ti1 O1 1.823(3) 1_555 1_555 no Ti1 O1 1.823(3) 1_555 4_555 no Ti1 O2 1.989(2) 1_555 1_555 no Ti1 O2 1.989(2) 1_555 4_555 no Ti1 O1Ac 1.973(4) 1_555 1_555 no Ti1 O1Ac 1.973(4) 1_555 4_555 no O1 C1 1.311(4) 1_555 1_555 no O2 C12 1.371(4) 1_555 1_555 no C1 C2 1.407(2) 1_555 1_555 no C1 C6 1.407(2) 1_555 1_555 no C2 C3 1.393(3) 1_555 1_555 no C2 C7 1.539(4) 1_555 1_555 no C3 C4 1.397(2) 1_555 1_555 no C4 C5 1.397(2) 1_555 1_555 no C4 C8 1.527(4) 1_555 1_555 no C4 C8' 1.527(4) 1_555 1_555 no C5 C6 1.393(3) 1_555 1_555 no C6 C18 1.517(4) 1_555 1_555 no C7 C17 1.520(4) 1_555 4_555 no C8 C9 1.528(3) 1_555 1_555 no C8 C10 1.528(3) 1_555 1_555 no C8 C11 1.528(3) 1_555 1_555 no C8' C9' 1.528(3) 1_555 1_555 no C8' C10' 1.528(3) 1_555 1_555 no C8' C11' 1.528(3) 1_555 1_555 no C12 C13 1.407(2) 1_555 1_555 no C12 C17 1.407(2) 1_555 1_555 no C13 C14 1.393(3) 1_555 1_555 no C13 C18 1.513(4) 1_555 1_555 no C14 C15 1.397(2) 1_555 1_555 no C15 C16 1.397(2) 1_555 1_555 no C15 C19 1.549(5) 1_555 1_555 no C16 C17 1.393(3) 1_555 1_555 no C17 C7 1.520(4) 1_555 4_555 no C19 C20 1.528(3) 1_555 1_555 no C19 C21 1.528(3) 1_555 1_555 no C19 C22 1.528(3) 1_555 1_555 no O1Ac C1Ac 1.180(10) 1_555 1_555 no C1Ac C2Ac 1.500(15) 1_555 1_555 no C1Ac C3Ac 1.495(4) 1_555 1_555 no C2Ac C1Ac 1.500(15) 1_555 4_555 no O1Me1 C1Me1 1.418(3) 1_555 1_555 no O1Me2 C1Me2 1.420(4) 1_555 1_555 no O1Me3 C1Me3 1.413(6) 1_555 1_555 no O1Me3' C1Me3' 1.412(12) 1_555 1_555 no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Cs1 O1 51.12(9) 1_555 1_555 4_555 no O1 Cs1 O1Me1 111.0(1) 1_555 1_555 1_555 no O1 Cs1 O1Me1 162.1(1) 1_555 1_555 4_555 no O1 Cs1 O1Me1 162.1(1) 4_555 1_555 1_555 no O1 Cs1 O1Me1 111.0(1) 4_555 1_555 4_555 no O1Me1 Cs1 O1Me1 86.8(2) 1_555 1_555 4_555 no O1 Ti1 O1 95.9(2) 1_555 1_555 4_555 no O1 Ti1 O2 88.3(1) 1_555 1_555 1_555 no O1 Ti1 O2 87.2(1) 1_555 1_555 4_555 no O1 Ti1 O1Ac 89.7(2) 1_555 1_555 1_555 no O1 Ti1 O1Ac 174.4(2) 1_555 1_555 4_555 no O1 Ti1 O2 87.2(1) 4_555 1_555 1_555 no O1 Ti1 O2 88.3(1) 4_555 1_555 4_555 no O1 Ti1 O1Ac 174.4(2) 4_555 1_555 1_555 no O1 Ti1 O1Ac 89.7(2) 4_555 1_555 4_555 no O2 Ti1 O2 173.2(2) 1_555 1_555 4_555 no O2 Ti1 O1Ac 93.6(1) 1_555 1_555 1_555 no O2 Ti1 O1Ac 91.4(1) 1_555 1_555 4_555 no O2 Ti1 O1Ac 91.4(1) 4_555 1_555 1_555 no O2 Ti1 O1Ac 93.6(1) 4_555 1_555 4_555 no O1Ac Ti1 O1Ac 84.7(4) 1_555 1_555 4_555 no Cs1 O1 Ti1 106.5(1) 1_555 1_555 1_555 no Cs1 O1 C1 99.0(2) 1_555 1_555 1_555 no Ti1 O1 C1 154.5(2) 1_555 1_555 1_555 no Ti1 O2 C12 115.9(2) 1_555 1_555 1_555 no O1 C1 C2 120.4(2) 1_555 1_555 1_555 no O1 C1 C6 118.8(2) 1_555 1_555 1_555 no C2 C1 C6 120.5(2) 1_555 1_555 1_555 no C1 C2 C3 118.5(2) 1_555 1_555 1_555 no C1 C2 C7 117.1(3) 1_555 1_555 1_555 no C3 C2 C7 123.9(2) 1_555 1_555 1_555 no C2 C3 C4 122.7(2) 1_555 1_555 1_555 no C3 C4 C5 117.1(2) 1_555 1_555 1_555 no C3 C4 C8 120.9(4) 1_555 1_555 1_555 no C3 C4 C8' 119.4(4) 1_555 1_555 1_555 no C5 C4 C8 121.8(4) 1_555 1_555 1_555 no C5 C4 C8' 123.5(4) 1_555 1_555 1_555 no C4 C5 C6 122.7(2) 1_555 1_555 1_555 no C1 C6 C5 118.5(2) 1_555 1_555 1_555 no C1 C6 C18 116.6(2) 1_555 1_555 1_555 no C5 C6 C18 124.4(2) 1_555 1_555 1_555 no C2 C7 C17 116.0(3) 1_555 1_555 4_555 no C4 C8 C9 110.2(5) 1_555 1_555 1_555 no C4 C8 C10 110.4(3) 1_555 1_555 1_555 no C4 C8 C11 110.5(3) 1_555 1_555 1_555 no C9 C8 C10 108.6(2) 1_555 1_555 1_555 no C9 C8 C11 108.6(2) 1_555 1_555 1_555 no C10 C8 C11 108.6(2) 1_555 1_555 1_555 no C4 C8' C9' 110.2(5) 1_555 1_555 1_555 no C4 C8' C10' 110.4(3) 1_555 1_555 1_555 no C4 C8' C11' 110.5(4) 1_555 1_555 1_555 no C9' C8' C10' 108.6(2) 1_555 1_555 1_555 no C9' C8' C11' 108.6(2) 1_555 1_555 1_555 no C10' C8' C11' 108.6(2) 1_555 1_555 1_555 no O2 C12 C13 119.2(2) 1_555 1_555 1_555 no O2 C12 C17 120.2(2) 1_555 1_555 1_555 no C13 C12 C17 120.5(2) 1_555 1_555 1_555 no C12 C13 C14 118.5(2) 1_555 1_555 1_555 no C12 C13 C18 121.9(2) 1_555 1_555 1_555 no C14 C13 C18 119.6(2) 1_555 1_555 1_555 no C13 C14 C15 122.7(2) 1_555 1_555 1_555 no C14 C15 C16 117.1(2) 1_555 1_555 1_555 no C14 C15 C19 120.8(2) 1_555 1_555 1_555 no C16 C15 C19 122.1(2) 1_555 1_555 1_555 no C15 C16 C17 122.7(2) 1_555 1_555 1_555 no C7 C17 C12 122.0(3) 4_555 1_555 1_555 no C7 C17 C16 119.5(3) 4_555 1_555 1_555 no C12 C17 C16 118.5(2) 1_555 1_555 1_555 no C6 C18 C13 114.7(3) 1_555 1_555 1_555 no C15 C19 C20 108.8(3) 1_555 1_555 1_555 no C15 C19 C21 111.3(3) 1_555 1_555 1_555 no C15 C19 C22 111.1(3) 1_555 1_555 1_555 no C20 C19 C21 108.6(2) 1_555 1_555 1_555 no C20 C19 C22 108.6(2) 1_555 1_555 1_555 no C21 C19 C22 108.6(2) 1_555 1_555 1_555 no Ti1 O1Ac C1Ac 138.9(9) 1_555 1_555 1_555 no O1Ac C1Ac C2Ac 113.8(10) 1_555 1_555 1_555 no O1Ac C1Ac C3Ac 121.0(10) 1_555 1_555 1_555 no C2Ac C1Ac C3Ac 125.2(7) 1_555 1_555 1_555 no C1Ac C2Ac C1Ac 129.6(9) 1_555 1_555 4_555 no Cs1 O1Me1 C1Me1 107.1(6) 1_555 1_555 1_555 no data_AJP5 _database_code_CSD 218775 _audit_creation_method 'RAELSPUB and manual entry' _publ_section_figure_captions ? _publ_section_exptl_prep ? _publ_section_exptl_refinement ? _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR92 (Altomare et al, 1994)' _computing_structure_refinement 'RAELS, (Rae, 1989)' _computing_molecular_graphics 'ORTEP-II, (Johnson, 1976)' _computing_publication_material 'Local programs' # CHEMICAL DATA _chemical_name_systematic ? _chemical_formula_moiety 'C44 H53 K O5 Ti,11(C H4 O)' _chemical_formula_sum 'C55 H97 K O16 Ti' _chemical_formula_iupac ? _chemical_formula_weight 1101.4 # CRYSTAL DATA _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M 'I 4 2 2' loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x,-y,z 3 -x,y,-z 4 x,-y,-z 5 y,x,-z 6 -y,-x,-z 7 -y,x,z 8 y,-x,z 9 1/2+x,1/2+y,1/2+z 10 