# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Francois Diederich' _publ_contact_author_email DIEDERICH@ORG.CHEM.ETHZ.CH _publ_section_title ; New Organofluorine Building Blocks: Inhibition of the Malarial Aspartic Proteases Plasmepsin II and IV by Alicyclic ?,?-Difluoroketone Hydrates ; loop_ _publ_author_name 'Francois Diederich' 'Lukas Baitsch' 'W. Bernd Schweizer' 'Daniel Bur' 'Christoph Fah' 'Leo A. Hardegger' ; S.Meyer ; # Attachment 'depCCDC.cif' data_11 _database_code_depnum_ccdc_archive 'CCDC 729039' _publ_section_comment ; Heavily disordered structure. The F-atoms have been refined on two positions. Geometries are tabulated below. All diagrams and calculations were performed using maXus (Bruker Nonius, Delft & MacScience, Japan). ; _publ_section_synopsis ; ; _publ_section_exptl_prep ; ; _publ_section_exptl_refinement ; ; _publ_section_figure_captions ; ; _publ_section_acknowledgements ; ; _chemical_compound_source 'Diederich laboratory' _exptl_crystal_description plate _exptl_crystal_size_max .5 _exptl_crystal_size_mid .32 _exptl_crystal_size_min .06 _exptl_crystal_F_000 1024.0 _exptl_crystal_colour Colourless _cell_measurement_temperature 223 _refine_ls_hydrogen_treatment constr _diffrn_measurement_device KappaCCD _computing_data_collection KappaCCD _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 loop_ _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_wavelength_id all _diffrn_orient_matrix_type X=UH _diffrn_orient_matrix_UB_11 0.07235 _diffrn_orient_matrix_UB_12 0.07430 _diffrn_orient_matrix_UB_13 -0.02451 _diffrn_orient_matrix_UB_21 -0.01249 _diffrn_orient_matrix_UB_22 -0.00733 _diffrn_orient_matrix_UB_23 -0.05911 _diffrn_orient_matrix_UB_31 -0.03688 _diffrn_orient_matrix_UB_32 0.04660 _diffrn_orient_matrix_UB_33 0.00201 _cell_formula_units_Z 4 _exptl_crystal_density_diffrn 1.220 _exptl_crystal_density_method 'not measured' _exptl_special_details ; ? ; _chemical_formula_weight 479.611 _diffrn_radiation_type ' MoK\a' loop_ _symmetry_equiv_pos_as_xyz +X,+Y,+Z -X,-Y,-Z '-X+ 1/2,+Y+ 1/2,-Z+ 1/2' '+X+ 1/2,-Y+ 1/2,+Z+ 1/2' _symmetry_space_group_name_H-M 'P 21/n ' _symmetry_cell_setting Monoclinic _chemical_formula_moiety 'C30 H35 F2 N O2 ' _chemical_formula_sum 'C30 H35 F2 N O2 ' _chemical_name_systematic ; ? ; _cell_length_a 9.4492(4) _cell_length_b 16.4318(8) _cell_length_c 16.9333(7) _cell_angle_alpha 90.00 _cell_angle_beta 96.750(3) _cell_angle_gamma 90.00 _cell_volume 2611.0(2) _diffrn_reflns_number 7607 _diffrn_reflns_theta_max 25.01 _diffrn_reflns_theta_min 3.30 _diffrn_reflns_theta_full 25.01 _cell_measurement_reflns_used 12427 _cell_measurement_theta_min 2.425 _cell_measurement_theta_max 25.028 _diffrn_measurement_method CCD _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SIR97(Altomare et al., J. Appl. Cryst.,1999)' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 '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' _exptl_absorpt_coefficient_mu 0.085 _reflns_number_total 4432 _reflns_number_gt 3262 _reflns_threshold_expression >2sigma(I) _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; The cyclohexyl ring is disordered (60:40) by rotating 180 deg around the N19-C20 bond and flipping the ring conformation. The F-atoms were refined on two positions. ; _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^)+ (0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4432 _refine_ls_number_parameters 334 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1894 _refine_ls_R_factor_gt 0.1624 _refine_ls_wR_factor_ref 0.4509 _refine_ls_wR_factor_gt 0.4312 _refine_ls_goodness_of_fit_ref 3.136 _refine_ls_restrained_S_all 3.136 _refine_ls_shift/su_max 0.010 _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 C1 C 0.5167(15) 0.4676(6) 0.3885(10) 0.206(8) Uani 1 1 d . . . C2 C 0.5619(11) 0.4089(5) 0.4207(6) 0.132(4) Uani 1 1 d . . . C3 C 0.7041(12) 0.4206(6) 0.4734(6) 0.142(4) Uani 1 1 d . . . C4 C 0.7749(10) 0.4911(6) 0.4808(5) 0.129(3) Uani 1 1 d . . . C5 C 0.7912(8) 0.6407(5) 0.4500(5) 0.110(2) Uani 1 1 d . . . C6 C 0.7310(8) 0.6981(3) 0.4019(4) 0.0891(18) Uani 1 1 d . . . C7 C 0.6094(11) 0.6797(5) 0.3532(4) 0.127(3) Uani 1 1 d . . . C8 C 0.5342(12) 0.6172(6) 0.3500(6) 0.136(3) Uani 1 1 d . . . C9 C 0.5880(7) 0.5560(5) 0.3877(5) 0.101(2) Uani 1 1 d . . . C10 C 0.7119(10) 0.5535(4) 0.4413(5) 0.126(3) Uani 1 1 d . . . C11 C 0.2983(6) 0.2006(3) 0.3603(3) 0.0708(13) Uani 1 1 d . . . C12 C 0.1666(7) 0.2294(4) 0.3330(3) 0.0875(17) Uani 1 1 d . . . C13 C 0.0485(6) 0.2079(4) 0.3714(3) 0.0924(18) Uani 1 1 d . . . C14 C 0.0631(6) 0.1583(4) 0.4365(3) 0.0793(15) Uani 1 1 d . . . C15 C 0.1964(6) 0.1306(3) 0.4631(3) 0.0751(14) Uani 1 1 d . . . C16 C 0.3165(5) 0.1510(3) 0.4267(3) 0.0672(12) Uani 1 1 d . . . C17 C 0.4898(10) 0.3280(4) 0.4190(6) 0.134(3) Uani 1 1 d . . . C18 C 0.5171(10) 0.2764(4) 0.3449(6) 0.136(4) Uani 1 1 d . . . C20 C 0.4325(8) 0.1718(3) 0.2471(3) 0.0919(18) Uani 1 1 d . . . C21 C 0.4802(5) 0.0848(3) 0.2636(2) 0.0647(12) Uani 1 1 d . A . C22 C 0.6303(5) 0.0786(3) 0.3029(3) 0.0796(14) Uani 1 1 d . . . C23 C 0.6734(6) -0.0094(4) 0.3163(4) 0.0854(16) Uani 1 1 d . A 2 C24 C 0.6563(7) -0.0606(3) 0.2440(4) 0.0867(17) Uani 1 1 d . . . C25 C 0.5065(8) -0.0517(3) 0.2012(4) 0.0902(17) Uani 1 1 d . A 1 C26 C 0.4626(6) 0.0355(3) 0.1856(3) 0.0787(14) Uani 1 1 d . . . C30 C -0.0643(8) 0.1333(6) 0.4756(4) 0.127(3) Uani 1 1 d . . . C31 C -0.0903(11) 0.1852(8) 0.5448(8) 