1/2-x,1/2-y,1/2+z 11 1/2-x,1/2+y,1/2-z 12 1/2+x,1/2-y,1/2-z 13 1/2+y,1/2+x,1/2-z 14 1/2-y,1/2-x,1/2-z 15 1/2-y,1/2+x,1/2+z 16 1/2+y,1/2-x,1/2+z _cell_length_a 15.558(3) _cell_length_b 15.558(3) _cell_length_c 26.922(8) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 6517(4) _cell_formula_units_Z 4 _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _cell_measurement_temperature 150 _exptl_crystal_description irregular _exptl_crystal_colour 'pale yellow' _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_size_rad 0.1 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist ? ? ? ? _exptl_crystal_density_diffrn 1.12 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2384.0 _exptl_absorpt_coefficient_mu 0.248 _exptl_absorpt_correction_type none _exptl_absorpt_process_details ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_ambient_temperature 150(2) _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_reflns_number 2208 _diffrn_reflns_av_R_equivalents 0.015 _diffrn_reflns_theta_max 22.6 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 29 _diffrn_standards_number ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? # REFINEMENT DATA _refine_special_details ; The data quality was poor, with a restricted theta range. The structure consists of layers of calixarene-Ti moieties separated by layers with K ions and poorly defined and disordered methanol molecules. The phenyl was modelled as a planar group with refineable mm2 symmetry, and the t-butyl as a group with trigonal symmetry. The t-butyl was refined with a TLX rigid-body thermal parameter, and other atoms with single atom thermal parameters. ; _reflns_number_total 2163 _reflns_number_gt 1753 _reflns_threshold_expression I>2\s(I) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.125 _refine_ls_wR_factor_ref 0.176 _refine_ls_hydrogen_treatment noref _refine_ls_number_reflns 1753 _refine_ls_number_parameters 167 _refine_ls_goodness_of_fit_ref 2.63 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[\s^2^(F) + 0.0004F^2^]' _refine_ls_shift/su_max 0.004 _refine_diff_density_max 1.18 _refine_diff_density_min -0.76 _refine_ls_extinction_method none _refine_ls_extinction_coef ? _atom_type_scat_source 'International Tables for X-ray Crystallography, Vol. IV' # ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_type_symbol _atom_site_occupancy Ti1 0.50000 0.50000 0.12663(8) 0.062(1) Uani Ti 1.0 O1 0.6233(3) 0.4992(5) 0.1421(2) 0.063(1) Uani O 1.0 O2 0.5000 0.5000 0.0651(3) 0.097(4) Uani O 1.0 C1 0.6679(3) 0.5020(6) 0.1853(2) 0.057(2) Uani C 1.0 C2 0.6905(5) 0.5793(5) 0.2076(2) 0.060(3) Uani C 1.0 C3 0.7361(4) 0.5786(6) 0.2521(3) 0.075(4) Uani C 1.0 C4 0.7596(3) 0.5018(6) 0.2748(2) 0.065(2) Uani C 1.0 C5 0.7364(4) 0.4251(4) 0.2519(3) 0.059(3) Uani C 1.0 C6 0.6908(4) 0.4246(5) 0.2073(3) 0.058(3) Uani C 1.0 C7 0.6623(7) 0.6620(7) 0.1857(3) 0.065(2) Uani C 1.0 C8 0.8091(5) 0.4937(7) 0.3242(3) 0.087(4) Uani C 1.0 C9 0.8857(9) 0.4395(12) 0.3184(7) 0.230(6) Uani C 1.0 C10 0.7542(10) 0.4552(12) 0.3625(5) 0.242(9) Uani C 1.0 C11 0.8367(11) 0.5787(8) 0.3416(6) 0.224(6) Uani C 1.0 K1 0.6085(3) 0.6085(3) 0.0000 0.094(2) Uani K 0.5 O1Me1 0.4090(9) 0.5911(9) 0.0000 0.094(2) Uani O 0.5 C1Me1 0.3519(21) 0.6392(23) 0.0262(10) 0.094(2) Uani C 0.5 O1Me2 0.2088(4) 0.0050(9) 0.4407(2) 0.156(4) Uani O 1.0 C1Me2 0.2956(5) 0.0118(27) 0.4284(4) 0.308(4) Uani C 1.0 O1Me3 0.4316(12) 0.5117(36) 0.3194(9) 0.170(7) Uani O 0.25 C1Me3 0.5000 0.5000 0.2871(6) 0.099(5) Uani C 1.0 O1Me4 0.7244(25) 0.7244(25) 0.0000 0.608(9) Uani O 1.0 C1Me4 0.7314(39) 0.7691(35) -0.0455(16) 0.321(9) Uani C 0.5 O1Me5 0.3909(14) 0.0000 0.0000 0.298(9) Uani O 1.0 C1Me5 0.3177(17) 0.0516(18) 0.0012(14) 0.237(9) Uani C 0.5 O1Me6 -0.0469(12) 0.1657(25) 0.0012(29) 0.343(9) Uani O 0.125 C1Me6 0.0469(12) 0.1657(25) -0.0012(29) 0.343(9) Uani C 0.125 O1Me7 0.5257(39) 0.5371(25) 0.4213(9) 0.265(9) Uani O 0.125 C1Me7 0.4743(39) 0.4629(25) 0.4213(9) 0.265(9) Uani C 0.125 HC3 0.7522 0.6343 0.2681 0.075 Uani H 1.0 HC5 0.7528 0.3693 0.2677 0.059 Uani H 1.0 H1C7 0.6564 0.6550 0.1490 0.065 Uani H 1.0 H2C7 0.7064 0.7069 0.1931 0.065 Uani H 1.0 H1C9 0.9166 0.4354 0.3509 0.249 Uani H 1.0 H2C9 0.8681 0.3808 0.3073 0.384 Uani H 1.0 H3C9 0.9247 0.4656 0.2930 0.383 Uani H 1.0 H1C10 0.7872 0.4504 0.3943 0.271 Uani H 1.0 H2C10 0.7025 0.4922 0.3679 0.398 Uani H 1.0 H3C10 0.7355 0.3967 0.3516 0.390 Uani H 1.0 H1C11 0.8687 0.5725 0.3736 0.248 Uani H 1.0 H2C11 0.8751 0.6056 0.3162 0.368 Uani H 1.0 H3C11 0.7852 0.6160 0.3469 0.377 Uani H 1.0 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 _atom_site_aniso_type_symbol Ti1 0.075(1) 0.075(1) 0.035(1) 0.0000 0.0000 0.0000 Ti O1 0.071(3) 0.073(3) 0.045(3) 0.009(4) 0.009(2) -0.012(5) O O2 0.128(6) 0.128(6) 0.035(5) 0.0000 0.0000 0.0000 O C1 0.064(4) 0.071(5) 0.036(3) 0.016(7) 0.011(3) 0.019(7) C C2 0.102(8) 0.057(7) 0.021(4) -0.015(6) 0.028(5) 0.000(4) C C3 0.037(5) 0.120(9) 0.069(8) -0.021(5) -0.008(6) 0.003(8) C C4 0.061(4) 0.068(5) 0.066(5) 0.029(6) -0.010(3) -0.019(8) C C5 0.089(8) 0.031(5) 0.057(7) -0.009(4) 0.013(6) -0.001(5) C C6 0.022(4) 0.061(7) 0.091(8) -0.006(4) 0.004(5) -0.012(5) C C7 0.066(8) 0.071(8) 0.057(4) -0.009(3) 0.007(6) 0.016(6) C C8 0.115(6) 0.086(5) 0.061(4) -0.024(6) -0.024(3) 0.014(5) C C9 0.225(7) 0.327(9) 0.140(8) 0.144(9) -0.096(5) -0.056(8) C C10 0.203(9) 0.436(9) 0.086(4) -0.148(8) -0.048(4) 0.120(7) C C11 0.404(9) 0.096(5) 0.173(7) -0.054(6) -0.199(8) 0.022(6) C K1 0.102(3) 0.102(3) 0.077(3) -0.005(3) -0.021(3) 0.021(3) K O1Me1 0.102(3) 0.102(3) 0.077(3) 0.005(3) -0.021(3) -0.021(3) O C1Me1 0.102(3) 0.102(3) 0.077(3) 0.005(3) -0.021(3) -0.021(3) C O1Me2 0.120(6) 0.295(9) 0.053(3) 0.033(9) -0.023(4) -0.028(9) O C1Me2 0.078(7) 0.779(9) 0.068(6) -0.015(9) -0.019(5) 0.083(9) C O1Me3 0.062(9) 0.355(9) 0.092(9) -0.089(9) 0.018(9) -0.131(9) O C1Me3 0.114(8) 0.114(8) 0.069(9) 0.0000 0.0000 0.0000 C O1Me4 0.608(9) 0.608(9) 0.608(9) 0.0000 0.0000 0.0000 O C1Me4 0.321(9) 0.321(9) 0.321(9) 0.0000 0.0000 0.0000 C O1Me5 0.455(9) 0.116(9) 0.324(9) 0.0000 0.0000 0.098(9) O C1Me5 0.427(9) 0.147(9) 0.138(9) 0.017(9) -0.118(9) -0.030(9) C O1Me6 0.255(9) 0.111(9) 0.661(9) 0.052(9) -0.259(9) -0.190(9) O C1Me6 0.255(9) 0.111(9) 0.661(9) -0.052(9) -0.259(9) 0.190(9) C O1Me7 0.611(9) 0.113(9) 0.070(9) -0.026(9) 0.014(9) -0.048(9) O C1Me7 0.611(9) 0.113(9) 0.070(9) -0.026(9) -0.014(9) 0.048(9) C # MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O1 1.963(4) 1_555 1_555 no Ti1 O1 1.963(4) 1_555 2_665 no Ti1 O1 1.963(4) 1_555 7_655 no Ti1 O1 1.963(4) 1_555 8_565 no Ti1 O2 1.657(9) 1_555 1_555 no O1 C1 1.355(8) 1_555 1_555 no O2 K1 2.962(8) 1_555 1_555 no O2 K1 2.962(8) 1_555 2_665 no C1 C2 1.390(6) 1_555 1_555 no C1 C6 1.390(6) 1_555 1_555 no C2 C3 1.393(7) 1_555 1_555 no C2 C7 1.481(14) 1_555 1_555 no C3 C4 1.390(6) 1_555 1_555 no C4 C5 1.390(6) 1_555 1_555 no C4 C8 1.542(10) 1_555 1_555 no C5 C6 1.393(7) 1_555 1_555 no C6 C7 1.537(14) 1_555 8_565 no C7 C6 1.537(14) 1_555 7_655 no C8 C9 1.468(8) 1_555 1_555 no C8 C10 1.468(8) 1_555 1_555 no C8 C11 1.468(8) 1_555 1_555 no K1 O1Me1 3.117(11) 1_555 1_555 no K1 O1Me1 3.117(11) 1_555 2_665 no K1 O1Me2 2.752(9) 1_555 9_554 no K1 O1Me2 2.846(10) 1_555 12_555 no K1 O1Me2 2.752(9) 1_555 13_555 no K1 O1Me2 2.846(10) 1_555 15_554 no K1 O1Me4 2.548(55) 1_555 1_555 no O1Me1 C1Me1 1.358(12) 1_555 1_555 no O1Me2 C1Me2 1.395(5) 1_555 1_555 no O1Me3 C1Me3 1.386(10) 1_555 1_555 no O1Me4 C1Me4 1.414(24) 1_555 1_555 no O1Me5 C1Me5 1.393(15) 1_555 1_555 no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Ti1 O1 155.6(3) 1_555 1_555 2_665 no O1 Ti1 O1 87.43(5) 1_555 1_555 7_655 no O1 Ti1 O1 87.43(5) 1_555 1_555 8_565 no O1 Ti1 O2 102.2(1) 1_555 1_555 1_555 no O1 Ti1 O1 87.43(5) 2_665 1_555 7_655 no O1 Ti1 O1 87.43(5) 2_665 1_555 8_565 no O1 Ti1 O2 102.2(1) 2_665 1_555 1_555 no O1 Ti1 O1 155.6(3) 7_655 1_555 8_565 no O1 Ti1 O2 102.2(1) 7_655 1_555 1_555 no O1 Ti1 O2 102.2(1) 8_565 1_555 1_555 no Ti1 O1 C1 133.0(3) 1_555 1_555 1_555 no Ti1 O2 K1 126.3(2) 1_555 1_555 1_555 no Ti1 O2 K1 126.3(2) 1_555 1_555 2_665 no K1 O2 K1 107.5(3) 1_555 1_555 2_665 no O1 C1 C2 121.9(7) 1_555 1_555 1_555 no O1 C1 C6 118.1(8) 1_555 1_555 1_555 no C2 C1 C6 120.0(6) 1_555 1_555 1_555 no C1 C2 C3 119.6(4) 1_555 1_555 1_555 no C1 C2 C7 120.4(7) 1_555 1_555 1_555 no C3 C2 C7 120.0(7) 1_555 1_555 1_555 no C2 C3 C4 121.2(5) 1_555 1_555 1_555 no C3 C4 C5 118.3(7) 1_555 1_555 1_555 no C3 C4 C8 125.4(7) 1_555 1_555 1_555 no C5 C4 C8 116.2(8) 1_555 1_555 1_555 no C4 C5 C6 121.2(5) 1_555 1_555 1_555 no C1 C6 C5 119.6(4) 1_555 1_555 1_555 no C1 C6 C7 121.7(8) 1_555 1_555 8_565 no C5 C6 C7 118.6(7) 1_555 1_555 8_565 no C2 C7 C6 111.3(5) 1_555 1_555 7_655 no C4 C8 C9 111.1(9) 1_555 1_555 1_555 no C4 C8 C10 110.5(8) 1_555 1_555 1_555 no C4 C8 C11 110.4(9) 1_555 1_555 1_555 no C9 C8 C10 108.3(5) 1_555 1_555 1_555 no C9 C8 C11 108.3(5) 1_555 1_555 1_555 no C10 C8 C11 108.3(5) 1_555 1_555 1_555 no O2 K1 O2 72.5(3) 1_555 1_555 3_655 no O2 K1 O1Me1 51.8(3) 1_555 1_555 1_555 no O2 K1 O1Me1 51.8(3) 1_555 1_555 2_665 no O2 K1 O1Me1 36.3(2) 1_555 1_555 3_655 no O2 K1 O1Me2 109.4(3) 1_555 1_555 9_554 no O2 K1 O1Me2 68.1(2) 1_555 1_555 12_555 no O2 K1 O1Me2 69.3(2) 1_555 1_555 13_555 no O2 K1 O1Me2 106.9(3) 1_555 1_555 15_554 no O2 K1 O1Me4 143.7(2) 1_555 1_555 1_555 no data_nati _database_code_CSD 218776 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C64 H70 Na2 O4 Ti2' _chemical_formula_weight 1236.98 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' Na Na 0.0362 0.0249 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 '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/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 12.1807(2) _cell_length_b 14.9482(2) _cell_length_c 16.5026(3) _cell_angle_alpha 90.00 _cell_angle_beta 94.770(2) _cell_angle_gamma 90.00 _cell_volume 2994.38(8) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.31 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.372 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1296 _exptl_absorpt_coefficient_mu 0.351 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8990 _exptl_absorpt_correction_T_max 0.9930 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 15 degree phi range. ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 53795 _diffrn_reflns_av_R_equivalents 0.0758 _diffrn_reflns_av_sigmaI/netI 0.0356 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.48 _diffrn_reflns_theta_max 26.00 _reflns_number_total 5880 _reflns_number_gt 5025 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1996)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; ORTEP3 for Windows (Farrugia, 1997) XSeed (Barbour, 2001) ; _computing_publication_material 'WC (Thornton-Pett, 2000)' _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^)+(0.0652P)^2^+1.9392P] 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 SHELXL _refine_ls_extinction_coef 0.0039(8) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 5880 _refine_ls_number_parameters 399 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0521 _refine_ls_R_factor_gt 0.0406 _refine_ls_wR_factor_ref 0.1205 _refine_ls_wR_factor_gt 0.1117 _refine_ls_goodness_of_fit_ref 1.038 _refine_ls_restrained_S_all 1.038 _refine_ls_shift/su_max 0.224 _refine_ls_shift/su_mean 0.003 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 -0.16204(15) 0.18718(13) 