0.190(6) Uani 1 1 d . . . C32 C -0.2405(16) 0.1715(15) 0.5713(12) 0.244(9) Uani 1 1 d . . . C33 C -0.2643(18) 0.0928(10) 0.5984(12) 0.232(10) Uani 1 1 d . . . C34 C -0.1453(18) 0.073(2) 0.672(2) 0.38(2) Uani 1 1 d . . . F28 F 0.5952(6) -0.0427(3) 0.3691(3) 0.0856(15) Uani 0.60 1 d P B 1 F29 F 0.8105(6) -0.0189(4) 0.3427(4) 0.109(2) Uani 0.60 1 d P C 1 F35 F 0.4318(10) -0.0904(5) 0.2473(6) 0.107(3) Uani 0.40 1 d P D 2 F36 F 0.5300(11) -0.0926(6) 0.1370(5) 0.116(3) Uani 0.40 1 d P E 2 N19 N 0.4198(6) 0.2192(2) 0.3194(3) 0.0896(15) Uani 1 1 d . . . O11 O 0.6268(9) 0.2862(3) 0.3140(6) 0.205(5) Uani 1 1 d . . . O27 O 0.6802(6) -0.1441(3) 0.2637(3) 0.130(2) Uani 1 1 d . A . H1 H 0.4247 0.4585 0.3593 0.247 Uiso 1 1 d R . . H3 H 0.7475 0.3758 0.5034 0.171 Uiso 1 1 d R . . H4 H 0.8657 0.4966 0.5124 0.154 Uiso 1 1 d R . . H5 H 0.8765 0.6531 0.4846 0.132 Uiso 1 1 d R . . H6 H 0.7709 0.7518 0.4024 0.107 Uiso 1 1 d R . . H7 H 0.5689 0.7196 0.3158 0.152 Uiso 1 1 d R . . H8 H 0.4434 0.6126 0.3184 0.163 Uiso 1 1 d R . . H12 H 0.1553 0.2643 0.2871 0.105 Uiso 1 1 d R . . H13 H -0.0447 0.2275 0.3518 0.111 Uiso 1 1 d R . . H15 H 0.2065 0.0954 0.5087 0.090 Uiso 1 1 d R . . H16 H 0.4099 0.1316 0.4464 0.081 Uiso 1 1 d R . . H17A H 0.3893 0.3365 0.4191 0.160 Uiso 1 1 d R . . H17B H 0.5268 0.2992 0.4663 0.160 Uiso 1 1 d R . . H20A H 0.3415 0.1706 0.2153 0.110 Uiso 1 1 d R . . H20B H 0.5013 0.1971 0.2176 0.110 Uiso 1 1 d R . . H21 H 0.4172 0.0623 0.2985 0.078 Uiso 1 1 d R . . H22A H 0.6928 0.1034 0.2692 0.095 Uiso 1 1 d R A . H22B H 0.6390 0.1062 0.3532 0.095 Uiso 1 1 d R . . H23A H 0.7725 -0.0112 0.3390 0.102 Uiso 0.40 1 calc PR A 2 H23B H 0.6170 -0.0327 0.3549 0.102 Uiso 0.40 1 calc PR A 2 H24 H 0.7244 -0.0432 0.2097 0.104 Uiso 1 1 d R A . H25A H 0.5009 -0.0804 0.1509 0.108 Uiso 0.60 1 calc PR A 1 H25B H 0.4398 -0.0771 0.2329 0.108 Uiso 0.60 1 calc PR A 1 H26A H 0.3648 0.0368 0.1628 0.094 Uiso 1 1 d R A . H26B H 0.5214 0.0590 0.1491 0.094 Uiso 1 1 d R . . H30A H -0.1483 0.1342 0.4378 0.152 Uiso 1 1 d R . . H30B H -0.0485 0.0790 0.4957 0.152 Uiso 1 1 d R . . H31A H -0.0210 0.1734 0.5895 0.228 Uiso 1 1 d R . . H31B H -0.0811 0.2410 0.5293 0.228 Uiso 1 1 d R . . H32A H -0.2557 0.2072 0.6144 0.293 Uiso 1 1 d R . . H32B H -0.3100 0.1827 0.5266 0.293 Uiso 1 1 d R . . H33A H -0.3601 0.0905 0.6119 0.279 Uiso 1 1 d R . . H33B H -0.2536 0.0547 0.5566 0.279 Uiso 1 1 d R . . H34A H -0.1661 0.0188 0.6893 0.461 Uiso 1 1 d R . . H34B H -0.1558 0.1106 0.7145 0.461 Uiso 1 1 d R . . H34C H -0.0492 0.0747 0.6592 0.461 Uiso 1 1 d R . . H27 H 0.7509 -0.1640 0.2243 0.156 Uiso 1 1 d 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 C1 0.261(14) 0.080(6) 0.324(17) -0.034(8) 0.238(14) -0.037(7) C2 0.171(8) 0.059(4) 0.193(8) -0.029(4) 0.128(7) -0.032(4) C3 0.171(8) 0.124(7) 0.146(6) -0.033(5) 0.075(6) -0.064(6) C4 0.126(6) 0.135(7) 0.127(6) -0.006(5) 0.024(5) -0.020(5) C5 0.113(5) 0.086(5) 0.141(5) -0.003(4) 0.060(4) -0.016(4) C6 0.124(5) 0.055(3) 0.097(4) -0.017(3) 0.047(3) -0.026(3) C7 0.175(8) 0.111(6) 0.102(4) -0.015(4) 0.043(5) -0.066(6) C8 0.164(8) 0.114(7) 0.130(6) -0.002(5) 0.019(5) -0.026(6) C9 0.085(4) 0.100(5) 0.120(5) -0.053(4) 0.019(4) 0.004(4) C10 0.171(7) 0.094(5) 0.136(5) 0.052(4) 0.112(6) 0.076(5) C11 0.094(3) 0.043(2) 0.083(3) 0.002(2) 0.040(3) 0.003(2) C12 0.111(4) 0.080(3) 0.074(3) 0.008(2) 0.018(3) 0.035(3) C13 0.078(3) 0.115(5) 0.084(3) -0.020(3) 0.009(3) 0.011(3) C14 0.080(3) 0.096(4) 0.063(3) -0.017(3) 0.015(2) -0.021(3) C15 0.087(4) 0.069(3) 0.071(3) 0.010(2) 0.019(2) -0.016(3) C16 0.071(3) 0.057(3) 0.075(3) 0.005(2) 0.013(2) 0.000(2) C17 0.173(7) 0.069(4) 0.181(7) -0.044(4) 0.117(6) -0.051(4) C18 0.181(7) 0.046(3) 0.211(8) -0.023(4) 0.145(7) -0.031(4) C20 0.139(5) 0.060(3) 0.089(3) 0.019(2) 0.061(3) 0.022(3) C21 0.079(3) 0.054(3) 0.066(2) 0.0037(18) 0.032(2) 0.004(2) C22 0.073(3) 0.074(3) 0.095(3) -0.013(3) 0.022(3) -0.008(2) C23 0.071(3) 0.078(3) 0.110(4) 0.008(3) 0.026(3) 0.011(3) C24 0.111(4) 0.057(3) 0.103(4) 0.015(3) 0.060(3) 0.021(3) C25 0.125(5) 0.064(3) 0.089(3) -0.020(3) 0.043(3) 0.003(3) C26 0.098(4) 0.073(3) 0.069(3) 0.001(2) 0.024(2) 0.011(3) C30 0.102(5) 0.174(8) 0.109(4) -0.057(5) 0.038(4) -0.057(5) C31 0.157(8) 0.232(12) 0.202(10) -0.112(9) 0.111(8) -0.117(9) C32 0.156(11) 0.33(3) 0.269(18) -0.099(17) 0.114(12) -0.049(13) C33 0.225(15) 0.194(13) 0.316(19) -0.120(13) 0.190(16) -0.132(12) C34 0.116(11) 0.54(5) 0.49(5) -0.11(4) 0.035(18) -0.020(18) F28 0.098(3) 0.091(4) 0.073(3) 0.017(2) 0.032(2) 0.024(3) F29 0.065(3) 0.126(5) 0.131(5) -0.006(4) -0.009(3) 0.011(3) F35 0.120(6) 0.067(5) 0.148(7) -0.022(5) 0.070(6) -0.027(4) F36 0.140(7) 0.102(6) 0.105(5) -0.051(5) 0.014(5) 0.013(6) N19 0.121(4) 0.047(2) 0.115(3) 0.005(2) 0.076(3) 0.008(2) O11 0.241(7) 0.079(3) 0.343(10) -0.077(5) 0.237(8) -0.073(4) O27 0.171(5) 0.067(3) 0.171(4) 0.029(3) 0.100(4) 0.039(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 C2 1.165(16) . ? C1 C9 1.601(12) . ? C2 C17 1.492(9) . ? C2 C3 1.534(15) . ? C3 C4 1.336(12) . ? C4 C10 1.327(12) . ? C5 C6 1.329(10) . ? C5 C10 1.616(12) . ? C6 C7 1.368(11) . ? C7 C8 1.246(11) . ? C8 C9 1.266(12) . ? C9 C10 1.395(12) . ? C11 C12 1.361(8) . ? C11 C16 1.381(7) . ? C11 N19 1.442(6) . ? C12 C13 1.402(9) . ? C13 C14 1.365(9) . ? C14 C15 1.364(8) . ? C14 C30 1.499(8) . ? C15 C16 1.396(7) . ? C17 C18 1.562(10) . ? C18 O11 1.225(8) . ? C18 N19 1.350(9) . ? C20 N19 1.468(7) . ? C20 C21 1.515(7) . ? C21 C22 1.498(7) . ? C21 C26 1.542(7) . ? C22 C23 1.511(8) . ? C23 C24 1.478(9) . ? C24 O27 1.423(6) . ? C24 C25 1.520(9) . ? C25 C26 1.506(8) . ? C30 C31 1.493(12) . ? C31 C32 1.554(15) . ? C32 C33 1.40(3) . ? C33 C34 1.62(4) . ? C1 H1 0.9601 . ? C3 H3 0.9600 . ? C4 H4 0.9600 . ? C5 H5 0.9599 . ? C6 H6 0.9599 . ? C7 H7 0.9600 . ? C8 H8 0.9599 . ? C12 H12 0.9600 . ? C13 H13 0.9600 . ? C15 H15 0.9601 . ? C16 H16 0.9600 . ? C17 H17A 0.9600 . ? C17 H17B 0.9601 . ? C20 H20A 0.9600 . ? C20 H20B 0.9600 . ? C21 H21 0.9600 . ? C22 H22A 0.9600 . ? C22 H22B 0.9599 . ? C23 H23A 0.9700 . ? C23 H23B 0.9700 . ? C24 H24 0.9600 . ? C25 H25A 0.9700 . ? C25 H25B 0.9700 . ? C26 H26A 0.9600 . ? C26 H26B 0.9600 . ? C30 H30A 0.9600 . ? C30 H30B 0.9601 . ? C31 H31A 0.9600 . ? C31 H31B 0.9601 . ? C32 H32A 0.9600 . ? C32 H32B 0.9600 . ? C33 H33A 0.9600 . ? C33 H33B 0.9600 . ? C34 H34A 0.9601 . ? C34 H34B 0.9600 . ? C34 H34C 0.9600 . ? O27 H27 1.0502 . ? 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 C2 C1 C9 128.6(15) . . ? C1 C2 C17 126.0(13) . . ? C1 C2 C3 114.6(10) . . ? C17 C2 C3 119.3(10) . . ? C4 C3 C2 124.0(10) . . ? C10 C4 C3 115.6(10) . . ? C6 C5 C10 114.3(7) . . ? C5 C6 C7 118.8(6) . . ? C8 C7 C6 130.0(10) . . ? C7 C8 C9 116.1(11) . . ? C8 C9 C10 127.4(8) . . ? C8 C9 C1 125.5(10) . . ? C10 C9 C1 106.9(10) . . ? C4 C10 C9 130.0(10) . . ? C4 C10 C5 117.6(9) . . ? C9 C10 C5 112.3(6) . . ? C12 C11 C16 120.3(5) . . ? C12 C11 N19 120.7(5) . . ? C16 C11 N19 119.1(5) . . ? C11 C12 C13 120.0(5) . . ? C14 C13 C12 121.0(5) . . ? C15 C14 C13 117.9(5) . . ? C15 C14 C30 121.3(6) . . ? C13 C14 C30 120.7(6) . . ? C14 C15 C16 122.7(5) . . ? C11 C16 C15 118.1(5) . . ? C2 C17 C18 112.4(5) . . ? O11 C18 N19 122.2(6) . . ? O11 C18 C17 120.0(7) . . ? N19 C18 C17 117.7(5) . . ? N19 C20 C21 113.5(4) . . ? C22 C21 C20 113.1(5) . . ? C22 C21 C26 110.2(4) . . ? C20 C21 C26 109.8(4) . . ? C21 C22 C23 110.9(4) . . ? C24 C23 C22 114.8(5) . . ? O27 C24 C23 110.8(5) . . ? O27 C24 C25 108.6(5) . . ? C23 C24 C25 110.2(4) . . ? C26 C25 C24 113.4(5) . . ? C25 C26 C21 110.5(4) . . ? C31 C30 C14 113.9(6) . . ? C30 C31 C32 112.5(9) . . ? C33 C32 C31 114.6(16) . . ? C32 C33 C34 108.6(17) . . ? C18 N19 C11 123.1(5) . . ? C18 N19 C20 121.1(5) . . ? C11 N19 C20 115.8(5) . . ? C2 C1 H1 111.8 . . ? C9 C1 H1 119.6 . . ? C4 C3 H3 116.0 . . ? C2 C3 H3 120.1 . . ? C10 C4 H4 121.8 . . ? C3 C4 H4 122.6 . . ? C6 C5 H5 119.5 . . ? C10 C5 H5 126.2 . . ? C5 C6 H6 120.5 . . ? C7 C6 H6 120.7 . . ? C8 C7 H7 110.7 . . ? C6 C7 H7 119.2 . . ? C7 C8 H8 123.9 . . ? C9 C8 H8 119.9 . . ? C11 C12 H12 119.6 . . ? C13 C12 H12 120.4 . . ? C14 C13 H13 118.8 . . ? C12 C13 H13 120.2 . . ? C14 C15 H15 117.9 . . ? C16 C15 H15 119.4 . . ? C11 C16 H16 120.1 . . ? C15 C16 H16 121.8 . . ? C2 C17 H17A 108.7 . . ? C18 C17 H17A 109.7 . . ? C2 C17 H17B 107.6 . . ? C18 C17 H17B 108.9 . . ? H17A C17 H17B 109.5 . . ? N19 C20 H20A 108.9 . . ? C21 C20 H20A 108.1 . . ? N19 C20 H20B 109.4 . . ? C21 C20 H20B 107.4 . . ? H20A C20 H20B 109.5 . . ? C22 C21 H21 108.8 . . ? C20 C21 H21 106.5 . . ? C26 C21 H21 108.2 . . ? C21 C22 H22A 108.8 . . ? C23 C22 H22A 108.7 . . ? C21 C22 H22B 109.8 . . ? C23 C22 H22B 109.1 . . ? H22A C22 H22B 109.5 . . ? C24 C23 H23A 108.6 . . ? C22 C23 H23A 108.6 . . ? C24 C23 H23B 108.6 . . ? C22 C23 H23B 108.6 . . ? H23A C23 H23B 107.5 . . ? O27 C24 H24 109.3 . . ? C23 C24 H24 108.4 . . ? C25 C24 H24 109.6 . . ? C26 C25 H25A 108.9 . . ? C24 C25 H25A 108.9 . . ? C26 C25 H25B 108.9 . . ? C24 C25 H25B 108.9 . . ? H25A C25 H25B 107.7 . . ? C25 C26 H26A 109.0 . . ? C21 C26 H26A 109.6 . . ? C25 C26 H26B 109.2 . . ? C21 C26 H26B 109.2 . . ? H26A C26 H26B 109.5 . . ? C31 C30 H30A 108.4 . . ? C14 C30 H30A 110.1 . . ? C31 C30 H30B 106.7 . . ? C14 C30 H30B 108.1 . . ? H30A C30 H30B 109.5 . . ? C30 C31 H31A 110.1 . . ? C32 C31 H31A 107.7 . . ? C30 C31 H31B 107.6 . . ? C32 C31 H31B 109.4 . . ? H31A C31 H31B 109.5 . . ? C33 C32 H32A 105.7 . . ? C31 C32 H32A 110.7 . . ? C33 C32 H32B 108.3 . . ? C31 C32 H32B 108.0 . . ? H32A C32 H32B 109.5 . . ? C32 C33 H33A 107.8 . . ? C34 C33 H33A 113.5 . . ? C32 C33 H33B 109.0 . . ? C34 C33 H33B 108.4 . . ? H33A C33 H33B 109.5 . . ? C33 C34 H34A 105.7 . . ? C33 C34 H34B 108.7 . . ? H34A C34 H34B 109.5 . . ? C33 C34 H34C 113.9 . . ? H34A C34 H34C 109.5 . . ? H34B C34 H34C 109.5 . . ? C24 O27 H27 104.3 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C9 C1 C2 C17 -179.9(7) . . . . ? C9 C1 C2 C3 4.4(13) . . . . ? C1 C2 C3 C4 -2.0(12) . . . . ? C17 C2 C3 C4 -177.9(7) . . . . ? C2 C3 C4 C10 2.3(12) . . . . ? C10 C5 C6 C7 2.2(8) . . . . ? C5 C6 C7 C8 6.7(13) . . . . ? C6 C7 C8 C9 -12.8(15) . . . . ? C7 C8 C9 C10 10.0(14) . . . . ? C7 C8 C9 C1 -176.2(8) . . . . ? C2 C1 C9 C8 178.5(10) . . . . ? C2 C1 C9 C10 -6.6(12) . . . . ? C3 C4 C10 C9 -5.8(12) . . . . ? C3 C4 C10 C5 178.6(6) . . . . ? C8 C9 C10 C4 -178.1(9) . . . . ? C1 C9 C10 C4 7.2(10) . . . . ? C8 C9 C10 C5 -2.3(10) . . . . ? C1 C9 C10 C5 -177.0(5) . . . . ? C6 C5 C10 C4 172.6(7) . . . . ? C6 C5 C10 C9 -3.8(7) . . . . ? C16 C11 C12 C13 -1.0(8) . . . . ? N19 C11 C12 C13 177.2(5) . . . . ? C11 C12 C13 C14 0.3(9) . . . . ? C12 C13 C14 C15 0.2(9) . . . . ? C12 C13 C14 C30 -178.0(6) . . . . ? C13 C14 C15 C16 0.1(8) . . . . ? C30 C14 C15 C16 178.2(5) . . . . ? C12 C11 C16 C15 1.2(7) . . . . ? N19 C11 C16 C15 -177.0(4) . . . . ? C14 C15 C16 C11 -0.8(8) . . . . ? C1 C2 C17 C18 85.1(11) . . . . ? C3 C2 C17 C18 -99.5(10) . . . . ? C2 