0.11124(12) 0.0259(4) Uani 1 1 d . . . O1 O -0.13618(11) 0.11486(9) 0.06606(8) 0.0259(3) Uani 1 1 d . . . C2 C -0.17436(16) 0.17694(14) 0.19553(12) 0.0287(4) Uani 1 1 d . . . C3 C -0.20797(18) 0.25050(16) 0.23934(14) 0.0367(5) Uani 1 1 d . . . H3 H -0.2171 0.2437 0.2956 0.044 Uiso 1 1 calc R . . C4 C -0.2283(2) 0.33268(16) 0.20332(15) 0.0416(5) Uani 1 1 d . . . H4 H -0.2525 0.3815 0.2341 0.050 Uiso 1 1 calc R . . C5 C -0.21277(18) 0.34305(14) 0.12124(14) 0.0357(5) Uani 1 1 d . . . H5 H -0.2263 0.3997 0.0963 0.043 Uiso 1 1 calc R . . C6 C -0.17776(16) 0.27210(14) 0.07479(13) 0.0290(4) Uani 1 1 d . . . C7 C -0.16039(16) 0.28922(14) -0.01418(13) 0.0300(4) Uani 1 1 d . . . H7A H -0.1683 0.2317 -0.0438 0.036 Uiso 1 1 calc R . . H7B H -0.2197 0.3294 -0.0371 0.036 Uiso 1 1 calc R . . C8 C 0.04624(16) 0.28092(13) -0.01154(11) 0.0256(4) Uani 1 1 d . . . O2 O 0.03914(11) 0.20390(9) 0.02770(8) 0.0264(3) Uani 1 1 d . . . C9 C -0.05042(16) 0.33027(13) -0.03036(12) 0.0278(4) Uani 1 1 d . . . C10 C -0.03933(19) 0.41221(14) -0.06893(13) 0.0337(5) Uani 1 1 d . . . H10 H -0.1028 0.4482 -0.0813 0.040 Uiso 1 1 calc R . . C11 C 0.06209(19) 0.44229(15) -0.08958(14) 0.0376(5) Uani 1 1 d . . . H11 H 0.0678 0.4989 -0.1151 0.045 Uiso 1 1 calc R . . C12 C 0.15537(18) 0.39026(15) -0.07329(13) 0.0342(5) Uani 1 1 d . . . H12 H 0.2244 0.4112 -0.0885 0.041 Uiso 1 1 calc R . . C13 C 0.14928(17) 0.30748(14) -0.03483(12) 0.0284(4) Uani 1 1 d . . . C14 C 0.24578(16) 0.24322(14) -0.02206(12) 0.0305(4) Uani 1 1 d . . . H14A H 0.2261 0.1869 -0.0513 0.037 Uiso 1 1 calc R . . H14B H 0.3095 0.2694 -0.0470 0.037 Uiso 1 1 calc R . . C15 C 0.24954(15) 0.14062(13) 0.10316(12) 0.0261(4) Uani 1 1 d . . . O3 O 0.18884(11) 0.07798(9) 0.05956(8) 0.0262(3) Uani 1 1 d . . . C16 C 0.28106(16) 0.22078(14) 0.06593(12) 0.0282(4) Uani 1 1 d . . . C17 C 0.34805(17) 0.28166(15) 0.11076(13) 0.0336(5) Uani 1 1 d . . . H17 H 0.3705 0.3348 0.0853 0.040 Uiso 1 1 calc R . . C18 C 0.38276(18) 0.26634(16) 0.19184(14) 0.0370(5) Uani 1 1 d . . . H18 H 0.4293 0.3081 0.2214 0.044 Uiso 1 1 calc R . . C19 C 0.34856(17) 0.18919(15) 0.22902(13) 0.0329(5) Uani 1 1 d . . . H19 H 0.3710 0.1791 0.2848 0.039 Uiso 1 1 calc R . . C20 C 0.28202(16) 0.12607(14) 0.18664(12) 0.0274(4) Uani 1 1 d . . . C21 C 0.25005(16) 0.04196(14) 0.23069(12) 0.0294(4) Uani 1 1 d . . . H21A H 0.3150 0.0211 0.2656 0.035 Uiso 1 1 calc R . . H21B H 0.2316 -0.0052 0.1897 0.035 Uiso 1 1 calc R . . C22 C 0.05047(16) 0.07684(13) 0.24655(11) 0.0256(4) Uani 1 1 d . . . O4 O 0.04221(11) 0.09801(9) 0.16777(8) 0.0267(3) Uani 1 1 d . . . C23 C 0.15372(16) 0.05159(13) 0.28324(12) 0.0271(4) Uani 1 1 d . . . C24 C 0.16010(18) 0.02953(16) 0.36504(13) 0.0367(5) Uani 1 1 d . . . H24 H 0.2287 0.0114 0.3915 0.044 Uiso 1 1 calc R . . C25 C 0.0681(2) 0.03348(19) 0.40873(14) 0.0458(6) Uani 1 1 d . . . H25 H 0.0748 0.0213 0.4654 0.055 Uiso 1 1 calc R . . C26 C -0.03412(19) 0.05523(18) 0.36991(14) 0.0414(6) Uani 1 1 d . . . H26 H -0.0971 0.0562 0.4002 0.050 Uiso 1 1 calc R . . C27 C -0.04538(17) 0.07558(14) 0.28747(12) 0.0297(4) Uani 1 1 d . . . C28 C -0.15598(17) 0.08798(14) 0.23870(12) 0.0304(4) Uani 1 1 d . . . H28A H -0.1645 0.0398 0.1975 0.037 Uiso 1 1 calc R . . H28B H -0.2149 0.0799 0.2759 0.037 Uiso 1 1 calc R . . Ti1 Ti 0.02380(3) 0.08836(2) 0.05747(2) 0.02268(12) Uani 1 1 d . . . O5 O -0.00098(12) 0.04538(9) -0.05871(8) 0.0279(3) Uani 1 1 d . . . C30 C -0.0050(2) 0.10089(15) -0.12908(13) 0.0414(6) Uani 1 1 d . . . H30A H -0.0779 0.1286 -0.1377 0.062 Uiso 1 1 calc R . . H30B H 0.0089 0.0646 -0.1766 0.062 Uiso 1 1 calc R . . H30C H 0.0513 0.1477 -0.1214 0.062 Uiso 1 1 calc R . . Na1 Na -0.27621(6) 0.03249(5) 0.00403(5) 0.0314(2) Uani 1 1 d . . . O6 O -0.41028(16) -0.00411(14) 0.08901(12) 0.0499(5) Uani 1 1 d . . . H31 H -0.459(3) -0.036(3) 0.081(2) 0.078(12) Uiso 1 1 d . A 2 C32 C -0.4382(2) 0.0541(2) 0.1515(2) 0.0681(9) Uani 1 1 d . . . H32A H -0.3857 0.1039 0.1564 0.102 Uiso 1 1 calc R . . H32B H -0.4356 0.0214 0.2030 0.102 Uiso 1 1 calc R . . H32C H -0.5127 0.0776 0.1383 0.102 Uiso 1 1 calc R . . O7 O -0.40127(15) 0.12210(12) -0.07758(12) 0.0438(4) Uani 1 1 d . . . H33 H -0.384(3) 0.136(2) -0.118(2) 0.072(12) Uiso 1 1 d . B 2 C34 C -0.4438(2) 0.2016(2) -0.0426(2) 0.0660(9) Uani 1 1 d . . . H34A H -0.5160 0.1888 -0.0232 0.099 Uiso 1 1 calc R . . H34B H -0.4512 0.2489 -0.0838 0.099 Uiso 1 1 calc R . . H34C H -0.3931 0.2214 0.0031 0.099 Uiso 1 1 calc R . . O1S O 0.15149(16) 0.32272(13) 0.27665(12) 0.0802(7) Uani 1 1 d . . . H1SA H 0.2076 0.2929 0.2673 0.120 Uiso 0.75 1 calc PR C 1 H1SB H 0.1819 0.3453 0.3194 0.120 Uiso 0.25 1 calc PR C 2 C1S C 0.08265(16) 0.33158(13) 0.20468(12) 0.0374(7) Uani 0.75 1 d PR C 1 H1S1 H 0.1246 0.3570 0.1621 0.056 Uiso 0.75 1 calc PR C 1 H1S2 H 0.0210 0.3712 0.2142 0.056 Uiso 0.75 1 calc PR C 1 H1S3 H 0.0542 0.2727 0.1874 0.056 Uiso 0.75 1 calc PR C 1 C2S C 0.0363(8) 0.3717(8) 0.2534(7) 0.051(3) Uani 0.25 1 d P C 2 H2S1 H 0.0266 0.3811 0.1945 0.076 Uiso 0.25 1 calc PR C 2 H2S2 H 0.0356 0.4297 0.2812 0.076 Uiso 0.25 1 calc PR C 2 H2S3 H -0.0239 0.3345 0.2704 0.076 Uiso 0.25 1 calc PR C 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 C1 0.0194(9) 0.0288(10) 0.0296(10) -0.0011(8) 0.0025(7) -0.0015(7) O1 0.0244(7) 0.0272(7) 0.0259(7) -0.0006(5) 0.0017(5) -0.0025(5) C2 0.0212(9) 0.0355(11) 0.0301(10) 0.0004(8) 0.0058(8) -0.0011(8) C3 0.0336(11) 0.0441(12) 0.0337(11) -0.0028(9) 0.0099(9) 0.0029(9) C4 0.0417(13) 0.0384(12) 0.0465(13) -0.0066(10) 0.0141(10) 0.0059(10) C5 0.0323(11) 0.0308(11) 0.0449(12) -0.0001(9) 0.0083(9) 0.0028(9) C6 0.0218(9) 0.0316(10) 0.0338(11) 0.0017(8) 0.0030(8) -0.0014(8) C7 0.0264(10) 0.0306(10) 0.0327(11) 0.0055(8) 0.0011(8) 0.0009(8) C8 0.0294(10) 0.0241(9) 0.0234(9) -0.0010(7) 0.0029(8) -0.0029(8) O2 0.0249(7) 0.0243(7) 0.0303(7) 0.0000(5) 0.0049(6) -0.0007(5) C9 0.0297(10) 0.0295(10) 0.0245(9) -0.0003(8) 0.0033(8) -0.0035(8) C10 0.0360(11) 0.0319(11) 0.0329(11) 0.0055(9) 0.0016(9) 0.0012(9) C11 0.0414(12) 0.0333(11) 0.0385(12) 0.0097(9) 0.0049(10) -0.0047(9) C12 0.0336(11) 0.0375(11) 0.0320(11) 0.0056(9) 0.0069(9) -0.0084(9) C13 0.0286(10) 0.0326(10) 0.0243(10) -0.0014(8) 0.0034(8) -0.0031(8) C14 0.0255(10) 0.0377(11) 0.0293(10) 0.0006(9) 0.0081(8) -0.0019(8) C15 0.0202(9) 0.0314(10) 0.0273(10) -0.0042(8) 0.0055(7) 0.0019(7) O3 0.0256(7) 0.0283(7) 0.0249(7) -0.0042(5) 0.0029(5) 0.0011(5) C16 0.0228(9) 0.0354(11) 0.0271(10) -0.0018(8) 0.0062(8) 0.0003(8) C17 0.0299(11) 0.0355(11) 0.0360(11) -0.0016(9) 0.0065(9) -0.0053(9) C18 0.0341(11) 0.0418(12) 0.0348(11) -0.0082(9) 0.0014(9) -0.0096(9) C19 0.0283(10) 0.0435(12) 0.0267(10) -0.0040(9) 0.0020(8) -0.0014(9) C20 0.0212(9) 0.0332(10) 0.0283(10) -0.0012(8) 0.0048(8) 0.0033(8) C21 0.0264(10) 0.0346(11) 0.0272(10) 0.0007(8) 0.0022(8) 0.0033(8) C22 0.0292(10) 0.0261(9) 0.0216(9) -0.0011(7) 0.0025(8) -0.0020(8) O4 0.0244(7) 0.0330(7) 0.0230(7) -0.0015(5) 0.0034(5) 0.0014(5) C23 0.0270(10) 0.0281(10) 0.0262(10) -0.0009(8) 0.0028(8) -0.0018(8) C24 0.0316(11) 0.0475(13) 0.0303(11) 0.0090(9) -0.0012(9) -0.0015(9) C25 0.0361(12) 0.0722(17) 0.0292(11) 0.0166(11) 0.0035(9) 0.0002(11) C26 0.0314(11) 0.0636(16) 0.0303(11) 0.0120(11) 0.0095(9) 0.0012(10) C27 0.0280(10) 0.0332(10) 0.0281(10) 0.0027(8) 0.0043(8) -0.0003(8) C28 0.0251(10) 0.0382(11) 0.0287(10) 0.0045(8) 0.0062(8) -0.0007(8) Ti1 0.0237(2) 0.0230(2) 0.02133(19) -0.00136(13) 0.00222(13) -0.00080(13) O5 0.0391(8) 0.0242(7) 0.0201(7) 0.0027(5) 0.0004(6) -0.0016(6) C30 0.0710(17) 0.0296(11) 0.0233(10) 0.0048(8) 0.0013(10) -0.0034(11) Na1 0.0247(4) 0.0329(4) 0.0368(5) -0.0081(3) 0.0039(3) -0.0003(3) O6 0.0404(10) 0.0571(11) 0.0544(11) -0.0102(9) 0.0164(8) -0.0113(9) C32 0.0391(15) 0.092(2) 0.075(2) -0.0339(18) 0.0184(14) -0.0098(15) O7 0.0381(9) 0.0438(10) 0.0497(11) 0.0054(8) 0.0050(8) 0.0024(7) C34 0.0431(15) 0.0504(16) 0.104(3) -0.0121(16) 0.0028(16) 0.0074(12) O1S 0.0707(15) 0.0906(17) 0.0790(16) -0.0284(13) 0.0050(12) 0.0182(13) C1S 0.0423(17) 0.0338(15) 0.0355(16) -0.0136(13) -0.0016(13) -0.0015(13) C2S 0.037(5) 0.069(7) 0.045(6) -0.009(5) -0.007(4) -0.010(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 1.365(2) . ? C1 C6 1.411(3) . ? C1 C2 1.420(3) . ? O1 Ti1 2.0051(14) . ? O1 Na1 2.2766(15) . ? C2 C3 1.396(3) . ? C2 C28 1.516(3) . ? C3 C4 1.378(3) . ? C4 C5 1.392(3) . ? C5 C6 1.396(3) . ? C6 C7 1.522(3) . ? C7 C9 1.517(3) . ? C8 O2 1.327(2) . ? C8 C13 1.400(3) . ? C8 C9 1.402(3) . ? O2 Ti1 1.8096(13) . ? C9 C10 1.392(3) . ? C10 C11 1.384(3) . ? C11 C12 1.385(3) . ? C12 C13 1.395(3) . ? C13 C14 1.519(3) . ? C14 C16 1.517(3) . ? C15 O3 1.361(2) . ? C15 C16 1.414(3) . ? C15 C20 1.418(3) . ? O3 Ti1 2.0137(14) . ? O3 Na1 2.2685(15) 3 ? C16 C17 1.393(3) . ? C17 C18 1.388(3) . ? C18 C19 1.386(3) . ? C19 C20 1.394(3) . ? C20 C21 1.519(3) . ? C21 C23 1.523(3) . ? C22 O4 1.334(2) . ? C22 C27 1.397(3) . ? C22 C23 1.402(3) . ? O4 Ti1 1.8211(14) . ? C23 C24 1.385(3) . ? C24 C25 1.383(3) . ? C25 C26 1.391(3) . ? C26 C27 1.390(3) . ? C27 C28 1.522(3) . ? Ti1 O5 2.0187(14) 3 ? Ti1 O5 2.0209(13) . ? Ti1 Ti1 3.2757(6) 3 ? Ti1 Na1 3.7769(8) 3 ? Ti1 Na1 3.7807(8) . ? O5 C30 1.425(2) . ? O5 Ti1 2.0187(14) 3 ? Na1 O3 2.2685(15) 3 ? Na1 O6 2.305(2) . ? Na1 O7 2.3639(19) . ? Na1 Ti1 3.7769(8) 3 ? O6 C32 1.412(3) . ? O7 C34 1.436(3) . ? O1S C1S 1.4020 . ? O1S C2S 1.602(11) . ? 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 C6 120.60(17) . . ? O1 C1 C2 119.85(17) . . ? C6 C1 C2 119.54(18) . . ? C1 O1 Ti1 117.70(11) . . ? C1 O1 Na1 118.41(11) . . ? Ti1 O1 Na1 123.89(7) . . ? C3 C2 C1 118.82(19) . . ? C3 C2 C28 119.05(19) . . ? C1 C2 C28 122.10(18) . . ? C4 C3 C2 121.9(2) . . ? C3 C4 C5 119.0(2) . . ? C4 C5 C6 121.5(2) . . ? C5 C6 C1 119.10(19) . . ? C5 C6 C7 118.37(19) . . ? C1 C6 C7 122.52(18) . . ? C9 C7 C6 115.68(17) . . ? O2 C8 C13 118.43(18) . . ? O2 C8 C9 118.48(17) . . ? C13 C8 C9 123.04(18) . . ? C8 O2 Ti1 166.59(13) . . ? C10 C9 C8 116.91(19) . . ? C10 C9 C7 123.85(19) . . ? C8 C9 C7 119.05(17) . . ? C11 C10 C9 121.4(2) . . ? C10 C11 C12 120.3(2) . . ? C11 C12 C13 120.8(2) . . ? C12 C13 C8 117.33(19) . . ? C12 C13 C14 123.65(19) . . ? C8 C13 C14 118.91(18) . . ? C16 C14 C13 115.27(17) . . ? O3 C15 C16 120.56(17) . . ? O3 C15 C20 120.22(17) . . ? C16 C15 C20 119.22(18) . . ? C15 O3 Ti1 116.98(11) . . ? C15 O3 Na1 119.35(11) . 3 ? Ti1 O3 Na1 123.66(7) . 3 ? C17 C16 C15 119.40(18) . . ? C17 C16 C14 118.08(18) . . ? C15 C16 C14 122.52(18) . . ? C18 C17 C16 121.5(2) . . ? C19 C18 C17 119.0(2) . . ? C18 C19 C20 121.6(2) . . ? C19 C20 C15 119.16(19) . . ? C19 C20 C21 118.80(18) . . ? C15 C20 C21 122.00(18) . . ? C20 C21 C23 115.76(17) . . ? O4 C22 C27 118.44(17) . . ? O4 C22 C23 118.52(17) . . ? C27 C22 C23 122.93(18) . . ? C22 O4 Ti1 161.54(13) . . ? C24 C23 C22 117.43(19) . . ? C24 C23 C21 123.29(18) . . ? C22 C23 C21 119.05(17) . . ? C25 C24 C23 121.0(2) . . ? C24 C25 C26 120.2(2) . . ? C27 C26 C25 120.9(2) . . ? C26 C27 C22 117.25(19) . . ? C26 C27 C28 123.73(19) . . ? C22 C27 C28 118.77(18) . . ? C2 C28 C27 116.40(17) . . ? O2 Ti1 O4 100.88(6) . . ? O2 Ti1 O1 87.34(6) . . ? O4 Ti1 O1 87.32(6) . . ? O2 Ti1 O3 87.29(6) . . ? O4 Ti1 O3 87.09(6) . . ? O1 Ti1 O3 171.39(6) . . ? O2 Ti1 O5 164.87(6) . 3 ? O4 Ti1 O5 94.24(6) . 3 ? O1 Ti1 O5 93.41(6) . 3 ? O3 Ti1 O5 93.53(6) . 3 ? O2 Ti1 O5 93.24(6) . . ? O4 Ti1 O5 165.88(6) . . ? O1 Ti1 O5 93.47(6) . . ? O3 Ti1 O5 93.55(6) . . ? O5 Ti1 O5 71.64(6) 3 . ? O2 Ti1 Ti1 129.03(5) . 