C17 C18 O11 28.1(15) . . . . ? C2 C17 C18 N19 -154.9(9) . . . . ? N19 C20 C21 C22 -67.4(6) . . . . ? N19 C20 C21 C26 169.1(5) . . . . ? C20 C21 C22 C23 -178.7(4) . . . . ? C26 C21 C22 C23 -55.4(5) . . . . ? C21 C22 C23 C24 55.2(6) . . . . ? C22 C23 C24 O27 -171.9(5) . . . . ? C22 C23 C24 C25 -51.7(6) . . . . ? O27 C24 C25 C26 173.3(4) . . . . ? C23 C24 C25 C26 51.8(6) . . . . ? C24 C25 C26 C21 -54.7(6) . . . . ? C22 C21 C26 C25 56.1(6) . . . . ? C20 C21 C26 C25 -178.8(5) . . . . ? C15 C14 C30 C31 86.4(11) . . . . ? C13 C14 C30 C31 -95.5(10) . . . . ? C14 C30 C31 C32 166.3(13) . . . . ? C30 C31 C32 C33 63(2) . . . . ? C31 C32 C33 C34 58(2) . . . . ? O11 C18 N19 C11 172.8(9) . . . . ? C17 C18 N19 C11 -4.1(12) . . . . ? O11 C18 N19 C20 -7.2(13) . . . . ? C17 C18 N19 C20 175.9(7) . . . . ? C12 C11 N19 C18 102.0(8) . . . . ? C16 C11 N19 C18 -79.8(8) . . . . ? C12 C11 N19 C20 -78.1(6) . . . . ? C16 C11 N19 C20 100.2(6) . . . . ? C21 C20 N19 C18 106.0(7) . . . . ? C21 C20 N19 C11 -74.0(7) . . . . ? _diffrn_measured_fraction_theta_max 0.964 _diffrn_measured_fraction_theta_full 0.964 _refine_diff_density_max 0.952 _refine_diff_density_min -0.373 _refine_diff_density_rms 0.066 _publ_section_references ; Mackay, S., Gilmore, C. J.,Edwards, C., Stewart, N. & Shankland, K. (1999). maXus Computer Program for the Solution and Refinement of Crystal Structures. Bruker Nonius, The Netherlands, MacScience, Japan & The University of Glasgow. Johnson, C. K. (1976). ORTEP-II. A Fortran Thermal-Ellipsoid Plot Program. Report ORNL-5138. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Otwinowski, Z. and Minor, W, (1997). In Methods in Enzymology, 276, edited by C.W. Carter, Jr. & R.M. Sweet pp. 307-326, New York:Academic Press. Altomare, A., Burla, M.C., Camalli, M., Cascarano, G.L., Giacovazzo, C., Guagliardi, A., Moliterni, A.G.G & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119. Sheldrick, G. M. (1997). SHELXL97. Program for the Refinement of Crystal Structures. University of G\"ottingen, Germany. ; data_27 _database_code_depnum_ccdc_archive 'CCDC 729040' _publ_section_exptl_refinement ; bondlenght and some of U's of disordered pentylgroups constraint. No success in refining in supergroup. ; _publ_section_figure_captions ; ; _publ_section_acknowledgements ; ; _chemical_compound_source 'Diederich laboratory' _exptl_crystal_description Cube _exptl_crystal_size_max .36 _exptl_crystal_size_mid .32 _exptl_crystal_size_min .16 _exptl_crystal_F_000 2112.0 _exptl_crystal_colour Colourless _cell_measurement_temperature 233 _refine_ls_hydrogen_treatment constr _diffrn_measurement_device KappaCCD _computing_data_collection KappaCCD _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 loop_ _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_wavelength_id all _diffrn_orient_matrix_type X=UH _diffrn_orient_matrix_UB_11 0.06401 _diffrn_orient_matrix_UB_12 -0.00447 _diffrn_orient_matrix_UB_13 -0.01675 _diffrn_orient_matrix_UB_21 0.01396 _diffrn_orient_matrix_UB_22 0.01781 _diffrn_orient_matrix_UB_23 0.04860 _diffrn_orient_matrix_UB_31 0.00116 _diffrn_orient_matrix_UB_32 -0.04775 _diffrn_orient_matrix_UB_33 0.01717 _cell_formula_units_Z 8 _exptl_crystal_density_diffrn 1.188 _exptl_crystal_density_method 'not measured' _exptl_special_details ; ? ; _chemical_formula_weight 495.610 _diffrn_radiation_type ' MoK\a' loop_ _symmetry_equiv_pos_as_xyz +X,+Y,+Z '-X,+Y+ 1/2,-Z' '-X+ 1/2,+Y+ 1/2,+Z+ 1/2' '+X+ 1/2,+Y,-Z+ 1/2' _symmetry_space_group_name_H-M 'P n 21 a ' _symmetry_cell_setting Orthorhombic _chemical_formula_moiety 'C30 H35 F2 N O3 ' _chemical_formula_sum 'C30 H35 F2 N O3 ' _chemical_name_systematic ; ? ; _cell_length_a 15.0801(5) _cell_length_b 18.6531(7) _cell_length_c 19.7040(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 5542.6(3) _diffrn_reflns_number 9715 _diffrn_reflns_theta_max 25.36 _diffrn_reflns_theta_min 2.47 _diffrn_reflns_theta_full 25.36 _cell_measurement_reflns_used 15871 _cell_measurement_theta_min 2.425 _cell_measurement_theta_max 25.350 _diffrn_measurement_method CCD _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SIR97(Cascarano al.,Acta Cryst.,1996,A52,C-79)' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 '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' _exptl_absorpt_coefficient_mu 0.085 _reflns_number_total 9408 _reflns_number_gt 6973 _reflns_threshold_expression >2sigma(I) _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; The phenyl substituents show multiple disorder. Where applicable two distinct positions for C-atoms have been refined with fixed occupancy of 50%, restrained distances of 1.53 A with DFIX. H-positions were only split on disordered atoms with two positions. ; _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^)+ (0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.1(11) _refine_ls_number_reflns 9408 _refine_ls_number_parameters 635 _refine_ls_number_restraints 17 _refine_ls_R_factor_all 0.1113 _refine_ls_R_factor_gt 0.0824 _refine_ls_wR_factor_ref 0.2229 _refine_ls_wR_factor_gt 0.2026 _refine_ls_goodness_of_fit_ref 1.373 _refine_ls_restrained_S_all 1.372 _refine_ls_shift/su_max 0.008 _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 F16 F 0.69560(19) 0.1228(2) 0.35176(16) 0.0835(9) Uani 1 1 d . . . F17 F 0.6896(2) 0.1321(2) 0.24157(15) 0.0812(8) Uani 1 1 d . . . F52 F -0.09574(19) 0.5287(2) 0.22143(14) 0.0725(7) Uani 1 1 d . . . F53 F -0.11876(16) 