3 ? O4 Ti1 Ti1 130.08(5) . 3 ? O1 Ti1 Ti1 94.24(4) . 3 ? O3 Ti1 Ti1 94.36(4) . 3 ? O5 Ti1 Ti1 35.84(4) 3 3 ? O5 Ti1 Ti1 35.80(4) . 3 ? O2 Ti1 Na1 106.19(5) . 3 ? O4 Ti1 Na1 105.74(4) . 3 ? O1 Ti1 Na1 158.61(4) . 3 ? O3 Ti1 Na1 29.99(4) . 3 ? O5 Ti1 Na1 69.20(4) 3 3 ? O5 Ti1 Na1 69.74(4) . 3 ? Ti1 Ti1 Na1 64.374(16) 3 3 ? O2 Ti1 Na1 105.49(5) . . ? O4 Ti1 Na1 106.68(5) . . ? O1 Ti1 Na1 29.99(4) . . ? O3 Ti1 Na1 158.62(4) . . ? O5 Ti1 Na1 69.66(4) 3 . ? O5 Ti1 Na1 69.10(4) . . ? Ti1 Ti1 Na1 64.256(16) 3 . ? Na1 Ti1 Na1 128.629(13) 3 . ? C30 O5 Ti1 126.13(12) . 3 ? C30 O5 Ti1 125.48(12) . . ? Ti1 O5 Ti1 108.36(6) 3 . ? O3 Na1 O1 103.82(6) 3 . ? O3 Na1 O6 119.47(7) 3 . ? O1 Na1 O6 113.39(7) . . ? O3 Na1 O7 116.99(7) 3 . ? O1 Na1 O7 111.89(6) . . ? O6 Na1 O7 91.46(8) . . ? O3 Na1 Ti1 26.34(4) 3 3 ? O1 Na1 Ti1 77.49(4) . 3 ? O6 Na1 Ti1 133.13(6) . 3 ? O7 Na1 Ti1 128.20(6) . 3 ? O3 Na1 Ti1 77.71(4) 3 . ? O1 Na1 Ti1 26.12(4) . . ? O6 Na1 Ti1 129.08(6) . . ? O7 Na1 Ti1 124.91(5) . . ? Ti1 Na1 Ti1 51.371(13) 3 . ? C32 O6 Na1 121.56(18) . . ? C34 O7 Na1 118.47(18) . . ? C1S O1S C2S 45.9(4) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.597 _refine_diff_density_min -0.631 _refine_diff_density_rms 0.149 data_AJP14 _database_code_CSD 219310 _audit_creation_method 'RAELSPUB and manual entry' _publ_section_abstract ? _publ_section_comment ? _publ_section_acknowledgements ? _publ_section_references ; Altomare, A., Burla, M.C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Polidori, G., J. Appl. Cryst., 1994, 27, 435. Ibers, J.A. and Hamilton, W.C., (Eds) International Tables for X-Ray Crystallography Vol. 4 , Kynoch Press, Birmingham, 1974. Johnson, C.K.,'ORTEP-II', Oak Ridge National Laboratory, Tennessee, U.S.A., 1976. Rae, A.D., RAELS. A comprehensive Constrained Least Squares Refinement Program, University of New South Wales, 1989. ; _publ_section_figure_captions ? _publ_section_exptl_prep ? _publ_section_exptl_refinement ? _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR92 (Altomare et al, 1994)' _computing_structure_refinement 'RAELS, (Rae, 1989)' _computing_molecular_graphics 'ORTEP-II, (Johnson, 1976)' _computing_publication_material 'Local programs' # CHEMICAL DATA _chemical_name_systematic ? _chemical_formula_moiety 'C33 H27 K O6 Ti,C H4 O, H2 O' _chemical_formula_sum 'C34 H33 K O8 Ti' _chemical_formula_iupac ? _chemical_formula_weight 656.6 # CRYSTAL DATA _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 1/2-x,-y,1/2+z 3 1/2+x,1/2-y,-z 4 -x,1/2+y,1/2-z _cell_length_a 12.190(2) _cell_length_b 15.107(3) _cell_length_c 16.424(3) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 3025(1) _cell_formula_units_Z 4 _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _cell_measurement_temperature 150 _exptl_crystal_description block _exptl_crystal_colour ? _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.48 _exptl_crystal_size_min 0.36 _exptl_crystal_size_rad ? _exptl_crystal_density_diffrn 1.44 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1368.0 _exptl_absorpt_coefficient_mu 0.467 _exptl_absorpt_correction_type none _exptl_absorpt_process_details ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_ambient_temperature 150(2) _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_reflns_number 38999 _diffrn_reflns_av_R_equivalents 0.048 _diffrn_reflns_theta_max 28.5 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_standards_number ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? # REFINEMENT DATA _refine_special_details ; Phenyl rings were modelled as four identical planar groups with refineable mm2 symmetry. Thermal motion was refined using a 15-parameter TLX rigid body thermal parameter for the calixarene and single atom anisotropic parameters for the other atoms. ; _reflns_number_total 7294 _reflns_number_gt 6641 _reflns_threshold_expression I>2\s(I) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.033 _refine_ls_wR_factor_ref 0.047 _refine_ls_hydrogen_treatment noref _refine_ls_number_reflns 6641 _refine_ls_number_parameters 177 _refine_ls_goodness_of_fit_ref 1.10 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[\s^2^(F) + 0.0004F^2^]' _refine_ls_shift/su_max 0.014 _refine_diff_density_max 0.52 _refine_diff_density_min -0.31 _refine_ls_extinction_method none _refine_ls_extinction_coef ? _atom_type_scat_source 'International Tables for X-ray Crystallography, Vol. IV' # ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_type_symbol _atom_site_occupancy Ti1 0.59490(3) 0.59277(2) 0.41869(2) 0.0167(1) Uani Ti 1.0 K1 0.63263(4) 0.44789(3) 0.23757(3) 0.0232(1) Uani K 1.0 O1 0.52072(10) 0.49671(9) 0.37189(7) 0.0175(2) Uani O 1.0 O2 0.68732(11) 0.50631(10) 0.47911(8) 0.0206(2) Uani O 1.0 O3 0.70432(10) 0.59321(10) 0.34289(7) 0.0176(2) Uani O 1.0 O4 0.50696(11) 0.66743(10) 0.34311(8) 0.0204(1) Uani O 1.0 C1 0.42800(9) 0.45353(9) 0.39080(8) 0.0192(1) Uani C 1.0 C2 0.32754(11) 0.48206(9) 0.35755(8) 0.0215(2) Uani C 1.0 C3 0.23166(9) 0.43999(10) 0.38313(8) 0.0253(3) Uani C 1.0 C4 0.23463(10) 0.37160(9) 0.43997(8) 0.0267(3) Uani C 1.0 C5 0.33489(11) 0.34443(9) 0.47207(8) 0.0250(3) Uani C 1.0 C6 0.43293(9) 0.38452(10) 0.44835(8) 0.0213(2) Uani C 1.0 C7 0.3204(2) 0.5628(2) 0.3016(1) 0.0229(2) Uani C 1.0 C8 0.71692(10) 0.43183(8) 0.43693(8) 0.0204(2) Uani C 1.0 C9 0.64245(10) 0.36060(9) 0.43450(7) 0.0211(2) Uani C 1.0 C10 0.66667(11) 0.28908(8) 0.38385(8) 0.0229(2) Uani C 1.0 C11 0.76175(10) 0.28774(9) 0.33683(8) 0.0243(2) Uani C 1.0 C12 0.83427(10) 0.35889(9) 0.34017(8) 0.0234(2) Uani C 1.0 C13 0.81354(10) 0.43188(8) 0.38991(8) 0.0213(2) Uani C 1.0 C14 0.5409(2) 0.3590(1) 0.4872(1) 0.0226(2) Uani C 1.0 C15 0.79353(9) 0.61467(9) 0.30251(7) 0.0188(1) Uani C 1.0 C16 0.89226(10) 0.56954(9) 0.31867(7) 0.0210(2) Uani C 1.0 C17 0.98369(9) 0.58950(10) 0.27097(8) 0.0243(2) Uani C 1.0 C18 0.97804(10) 0.65226(10) 0.20899(8) 0.0254(3) Uani C 1.0 C19 0.87956(11) 0.69611(9) 0.19406(7) 0.0237(2) Uani C 1.0 C20 0.78596(9) 0.67838(9) 0.24015(8) 0.0205(1) Uani C 1.0 C21 0.8958(2) 0.5073(2) 0.3920(1) 0.0226(2) Uani C 1.0 C22 0.49964(9) 0.63899(9) 0.26408(7) 0.0200(1) Uani C 1.0 C23 0.58223(10) 0.66202(9) 0.20798(8) 0.0206(1) Uani C 1.0 C24 0.57626(10) 0.62675(10) 0.12959(7) 0.0226(2) Uani C 1.0 C25 0.49120(10) 0.57029(10) 0.10704(7) 0.0239(3) Uani C 1.0 C26 0.41038(10) 0.54839(9) 0.16350(8) 0.0229(2) Uani C 1.0 C27 0.41288(9) 0.58202(10) 0.24260(7) 0.0210(2) Uani C 1.0 C28 0.6759(2) 0.7246(1) 0.2295(1) 0.0217(1) Uani C 1.0 O7 0.64092(12) 0.70499(10) 0.47107(8) 0.0255(3) Uani O 1.0 O8 0.48693(11) 0.59044(11) 0.51127(8) 0.0241(3) Uani O 1.0 C1Ac 0.6405(2) 0.8472(2) 0.5309(2) 0.0377(5) Uani C 1.0 C2Ac 0.5990(2) 0.7540(2) 0.5267(1) 0.0272(4) Uani C 1.0 C3Ac 0.5183(2) 0.7244(2) 0.5801(1) 0.0323(5) Uani C 1.0 C4Ac 0.4680(2) 0.6421(2) 0.5712(1) 0.0279(4) Uani C 1.0 C5Ac 0.3861(2) 0.6103(2) 0.6326(2) 0.0449(7) Uani C 1.0 O5 0.5524(1) 0.3349(1) 0.1280(1) 0.0328(4) Uani O 1.0 C1Me 0.6489(2) 0.3177(2) 0.0820(2) 0.0383(6) Uani C 1.0 O6 0.81400(14) 0.47406(13) 0.14681(9) 0.0331(4) Uani O 1.0 HC3 0.1595 0.4593 0.3602 0.029 Uani H 1.0 HC4 0.1651 0.3422 0.4576 0.031 Uani H 1.0 HC5 0.3366 0.2953 0.5129 0.028 Uani H 1.0 H1C7 0.3131 0.6159 0.3376 0.024 Uani H 1.0 H2C7 0.2522 0.5557 0.2684 0.026 Uani H 1.0 HC10 0.6148 0.2378 0.3813 0.025 Uani H 1.0 HC11 0.7779 0.2359 0.3009 0.027 Uani H 1.0 HC12 0.9024 0.3576 0.3063 0.026 Uani H 1.0 H1C14 0.5538 0.4006 0.5336 0.024 Uani H 1.0 H2C14 0.5327 0.2974 0.5086 0.026 Uani H 1.0 HC17 1.0546 0.5582 0.2815 0.028 Uani H 1.0 HC18 1.0444 0.6658 0.1754 0.029 Uani H 1.0 HC19 0.8759 0.7411 0.1495 0.026 Uani H 1.0 H1C21 0.8814 0.5432 0.4421 0.023 Uani H 1.0 H2C21 0.9710 0.4811 0.3952 0.026 Uani H 1.0 HC24 0.6341 0.6423 0.0889 0.024 Uani H 1.0 HC25 0.4882 0.5456 0.0506 0.027 Uani H 1.0 HC26 0.3495 0.5078 0.1471 0.025 Uani H 1.0 H1C28 0.6572 0.7554 0.2816 0.022 Uani H 1.0 H2C28 0.6832 0.7693 0.1849 0.025 Uani H 1.0 H1C1Ac 0.6978 0.8563 0.4882 0.038 Uani H 1.0 H2C1Ac 0.5784 0.8892 0.5215 0.038 Uani H 1.0 H3C1Ac 0.6731 0.8583 0.5859 0.038 Uani H 1.0 HC3Ac 0.4957 0.7634 0.6263 0.032 Uani H 1.0 H1C5Ac 0.3588 0.5504 0.6164 0.045 Uani H 1.0 H2C5Ac 0.4217 0.6067 0.6873 0.045 Uani H 1.0 H3C5Ac 0.3231 0.6526 0.6350 0.045 Uani H 1.0 H1O5 0.5302 0.2722 0.1388 0.033 Uani H 1.0 H1C1Me 0.6833 0.3750 0.0655 0.038 Uani H 1.0 H2C1Me 0.7019 0.2832 0.1160 0.038 Uani H 1.0 H3C1Me 0.6295 0.2828 0.0324 0.038 Uani H 1.0 H1O6 0.8244 0.4841 0.0871 0.033 Uani H 1.0 H2O6 0.8730 0.5142 0.1675 0.033 Uani H 1.0 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 _atom_site_aniso_type_symbol Ti1 0.0167(1) 0.0187(2) 0.0148(1) -0.0003(1) 0.0017(1) -0.0019(1) Ti K1 0.0242(2) 0.0255(2) 0.0199(2) 0.0022(2) 0.0012(2) -0.0030(2) K O1 0.0168(2) 0.0194(2) 0.0162(2) 0.0010(1) 0.0006(1) -0.0013(2) O O2 0.0211(2) 0.0247(3) 0.0160(2) -0.0008(2) -0.0018(1) -0.0001(2) O O3 0.0171(2) 0.0192(2) 0.0165(2) 0.0006(1) -0.0001(1) -0.0015(2) O O4 0.0193(2) 0.0192(2) 0.0227(3) 0.0030(2) 0.0013(2) -0.0018(2) O C1 0.0177(2) 0.0217(2) 0.0182(2) -0.0002(1) 0.0017(1) -0.0016(1) C C2 0.0166(2) 0.0250(2) 0.0229(2) 0.0004(1) 0.0016(2) -0.0023(2) C C3 0.0177(2) 0.0304(4) 0.0277(4) -0.0019(2) 0.0035(2) -0.0034(3) C C4 0.0219(2) 0.0314(4) 0.0267(4) -0.0054(2) 0.0059(2) -0.0030(3) C C5 0.0249(2) 0.0278(4) 0.0223(3) -0.0053(2) 0.0049(2) -0.0006(2) C C6 0.0219(2) 0.0235(3) 0.0187(2) -0.0023(2) 0.0024(2) -0.0002(2) C C7 0.0164(2) 0.0258(3) 0.0264(3) 0.0031(2) -0.0006(2) -0.0009(2) C C8 0.0199(2) 0.0228(2) 0.0185(2) 0.0014(2) -0.0025(1) 0.0017(2) C C9 0.0221(2) 0.0214(2) 0.0198(2) 0.0012(2) -0.0015(2) 0.0026(2) C C10 0.0238(2) 0.0196(3) 0.0252(3) 0.0028(2) -0.0007(2) 0.0024(2) C C11 0.0228(3) 0.0203(3) 0.0297(4) 0.0051(2) 0.0000(2) 0.0009(2) C C12 0.0193(2) 0.0227(3) 0.0280(3) 0.0051(2) -0.0009(2) 0.0007(2) C C13 0.0181(2) 0.0235(3) 0.0223(2) 0.0029(2) -0.0027(2) 0.0013(2) C C14 0.0252(2) 0.0241(3) 0.0185(2) -0.0017(2) 0.0002(2) 0.0027(2) C C15 0.0175(2) 0.0208(2) 0.0182(2) -0.0004(2) 0.0004(1) -0.0015(2) C C16 0.0165(2) 0.0248(2) 0.0217(2) -0.0002(2) -0.0002(1) -0.0018(2) C C17 0.0172(2) 0.0293(4) 0.0265(3) -0.0017(2) 0.0020(2) -0.0028(3) C C18 0.0208(2) 0.0296(4) 0.0257(3) -0.0047(2) 0.0046(2) -0.0027(3) C C19 0.0235(2) 0.0253(3) 0.0222(3) -0.0045(2) 0.0036(2) -0.0006(2) C C20 0.0209(2) 0.0211(2) 0.0196(2) -0.0017(2) 0.0015(2) -0.0004(2) C C21 0.0172(2) 0.0272(3) 0.0234(2) 0.0013(2) -0.0032(2) 0.0001(2) C C22 0.0187(2) 0.0201(2) 0.0213(2) 0.0031(2) -0.0010(2) 0.0007(2) C C23 0.0213(2) 0.0206(2) 0.0199(2) 0.0016(1) -0.0013(2) 0.0021(2) C C24 0.0242(2) 0.0251(3) 0.0184(2) -0.0002(2) -0.0025(2) 0.0033(2) C C25 0.0243(3) 0.0289(4) 0.0185(2) -0.0008(2) -0.0045(2) 0.0029(2) C C26 0.0203(2) 0.0275(3) 0.0208(2) 0.0008(2) -0.0047(2) 0.0019(2) C C27 0.0177(2) 0.0233(2) 0.0221(2) 0.0029(2) -0.0024(2) 0.0009(2) C C28 0.0236(2) 0.0196(2) 0.0218(3) 0.0000(1) 0.0005(2) 0.0015(2) C O7 0.0278(7) 0.0248(8) 0.0238(7) -0.0034(6) -0.0014(6) -0.0070(6) O O8 0.0234(6) 0.0284(8) 0.0203(6) -0.0015(6) 0.0046(5) -0.0035(6) O C1Ac 0.045(1) 0.027(1) 0.042(1) -0.001(1) -0.007(1) -0.012(1) C C2Ac 0.029(1) 0.026(1) 0.026(1) 0.0034(9) -0.0089(8) -0.0060(8) C C3Ac 0.039(1) 0.033(1) 0.026(1) 0.006(1) 0.0033(9) -0.0104(9) C C4Ac 0.027(1) 0.036(1) 0.0202(9) 0.0098(9) 0.0011(8) -0.0021(9) C C5Ac 0.048(2) 0.054(2) 0.033(1) 0.003(1) 0.020(1) -0.003(1) C O5 0.0377(8) 0.0242(8) 