0.52490(19) 0.33013(13) 0.0661(7) Uani 1 1 d . . . O15 O 0.4015(2) 0.2357(2) 0.32356(17) 0.0708(9) Uani 1 1 d . . . O18 O 0.81228(19) 0.2202(2) 0.30582(17) 0.0706(9) Uani 1 1 d . . . O19 O 0.69864(18) 0.2774(2) 0.24794(14) 0.0606(7) Uani 1 1 d . . . O51 O 0.20094(19) 0.4722(2) 0.32877(17) 0.0719(9) Uani 1 1 d . . . O54 O -0.0704(2) 0.3869(2) 0.21289(15) 0.0643(8) Uani 1 1 d . . . O55 O -0.20144(18) 0.4110(2) 0.26995(16) 0.0623(8) Uani 1 1 d . . . N13 N 0.4089(2) 0.2358(2) 0.43746(19) 0.0560(9) Uani 1 1 d . . . N49 N 0.1720(2) 0.4442(2) 0.43663(17) 0.0530(8) Uani 1 1 d . . . C1 C 0.1289(3) 0.1622(3) 0.5199(2) 0.0574(10) Uani 1 1 d . . . C2 C 0.1698(3) 0.1733(3) 0.4588(2) 0.0544(9) Uani 1 1 d . . . C3 C 0.1177(3) 0.1913(3) 0.4028(2) 0.0585(10) Uani 1 1 d . . . C4 C 0.0278(3) 0.1970(3) 0.4076(2) 0.0609(11) Uani 1 1 d . . . C5 C -0.1094(3) 0.1950(4) 0.4778(3) 0.0773(14) Uani 1 1 d . . . C6 C -0.1483(3) 0.1860(4) 0.5378(3) 0.0872(17) Uani 1 1 d . . . C7 C -0.0989(4) 0.1664(4) 0.5942(3) 0.0876(17) Uani 1 1 d . . . C8 C -0.0088(3) 0.1602(3) 0.5908(3) 0.0719(13) Uani 1 1 d . . . C9 C 0.0353(3) 0.1693(3) 0.5271(2) 0.0550(10) Uani 1 1 d . . . C10 C -0.0156(3) 0.1871(3) 0.4702(2) 0.0560(10) Uani 1 1 d . . . C11 C 0.2703(3) 0.1681(3) 0.4510(3) 0.0666(12) Uani 1 1 d . . . C12 C 0.3119(3) 0.2414(3) 0.4432(3) 0.0613(11) Uani 1 1 d . . . C14 C 0.4464(3) 0.2299(3) 0.3753(2) 0.0536(10) Uani 1 1 d . . . C20 C 0.5458(3) 0.2171(3) 0.3709(2) 0.0550(10) Uani 1 1 d . . . C21 C 0.5683(3) 0.1781(3) 0.3054(2) 0.0593(11) Uani 1 1 d . . . C22 C 0.6676(3) 0.1675(3) 0.2996(2) 0.0601(11) Uani 1 1 d . . . C23 C 0.7211(3) 0.2358(3) 0.3046(2) 0.0559(10) Uani 1 1 d . . . C24 C 0.6969(3) 0.2737(3) 0.3713(2) 0.0639(11) Uani 1 1 d . . . C25 C 0.5976(2) 0.2870(3) 0.3763(2) 0.0557(10) Uani 1 1 d . . . C26 C 0.4581(3) 0.2359(3) 0.5007(2) 0.0555(10) Uani 1 1 d . . . C27 C 0.4746(3) 0.2999(3) 0.5331(3) 0.0664(12) Uani 1 1 d . . . C28 C 0.5154(4) 0.3003(3) 0.5956(3) 0.0810(15) Uani 1 1 d . . . C29 C 0.5396(4) 0.2363(3) 0.6273(3) 0.0775(14) Uani 1 1 d . . . C30 C 0.5257(4) 0.1738(3) 0.5930(3) 0.0789(15) Uani 1 1 d . . . C31 C 0.4832(3) 0.1724(3) 0.5310(2) 0.0650(11) Uani 1 1 d . . . C32 C 0.5799(5) 0.2354(5) 0.6982(3) 0.104(2) Uani 1 1 d . B . C33 C 0.6726(5) 0.2111(5) 0.7039(3) 0.111(2) Uani 1 1 d D . . C34 C 0.7006(8) 0.2215(10) 0.7780(4) 0.096(4) Uiso 0.50 1 d PD B 1 C35 C 0.7983(8) 0.2051(10) 0.7923(8) 0.121(5) Uiso 0.50 1 d PD B 1 C74 C 0.7145(9) 0.1866(10) 0.7707(4) 0.116(5) Uiso 0.50 1 d PD B 2 C75 C 0.8004(8) 0.1429(8) 0.7729(6) 0.092(3) Uiso 0.50 1 d PD B 2 C36 C 0.8434(16) 0.1540(11) 0.8423(8) 0.296(10) Uiso 1 1 d D . . C37 C 0.4667(3) 0.4878(3) 0.4439(3) 0.0609(11) Uani 1 1 d . . . C38 C 0.4052(3) 0.5015(3) 0.4916(2) 0.0568(10) Uani 1 1 d . . . C39 C 0.4297(3) 0.5068(3) 0.5592(3) 0.0683(12) Uani 1 1 d . . . C40 C 0.5160(3) 0.4981(3) 0.5795(3) 0.0731(13) Uani 1 1 d . . . C41 C 0.6741(4) 0.4779(4) 0.5497(3) 0.0832(15) Uani 1 1 d . . . C42 C 0.7340(4) 0.4696(4) 0.5039(4) 0.101(2) Uani 1 1 d . . . C43 C 0.7120(4) 0.4661(4) 0.4333(4) 0.0952(19) Uani 1 1 d . . . C44 C 0.6239(4) 0.4714(3) 0.4146(3) 0.0809(15) Uani 1 1 d . . . C45 C 0.5580(3) 0.4803(3) 0.4630(3) 0.0619(11) Uani 1 1 d . . . C46 C 0.5815(3) 0.4859(3) 0.5320(2) 0.0637(12) Uani 1 1 d . . . C47 C 0.3080(3) 0.5109(3) 0.4706(3) 0.0664(12) Uani 1 1 d . . . C48 C 0.2673(3) 0.4392(3) 0.4521(3) 0.0610(11) Uani 1 1 d . . . C50 C 0.1464(2) 0.4594(3) 0.3729(2) 0.0511(9) Uani 1 1 d . . . C56 C 0.0476(2) 0.4561(3) 0.3564(2) 0.0500(9) Uani 1 1 d . . . C57 C 0.0244(3) 0.4971(3) 0.2929(2) 0.0519(9) Uani 1 1 d . . . C58 C -0.0736(3) 0.4914(3) 0.2790(2) 0.0528(9) Uani 1 1 d . . . C59 C -0.1070(2) 0.4132(3) 0.2727(2) 0.0512(9) Uani 1 1 d . . . C60 C -0.0794(3) 0.3714(3) 0.3344(2) 0.0584(10) Uani 1 1 d . . . C61 C 0.0198(3) 0.3774(3) 0.3487(2) 0.0584(10) Uani 1 1 d . . . C62 C 0.1104(3) 0.4372(3) 0.4931(2) 0.0537(10) Uani 1 1 d . . . C63 C 0.0703(3) 0.4972(3) 0.5212(2) 0.0697(12) Uani 1 1 d . D . C64 C 0.0104(5) 0.4897(4) 0.5736(3) 0.106(2) Uani 1 1 d . . . C65 C -0.0211(6) 0.4192(6) 0.5945(5) 0.059(2) Uiso 0.50 1 d PD D 1 C85 C 0.0134(11) 0.4316(9) 0.6132(7) 0.101(4) Uiso 0.50 1 d PD D 2 C66 C 0.0328(5) 0.3625(4) 0.5721(3) 0.0984(19) Uani 1 1 d . . . C67 C 0.0916(3) 0.3698(3) 0.5190(3) 0.0718(13) Uani 1 1 d . D . C68 C -0.0975(7) 0.4070(9) 0.6442(5) 0.093(3) Uiso 0.50 1 d PDU D 1 C69 C -0.0680(16) 0.413(2) 0.7182(7) 0.196(11) Uiso 0.50 1 d PDU D 1 C70 C -0.1348(17) 0.3990(18) 0.7752(13) 0.184(9) Uiso 0.50 1 d PDU D 1 C71 C -0.217(3) 0.447(2) 0.7693(17) 0.257(19) Uiso 0.50 1 d PDU D 1 C72 C -0.247(2) 0.4150(18) 0.8373(15) 0.194(10) Uiso 0.50 1 d PDU D 1 C88 C -0.0473(12) 0.4139(13) 0.6731(10) 0.158(7) Uiso 0.50 1 d PDU D 2 C89 C -0.1371(13) 0.4512(14) 0.6812(10) 0.162(8) Uiso 0.50 1 d PDU D 2 C90 C -0.1775(16) 0.442(2) 0.7520(11) 0.178(9) Uiso 0.50 1 d PDU D 2 C91 C -0.2740(16) 0.465(2) 0.7418(10) 0.200 Uiso 0.50 1 d PDU D 2 C92 C -0.2980(17) 0.4534(16) 0.8164(10) 0.161(8) Uiso 0.50 1 d PDU D 2 H18 H 0.8342 0.2302 0.2690 0.106 Uiso 1 1 calc R . . H19 H 0.7180 0.3181 0.2528 0.091 Uiso 1 1 calc R . . H54 H -0.0832 0.3444 0.2087 0.096 Uiso 1 1 calc R . . H55 H -0.2186 0.4316 0.2356 0.093 Uiso 1 1 calc R . . H1 H 0.1628 0.1498 0.5576 0.069 Uiso 1 1 calc R . . H3 H 0.1450 0.1997 0.3612 0.070 Uiso 1 1 calc R . . H4 H -0.0053 0.2075 0.3690 0.073 Uiso 1 1 calc R . . H5 H -0.1437 0.2066 0.4402 0.093 Uiso 1 1 calc