0.0364(8) -0.0069(7) 0.0024(7) -0.0022(7) O C1Me 0.038(1) 0.042(2) 0.035(1) -0.016(1) 0.003(1) -0.003(1) C O6 0.0384(8) 0.042(1) 0.0185(7) -0.0094(7) 0.0039(6) -0.0059(6) O # MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 O1 1.875(1) 1_555 1_555 no Ti1 O2 1.990(1) 1_555 1_555 no Ti1 O3 1.825(1) 1_555 1_555 no Ti1 O4 1.991(1) 1_555 1_555 no Ti1 O7 1.982(2) 1_555 1_555 no Ti1 O8 2.011(1) 1_555 1_555 no K1 O1 2.697(1) 1_555 1_555 no K1 O3 2.928(1) 1_555 1_555 no K1 O5 2.667(2) 1_555 1_555 no K1 O6 2.696(2) 1_555 1_555 no O1 C1 1.341(2) 1_555 1_555 no O2 C8 1.370(2) 1_555 1_555 no O3 C15 1.314(2) 1_555 1_555 no O4 C22 1.370(2) 1_555 1_555 no C1 C2 1.408(1) 1_555 1_555 no C1 C6 1.408(1) 1_555 1_555 no C2 C3 1.395(1) 1_555 1_555 no C2 C7 1.529(2) 1_555 1_555 no C3 C4 1.393(1) 1_555 1_555 no C4 C5 1.393(1) 1_555 1_555 no C5 C6 1.395(1) 1_555 1_555 no C6 C14 1.513(2) 1_555 1_555 no C7 C27 1.515(2) 1_555 1_555 no C8 C9 1.408(1) 1_555 1_555 no C8 C13 1.408(1) 1_555 1_555 no C9 C10 1.395(1) 1_555 1_555 no C9 C14 1.510(2) 1_555 1_555 no C10 C11 1.393(1) 1_555 1_555 no C11 C12 1.393(1) 1_555 1_555 no C12 C13 1.395(1) 1_555 1_555 no C13 C21 1.518(2) 1_555 1_555 no C15 C16 1.408(1) 1_555 1_555 no C15 C20 1.408(1) 1_555 1_555 no C16 C17 1.395(1) 1_555 1_555 no C16 C21 1.529(2) 1_555 1_555 no C17 C18 1.393(1) 1_555 1_555 no C18 C19 1.393(1) 1_555 1_555 no C19 C20 1.395(1) 1_555 1_555 no C20 C28 1.523(2) 1_555 1_555 no C22 C23 1.408(1) 1_555 1_555 no C22 C27 1.408(1) 1_555 1_555 no C23 C24 1.395(1) 1_555 1_555 no C23 C28 1.524(2) 1_555 1_555 no C24 C25 1.393(1) 1_555 1_555 no C25 C26 1.393(1) 1_555 1_555 no C26 C27 1.395(1) 1_555 1_555 no O7 C2Ac 1.282(3) 1_555 1_555 no O8 C4Ac 1.278(3) 1_555 1_555 no C1Ac C2Ac 1.498(3) 1_555 1_555 no C2Ac C3Ac 1.391(3) 1_555 1_555 no C3Ac C4Ac 1.393(3) 1_555 1_555 no C4Ac C5Ac 1.497(3) 1_555 1_555 no O5 C1Me 1.422(3) 1_555 1_555 no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Ti1 O2 88.25(6) 1_555 1_555 1_555 no O1 Ti1 O3 94.34(6) 1_555 1_555 1_555 no O1 Ti1 O4 85.59(6) 1_555 1_555 1_555 no O1 Ti1 O7 167.57(6) 1_555 1_555 1_555 no O1 Ti1 O8 88.90(6) 1_555 1_555 1_555 no O2 Ti1 O3 85.91(6) 1_555 1_555 1_555 no O2 Ti1 O4 171.03(6) 1_555 1_555 1_555 no O2 Ti1 O7 100.65(6) 1_555 1_555 1_555 no O2 Ti1 O8 88.97(6) 1_555 1_555 1_555 no O3 Ti1 O4 88.05(6) 1_555 1_555 1_555 no O3 Ti1 O7 94.94(6) 1_555 1_555 1_555 no O3 Ti1 O8 173.86(6) 1_555 1_555 1_555 no O4 Ti1 O7 86.47(6) 1_555 1_555 1_555 no O4 Ti1 O8 97.41(6) 1_555 1_555 1_555 no O7 Ti1 O8 82.65(6) 1_555 1_555 1_555 no O1 K1 O3 57.50(4) 1_555 1_555 1_555 no O1 K1 O5 122.80(5) 1_555 1_555 1_555 no O1 K1 O6 145.81(5) 1_555 1_555 1_555 no O3 K1 O5 171.17(5) 1_555 1_555 1_555 no O3 K1 O6 88.39(4) 1_555 1_555 1_555 no O5 K1 O6 91.23(5) 1_555 1_555 1_555 no Ti1 O1 K1 107.65(6) 1_555 1_555 1_555 no Ti1 O1 C1 133.5(1) 1_555 1_555 1_555 no K1 O1 C1 118.9(1) 1_555 1_555 1_555 no Ti1 O2 C8 115.86(9) 1_555 1_555 1_555 no Ti1 O3 K1 100.50(5) 1_555 1_555 1_555 no Ti1 O3 C15 161.8(1) 1_555 1_555 1_555 no K1 O3 C15 97.69(9) 1_555 1_555 1_555 no Ti1 O4 C22 116.6(1) 1_555 1_555 1_555 no O1 C1 C2 119.6(1) 1_555 1_555 1_555 no O1 C1 C6 118.7(1) 1_555 1_555 1_555 no C2 C1 C6 121.59(9) 1_555 1_555 1_555 no C1 C2 C3 118.17(7) 1_555 1_555 1_555 no C1 C2 C7 121.8(1) 1_555 1_555 1_555 no C3 C2 C7 119.8(1) 1_555 1_555 1_555 no C2 C3 C4 121.19(7) 1_555 1_555 1_555 no C3 C4 C5 119.68(9) 1_555 1_555 1_555 no C4 C5 C6 121.19(7) 1_555 1_555 1_555 no C1 C6 C5 118.17(7) 1_555 1_555 1_555 no C1 C6 C14 120.6(1) 1_555 1_555 1_555 no C5 C6 C14 121.1(1) 1_555 1_555 1_555 no C2 C7 C27 119.7(2) 1_555 1_555 1_555 no O2 C8 C9 118.2(1) 1_555 1_555 1_555 no O2 C8 C13 119.8(1) 1_555 1_555 1_555 no C9 C8 C13 121.59(9) 1_555 1_555 1_555 no C8 C9 C10 118.17(7) 1_555 1_555 1_555 no C8 C9 C14 121.6(1) 1_555 1_555 1_555 no C10 C9 C14 120.2(1) 1_555 1_555 1_555 no C9 C10 C11 121.19(7) 1_555 1_555 1_555 no C10 C11 C12 119.68(9) 1_555 1_555 1_555 no C11 C12 C13 121.19(7) 1_555 1_555 1_555 no C8 C13 C12 118.17(7) 1_555 1_555 1_555 no C8 C13 C21 122.7(1) 1_555 1_555 1_555 no C12 C13 C21 119.1(1) 1_555 1_555 1_555 no C6 C14 C9 117.8(1) 1_555 1_555 1_555 no O3 C15 C16 119.5(1) 1_555 1_555 1_555 no O3 C15 C20 118.8(1) 1_555 1_555 1_555 no C16 C15 C20 121.59(9) 1_555 1_555 1_555 no C15 C16 C17 118.17(7) 1_555 1_555 1_555 no C15 C16 C21 118.1(1) 1_555 1_555 1_555 no C17 C16 C21 123.6(1) 1_555 1_555 1_555 no C16 C17 C18 121.19(7) 1_555 1_555 1_555 no C17 C18 C19 119.68(9) 1_555 1_555 1_555 no C18 C19 C20 121.19(7) 1_555 1_555 1_555 no C15 C20 C19 118.17(7) 1_555 1_555 1_555 no C15 C20 C28 117.1(1) 1_555 1_555 1_555 no C19 C20 C28 124.8(1) 1_555 1_555 1_555 no C13 C21 C16 115.1(1) 1_555 1_555 1_555 no O4 C22 C23 119.7(1) 1_555 1_555 1_555 no O4 C22 C27 118.5(1) 1_555 1_555 1_555 no C23 C22 C27 121.59(9) 1_555 1_555 1_555 no C22 C23 C24 118.17(7) 1_555 1_555 1_555 no C22 C23 C28 122.5(1) 1_555 1_555 1_555 no C24 C23 C28 119.3(1) 1_555 1_555 1_555 no C23 C24 C25 121.19(7) 1_555 1_555 1_555 no C24 C25 C26 119.68(9) 1_555 1_555 1_555 no C25 C26 C27 121.19(7) 1_555 1_555 1_555 no C7 C27 C22 121.1(1) 1_555 1_555 1_555 no C7 C27 C26 120.6(1) 1_555 1_555 1_555 no C22 C27 C26 118.17(7) 1_555 1_555 1_555 no C20 C28 C23 113.7(2) 1_555 1_555 1_555 no Ti1 O7 C2Ac 133.6(2) 1_555 1_555 1_555 no Ti1 O8 C4Ac 133.6(2) 1_555 1_555 1_555 no O7 C2Ac C1Ac 116.2(2) 1_555 1_555 1_555 no O7 C2Ac C3Ac 123.1(2) 1_555 1_555 1_555 no C1Ac C2Ac C3Ac 120.8(2) 1_555 1_555 1_555 no C2Ac C3Ac C4Ac 122.2(2) 1_555 1_555 1_555 no O8 C4Ac C3Ac 123.1(2) 1_555 1_555 1_555 no O8 C4Ac C5Ac 116.3(2) 1_555 1_555 1_555 no C3Ac C4Ac C5Ac 120.6(2) 1_555 1_555 1_555 no K1 O5 C1Me 99.9(1) 1_555 1_555 1_555 no