R . . H6 H -0.2092 0.1930 0.5420 0.105 Uiso 1 1 calc R . . H7 H -0.1277 0.1573 0.6350 0.105 Uiso 1 1 calc R . . H8 H 0.0237 0.1501 0.6297 0.086 Uiso 1 1 calc R . . H11A H 0.2952 0.1446 0.4905 0.080 Uiso 1 1 calc R . . H11B H 0.2842 0.1392 0.4115 0.080 Uiso 1 1 calc R . . H12A H 0.2884 0.2646 0.4029 0.074 Uiso 1 1 calc R . . H12B H 0.2969 0.2708 0.4821 0.074 Uiso 1 1 calc R . . H20 H 0.5631 0.1864 0.4090 0.066 Uiso 1 1 calc R . . H21A H 0.5388 0.1319 0.3047 0.071 Uiso 1 1 calc R . . H21B H 0.5472 0.2058 0.2669 0.071 Uiso 1 1 calc R . . H24A H 0.7157 0.2443 0.4094 0.077 Uiso 1 1 calc R . . H24B H 0.7280 0.3191 0.3740 0.077 Uiso 1 1 calc R . . H25A H 0.5794 0.3191 0.3401 0.067 Uiso 1 1 calc R . . H25B H 0.5842 0.3099 0.4192 0.067 Uiso 1 1 calc R . . H27 H 0.4582 0.3429 0.5127 0.080 Uiso 1 1 calc R . . H28 H 0.5269 0.3437 0.6170 0.097 Uiso 1 1 calc R . . H30 H 0.5454 0.1310 0.6119 0.095 Uiso 1 1 calc R . . H31 H 0.4716 0.1289 0.5097 0.078 Uiso 1 1 calc R . . H32A H 0.5761 0.2835 0.7167 0.125 Uiso 1 1 calc R . . H32B H 0.5435 0.2046 0.7265 0.125 Uiso 1 1 calc R . . H33A H 0.7104 0.2391 0.6741 0.133 Uiso 1 1 calc R A 1 H33B H 0.6774 0.1610 0.6913 0.133 Uiso 1 1 calc R A 1 H34A H 0.6887 0.2708 0.7910 0.115 Uiso 0.50 1 calc PR B 1 H34B H 0.6643 0.1909 0.8065 0.115 Uiso 0.50 1 calc PR B 1 H35A H 0.8221 0.1915 0.7484 0.145 Uiso 0.50 1 calc PR B 1 H35B H 0.8242 0.2515 0.8023 0.145 Uiso 0.50 1 calc PR B 1 H74A H 0.6699 0.1589 0.7945 0.140 Uiso 0.50 1 calc PR B 2 H74B H 0.7247 0.2295 0.7975 0.140 Uiso 0.50 1 calc PR B 2 H75A H 0.7875 0.0925 0.7659 0.111 Uiso 0.50 1 calc PR B 2 H75B H 0.8403 0.1587 0.7373 0.111 Uiso 0.50 1 calc PR B 2 H36A H 0.9065 0.1601 0.8397 0.444 Uiso 1 1 calc R B 1 H36B H 0.8283 0.1055 0.8310 0.444 Uiso 1 1 calc R B 1 H36C H 0.8237 0.1645 0.8875 0.444 Uiso 1 1 calc R B 1 H37 H 0.4501 0.4832 0.3987 0.073 Uiso 1 1 calc R . . H39 H 0.3866 0.5165 0.5917 0.082 Uiso 1 1 calc R . . H40 H 0.5304 0.5004 0.6253 0.088 Uiso 1 1 calc R . . H41 H 0.6906 0.4788 0.5951 0.100 Uiso 1 1 calc R . . H42 H 0.7930 0.4659 0.5169 0.122 Uiso 1 1 calc R . . H43 H 0.7561 0.4604 0.4007 0.114 Uiso 1 1 calc R . . H44 H 0.6086 0.4689 0.3689 0.097 Uiso 1 1 calc R . . H47A H 0.2750 0.5322 0.5078 0.080 Uiso 1 1 calc R . . H47B H 0.3045 0.5430 0.4320 0.080 Uiso 1 1 calc R . . H48A H 0.2980 0.4198 0.4129 0.073 Uiso 1 1 calc R . . H48B H 0.2756 0.4061 0.4895 0.073 Uiso 1 1 calc R . . H56 H 0.0146 0.4769 0.3945 0.060 Uiso 1 1 calc R . . H57A H 0.0575 0.4779 0.2548 0.062 Uiso 1 1 calc R . . H57B H 0.0407 0.5471 0.2985 0.062 Uiso 1 1 calc R . . H60A H -0.0946 0.3213 0.3279 0.070 Uiso 1 1 calc R . . H60B H -0.1121 0.3887 0.3735 0.070 Uiso 1 1 calc R . . H61A H 0.0528 0.3556 0.3118 0.070 Uiso 1 1 calc R . . H61B H 0.0338 0.3515 0.3901 0.070 Uiso 1 1 calc R . . H63 H 0.0839 0.5426 0.5047 0.084 Uiso 1 1 calc R . . H64 H -0.0102 0.5303 0.5960 0.127 Uiso 1 1 calc R C 1 H66 H 0.0286 0.3184 0.5939 0.118 Uiso 1 1 calc R D 1 H67 H 0.1186 0.3295 0.5005 0.086 Uiso 1 1 calc R . . H68A H -0.1437 0.4420 0.6354 0.112 Uiso 0.50 1 calc PR D 1 H68B H -0.1224 0.3597 0.6366 0.112 Uiso 0.50 1 calc PR D 1 H69A H -0.0449 0.4612 0.7247 0.235 Uiso 0.50 1 calc PR D 1 H69B H -0.0188 0.3803 0.7246 0.235 Uiso 0.50 1 calc PR D 1 H70A H -0.1528 0.3491 0.7737 0.221 Uiso 0.50 1 calc PR D 1 H70B H -0.1064 0.4076 0.8186 0.221 Uiso 0.50 1 calc PR D 1 H71A H -0.2554 0.4348 0.7315 0.309 Uiso 0.50 1 calc PR D 1 H71B H -0.2044 0.4977 0.7709 0.309 Uiso 0.50 1 calc PR D 1 H72A H -0.3102 0.4105 0.8377 0.291 Uiso 0.50 1 calc PR D 1 H72B H -0.2285 0.4460 0.8735 0.291 Uiso 0.50 1 calc PR D 1 H72C H -0.2203 0.3686 0.8433 0.291 Uiso 0.50 1 calc PR D 1 H88A H -0.0587 0.3627 0.6716 0.189 Uiso 0.50 1 calc PR D 2 H88B H -0.0138 0.4229 0.7142 0.189 Uiso 0.50 1 calc PR D 2 H89A H -0.1780 0.4319 0.6479 0.194 Uiso 0.50 1 calc PR D 2 H89B H -0.1298 0.5019 0.6718 0.194 Uiso 0.50 1 calc PR D 2 H90A H -0.1737 0.3931 0.7672 0.213 Uiso 0.50 1 calc PR D 2 H90B H -0.1480 0.4731 0.7847 0.213 Uiso 0.50 1 calc PR D 2 H91A H -0.3063 0.4339 0.7113 0.240 Uiso 0.50 1 calc PR D 2 H91B H -0.2800 0.5148 0.7277 0.240 Uiso 0.50 1 calc PR D 2 H92A H -0.3567 0.4712 0.8248 0.242 Uiso 0.50 1 calc PR D 2 H92B H -0.2565 0.4785 0.8447 0.242 Uiso 0.50 1 calc PR D 2 H92C H -0.2959 0.4031 0.8266 0.242 Uiso 0.50 1 calc PR D 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 F16 0.0744(18) 0.082(2) 0.0938(19) 0.0306(16) 0.0126(14) 0.0171(15) F17 0.0853(19) 0.070(2) 0.0881(19) -0.0111(15) 0.0122(14) 0.0015(15) F52 0.0818(17) 0.0609(17) 0.0747(15) 0.0158(13) -0.0135(13) -0.0001(13) F53 0.0571(14) 0.0639(17) 0.0771(15) -0.0087(13) 0.0026(11) 0.0122(12) O15 0.0479(16) 0.086(2) 0.078(2) 0.0174(17) -0.0149(14) -0.0039(16) O18 0.0435(15) 0.094(3) 0.0742(18) 0.0083(17) 0.0016(13) -0.0002(15) O19 0.0518(15) 0.064(2) 0.0659(17) 0.0097(14) -0.0013(12) -0.0114(14) O51 0.0406(15) 0.097(3) 0.0776(19) -0.0054(17) 0.0200(14) -0.0029(15) O54 0.0663(18) 0.058(2) 0.0684(18) -0.0070(14) 0.0008(14) -0.0016(14) O55 0.0427(14) 0.067(2) 0.0768(18) 0.0131(15) -0.0105(12) -0.0049(13) N13 0.0386(16) 0.049(2) 0.081(2) 0.0163(17) -0.0031(15) -0.0005(15) N49 0.0327(14) 0.053(2) 0.073(2) -0.0045(16) -0.0023(14) -0.0012(14) C1 0.047(2) 0.058(3) 0.067(2) 0.018(2) -0.0048(18) -0.0002(19) C2 0.043(2) 0.050(2) 0.071(2) 0.0119(19) 0.0069(18) -0.0007(17) C3 0.058(2) 0.059(3) 0.059(2) 0.0118(19) 0.0114(18) -0.003(2) C4 0.054(2) 0.066(3) 0.063(2) 0.019(2) -0.0053(19) -0.003(2) C5 0.052(2) 0.080(4) 0.099(4) 0.024(3) 0.003(2) 0.007(2) C6 0.051(3) 0.090(4) 0.120(5) 0.025(3) 0.021(3) 0.007(3) C7 0.078(4) 0.091(4) 0.094(4) 0.015(3) 0.040(3) 0.006(3) C8 0.071(3) 0.076(3) 0.069(3) 0.020(2) 0.012(2) 0.000(3) C9 0.052(2) 0.055(3) 0.059(2) 0.0151(19) 0.0023(17) -0.0013(18) C10 0.043(2) 0.053(3) 0.072(3) 0.0148(19) -0.0015(18) 0.0020(18) C11 0.048(2) 0.054(3) 0.098(3) 0.015(2) 0.009(2) 0.0028(19) C12 0.0404(19) 0.048(2) 0.095(3) 0.011(2) 0.0097(19) 0.0026(18) C14 0.044(2) 0.049(2) 0.068(3) 0.0099(19) -0.0020(19) -0.0097(17) C20 0.045(2) 0.061(3) 0.059(2) 0.0135(19) -0.0003(17) -0.0017(18) C21 0.057(2) 0.055(3) 0.066(2) 0.000(2) -0.0027(19) -0.012(2) C22 0.053(2) 0.064(3) 0.064(2) 0.006(2) 0.0024(19) 0.006(2) C23 0.043(2) 0.070(3) 0.056(2) 0.008(2) -0.0018(16) -0.002(2) C24 0.046(2) 0.074(3) 0.072(3) -0.002(2) -0.0017(19) -0.003(2) C25 0.040(2) 0.063(3) 0.064(2) -0.003(2) -0.0018(16) -0.0054(18) C26 0.050(2) 0.045(2) 0.072(3) 0.012(2) 0.0020(18) 0.0030(18) C27 0.071(3) 0.040(3) 0.088(3) 0.004(2) 0.002(2) 0.007(2) C28 0.100(4) 0.053(3) 0.091(3) -0.008(3) -0.016(3) 0.006(3) C29 0.088(4) 0.065(3) 0.079(3) 0.000(3) -0.013(3) 0.019(3) C30 0.105(4) 0.053(3) 0.078(3) 0.006(3) -0.015(3) 0.017(3) C31 0.078(3) 0.044(3) 0.073(3) 0.007(2) -0.005(2) 0.009(2) C32 0.120(5) 0.097(5) 0.095(4) -0.005(4) -0.014(4) 0.018(4) C33 0.080(4) 0.131(7) 0.121(5) 0.031(4) -0.012(3) 0.002(4) C37 0.060(2) 0.040(2) 0.082(3) 0.002(2) -0.008(2) -0.0003(19) C38 0.045(2) 0.041(2) 0.084(3) -0.003(2) -0.013(2) -0.0019(17) C39 0.056(2) 0.049(3) 0.100(4) -0.009(2) 0.002(2) -0.003(2) C40 0.072(3) 0.072(3) 0.075(3) -0.006(2) -0.011(2) 0.003(3) C41 0.061(3) 0.076(4) 0.112(4) -0.001(3) -0.015(3) 0.005(3) C42 0.066(3) 0.088(5) 0.150(6) 0.006(4) -0.001(4) 0.009(3) C43 0.062(3) 0.089(5) 0.134(6) -0.008(4) 0.025(3) 0.006(3) C44 0.085(4) 0.073(4) 0.084(3) -0.012(3) 0.006(3) 0.001(3) C45 0.052(2) 0.041(2) 0.093(3) -0.003(2) 0.010(2) 0.0032(18) C46 0.062(3) 0.049(3) 0.079(3) 0.004(2) -0.020(2) -0.008(2) C47 0.042(2) 0.044(3) 0.112(4) 0.000(2) -0.011(2) 0.0034(18) C48 0.041(2) 0.048(2) 0.095(3) -0.001(2) -0.009(2) 0.0030(17) C50 0.0358(19) 0.057(2) 0.061(2) -0.0056(18) 0.0098(17) -0.0016(17) C56 0.0320(17) 0.059(3) 0.059(2) 0.0028(18) 0.0075(15) 0.0063(16) C57 0.047(2) 0.051(2) 0.057(2) -0.0029(17) 0.0108(16) -0.0040(17) C58 0.050(2) 0.059(3) 0.050(2) 0.0045(18) 0.0052(16) 0.0081(19) C59 0.0383(18) 0.060(3) 0.055(2) 0.0045(18) -0.0047(15) 0.0008(17) C60 0.047(2) 0.054(3) 0.073(3) 0.011(2) -0.0099(19) -0.0045(18) C61 0.042(2) 0.061(3) 0.073(2) 0.011(2) -0.0068(18) 0.0011(18) C62 0.050(2) 0.056(3) 0.054(2) -0.0026(18) -0.0042(17) 0.0060(18) C63 0.081(3) 0.061(3) 0.067(3) 0.003(2) 0.011(2) 0.011(2) C64 0.138(6) 0.089(5) 0.089(4) 0.004(3) 0.029(4) 0.043(4) C66 0.123(5) 0.081(4) 0.091(4) 0.017(3) 0.026(4) 0.001(4) C67 0.072(3) 0.064(3) 0.080(3) 0.004(2) 0.005(2) 0.001(2) _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 F16 C22 1.389(5) . ? F17 C22 1.361(5) . ? F52 C58 1.371(5) . ? F53 C58 1.368(5) . ? O15 C14 1.228(5) . ? O18 C23 1.405(5) . ? O19 C23 1.402(5) . ? O51 C50 1.220(5) . ? O54 C59 1.390(5) . ? O55 C59 1.425(5) . ? N13 C14 1.354(6) . ? N13 C26 1.451(6) . ? N13 C12 1.471(5) . ? N49 C50 1.344(5) . ? N49 C62 1.456(5) . ? N49 C48 1.471(5) . ? C1 C2 1.369(6) . ? C1 C9 1.425(6) . ? C2 C3 1.397(6) . ? C2 C11 1.525(6) . ? C3 C4 1.364(6) . ? C4 C10 1.408(7) . ? C5 C6 1.331(8) . ? C5 C10 1.430(6) . ? C6 C7 1.386(9) . ? C7 C8 1.365(8) . ? C8 C9 1.431(6) . ? C9 C10 1.398(6) . ? C11 C12 1.513(7) . ? C14 C20 1.521(6) . ? C20 C21 1.520(6) . ? C20 C25 1.522(6) . ? C21 C22 1.515(6) . ? C22 C23 1.512(7) . ? C23 C24 1.536(7) . ? C24 C25 1.521(6) . ? C26 C27 1.375(7) . ? C26 C31 1.379(6) . ? C27 C28 1.377(8) . ? C28 C29 1.396(8) . ? C29 C30 1.363(8) . ? C29 C32 1.522(9) . ? C30 C31 1.381(7) . ? C32 C33 1.474(10) . ? C33 C74 1.530(2) . ? C33 C34 1.533(2) . ? C34 C35 1.530(2) . ? C35 C36 1.530(2) . ? C74 C75 1.531(2) . ? C75 C36 1.528(2) . ? C37 C38 1.345(7) . ? C37 C45 1.435(6) . ? C38 C39 1.386(7) . ? C38 C47 1.532(6) . ? C39 C40 1.370(7) . ? C40 C46 1.379(8) . ? C41 C42 1.286(9) . ? C41 C46 1.447(7) . ? C42 C43 1.430(11) . ? C43 C44 1.382(9) . ? C44 C45 1.388(7) . ? C45 C46 1.408(7) . ? C47 C48 1.517(6) . ? C50 C56 1.527(5) . ? C56 C57 1.507(6) . ? C56 C61 1.535(6) . ? C57 C58 1.507(6) . ? C58 C59 1.548(6) . ? C59 C60 1.504(6) . ? C60 C61 1.526(6) . ? C62 C67 1.385(7) . ? C62 C63 1.388(7) . ? C63 C64 1.378(8) . ? C64 C85 1.337(17) . ? C64 C65 1.458(13) . ? C65 C66 1.404(12) . ? C65 C68 1.530(2) . ? C85 C88 1.530(2) . ? C85 C66 1.550(18) . ? C66 C67 1.379(8) . ? C68 C69 1.529(2) . ? C69 C70 1.531(2) . ? C70 C71 1.529(2) . ? C71 C72 1.531(2) . ? C88 C89 1.530(2) . ? C89 C90 1.530(2) . ? C90 C91 1.530(2) . ? C91 C92 1.530(2) . ? O18 H18 0.8200 . ? O19 H19 0.8200 . ? O54 H54 0.8200 . ? O55 H55 0.8200 . ? C1 H1 0.9300 . ? C3 H3 0.9300 . ? C4 H4 0.9300 . ? C5 H5 0.9300 . ? C6 H6 0.9300 . ? C7 H7 0.9300 . ? C8 H8 0.9300 . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C20 H20 0.9800 . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C24 H24A 0.9700 . ? C24 H24B 0.9700 . ? C25 H25A 0.9700 . ? C25 H25B 0.9700 . ? C27 H27 0.9300 . ? C28 H28 0.9300 . ? C30 H30 0.9300 . ? C31 H31 0.9300 . ? C32 H32A 0.9700 . ? C32 H32B 0.9700 . ? C33 H33A 0.9700 . ? C33 H33B 0.9700 . ? C34 H34A 0.9700 . ? C34 H34B 0.9700 . ? C35 H35A 0.9700 . ? C35 H35B 0.9700 . ? C74 H74A 0.9700 . ? C74 H74B 0.9700 . ? C75 H75A 0.9700 . ? C75 H75B 0.9700 . ? C36 H36A 0.9600 . ? C36 H36B 0.9600 . ? C36 H36C 0.9600 . ? C37 H37 0.9300 . ? C39 H39 0.9300 . ? C40 H40 0.9300 . ? C41 H41 0.9300 . ? C42 H42 0.9300 . ? C43 H43 0.9300 . ? C44 H44 0.9300 . ? C47 H47A 0.9700 . ? C47 H47B 0.9700 . ? C48 H48A 0.9700 . ? C48 H48B 0.9700 . ? C56 H56 0.9800 . ? C57 H57A 0.9700 . ? C57 H57B 0.9700 . ? C60 H60A 0.9700 . ? C60 H60B 0.9700 . ? C61 H61A 0.9700 . ? C61 H61B 0.9700 . ? C63 H63 0.9300 . ? C64 H64 0.9300 . ? C66 H66 0.9300 . ? C67 H67 0.9300 . ? C68 H68A 0.9700 . ? C68 H68B 0.9700 . ? C69 H69A 0.9700 . ? C69 H69B 0.9700 . ? C70 H70A 0.9700 . ? C70 H70B 0.9700 . ? C71 H71A 0.9700 . ? C71 H71B 0.9700 . ? C72 H72A 0.9600 . ? C72 H72B 0.9600 . ? C72 H72C 0.9600 . ? C88 H88A 0.9700 . ? C88 H88B 0.9700 . ? C89 H89A 0.9700 . ? C89 H89B 0.9700 . ? C90 H90A 0.9700 . ? C90 H90B 0.9700 . ? C91 H91A 0.9700 . ? C91 H91B 0.9700 . ? C92 H92A 0.9600 . ? C92 H92B 0.9600 . ? C92 H92C 0.9600 . ? 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 C14 N13 C26 124.4(3) . . ? C14 N13 C12 119.3(4) . . ? C26 N13 C12 116.3(4) . . ? C50 N49 C62 123.4(3) . . ? C50 N49 C48 119.2(3) . . ? C62 N49 C48 117.3(3) . . ? C2 C1 C9 121.3(4) . . ? C1 C2 C3 118.6(4) . . ? C1 C2 C11 121.8(4) . . ? C3 C2 C11 119.6(4) . . ? C4 C3 C2 121.5(4) . . ? C3 C4 C10 120.8(4) . . ? C6 C5 C10 121.2(5) . . ? C5 C6 C7 120.5(5) . . ? C8 C7 C6 121.2(5) . . ? C7 C8 C9 119.7(5) . . ? C10 C9 C1 119.1(4) . . ? C10 C9 C8 118.5(4) . . ? C1 C9 C8 122.4(4) . . ? C9 C10 C4 118.6(4) . . ? C9 C10 C5 118.8(4) . . ? C4 C10 C5 122.6(4) . . ? C12 C11 C2 111.4(4) . . ? N13 C12 C11 110.9(4) . . ? O15 C14 N13 120.9(4) . . ? O15 C14 C20 120.7(4) . . ? N13 C14 C20 118.4(3) . . ? C21 C20 C14 110.0(3) . . ? C21 C20 C25 110.8(3) . . ? C14 C20 C25 111.5(4) . . ? C22 C21 C20 110.3(3) . . ? F17 C22 F16 104.9(4) . . ? F17 C22 C23 109.5(4) . . ? F16 C22 C23 107.2(4) . . ? F17 C22 C21 111.5(4) . . ? F16 C22 C21 108.9(4) . . ? C23 C22 C21 114.4(4) . . ? O19 C23 O18 111.4(3) . . ? O19 C23 C22 106.5(3) . . ? O18 C23 C22 110.4(4) . . ? O19 C23 C24 111.7(4) . . ? O18 C23 C24 108.3(3) . . ? C22 C23 C24 108.5(3) . . ? C25 C24 C23 111.3(3) . . ? C24 C25 C20 111.1(4) . . ? C27 C26 C31 119.7(4) . . ? C27 C26 N13 119.4(4) . . ? C31 C26 N13 120.7(4) . . ? C26 C27 C28 120.0(4) . . ? C27 C28 C29 120.9(5) . . ? C30 C29 C28 117.9(5) . . ? C30 C29 C32 120.4(5) . . ? C28 C29 C32 121.7(6) . . ? C29 C30 C31 121.8(5) . . ? C26 C31 C30 119.5(5) . . ? C33 C32 C29 116.9(6) . . ? C32 C33 C74 123.3(7) . . ? C32 C33 C34 107.2(7) . . ? C74 C33 C34 26.4(8) . . ? C35 C34 C33 114.5(9) . . ? C36 C35 C34 132.1(15) . . ? C33 C74 C75 122.2(10) . . ? C36 C75 C74 108.2(10) . . ? C75 C36 C35 47.1(9) . . ? C38 C37 C45 119.8(4) . . ? C37 C38 C39 120.1(4) . . ? C37 C38 C47 119.5(4) . . ? C39 C38 C47 120.4(4) . . ? C40 C39 C38 121.6(5) . . ? C39 C40 C46 120.1(5) . . ? C42 C41 C46 121.4(6) . . ? C41 C42 C43 121.7(6) . . ? C44 C43 C42 118.6(5) . . ? C43 C44 C45 120.8(6) . . ? C44 C45 C46 119.6(5) . . ? C44 C45 C37 121.2(5) . . ? C46 C45 C37 119.2(4) . . ? C40 C46 C45 119.2(4) . . ? C40 C46 C41 123.0(5) . . ? C45 C46 C41 117.8(5) . . ? C48 C47 C38 110.6(3) . . ? N49 C48 C47 112.9(3) . . ? O51 C50 N49 120.9(4) . . ? O51 C50 C56 120.9(4) . . ? N49 C50 C56 118.1(3) . . ? C57 C56 C50 112.5(3) . . ? C57 C56 C61 109.9(3) . . ? C50 C56 C61 109.0(3) . . ? C56 C57 C58 110.1(3) . . ? F53 C58 F52 104.9(3) . . ? F53 C58 C57 108.7(3) . . ? F52 C58 C57 110.7(3) . . ? F53 C58 C59 109.1(3) . . ? F52 C58 C59 109.4(3) . . ? C57 C58 C59 113.6(3) . . ? O54 C59 O55 110.8(3) . . ? O54 C59 C60 113.1(4) . . ? O55 C59 C60 107.0(3) . . ? O54 C59 C58 105.7(3) . . ? O55 C59 C58 110.8(3) . . ? C60 C59 C58 109.5(3) . . ? C59 C60 C61 112.5(4) . . ? C60 C61 C56 110.9(4) . . ? C67 C62 C63 119.7(4) . . ? C67 C62 N49 119.6(4) . . ? C63 C62 N49 120.6(4) . . ? C64 C63 C62 120.1(5) . . ? C85 C64 C63 119.8(8) . . ? C85 C64 C65 27.7(7) . . ? C63 C64 C65 121.1(6) . . ? C66 C65 C64 113.8(6) . . ? C66 C65 C68 121.6(10) . . ? C64 C65 C68 124.0(9) . . ? C64 C85 C88 127.2(14) . . ? C64 C85 C66 112.1(10) . . ? C88 C85 C66 109.7(15) . . ? C67 C66 C65 122.3(6) . . ? C67 C66 C85 115.8(7) . . ? C65 C66 C85 26.0(6) . . ? C66 C67 C62 120.1(5) . . ? C69 C68 C65 112.4(12) . . ? C68 C69 C70 119.7(18) . . ? C71 C70 C69 112(3) . . ? C70 C71 C72 87(2) . . ? C89 C88 C85 120.8(16) . . ? C88 C89 C90 113.5(17) . . ? C91 C90 C89 103.3(15) . . ? C90 C91 C92 93.4(17) . . ? C23 O18 H18 109.5 . . ? C23 O19 H19 109.5 . . ? C59 O54 H54 109.5 . . ? C59 O55 H55 109.5 . . ? C2 C1 H1 119.4 . . ? C9 C1 H1 119.4 . . ? C4 C3 H3 119.2 . . ? C2 C3 H3 119.2 . . ? C3 C4 H4 119.6 . . ? C10 C4 H4 119.6 . . ? C6 C5 H5 119.4 . . ? C10 C5 H5 119.4 . . ? C5 C6 H6 119.8 . . ? C7 C6 H6 119.8 . . ? C8 C7 H7 119.4 . . ? C6 C7 H7 119.4 . . ? C7 C8 H8 120.2 . . ? C9 C8 H8 120.2 . . ? C12 C11 H11A 109.3 . . ? C2 C11 H11A 109.3 . . ? C12 C11 H11B 109.3 . . ? C2 C11 H11B 109.3 . . ? H11A C11 H11B 108.0 . . ? N13 C12 H12A 109.5 . . ? C11 C12 H12A 109.5 . . ? N13 C12 H12B 109.5 . . ? C11 C12 H12B 109.5 . . ? H12A C12 H12B 108.1 . . ? C21 C20 H20 108.1 . . ? C14 C20 H20 108.1 . . ? C25 C20 H20 108.1 . . ? C22 C21 H21A 109.6 . . ? C20 C21 H21A 109.6 . . ? C22 C21 H21B 109.6 . . ? C20 C21 H21B 109.6 . . ? H21A C21 H21B 108.1 . . ? C25 C24 H24A 109.4 . . ? C23 C24 H24A 109.4 . . ? C25 C24 H24B 109.4 . . ? C23 C24 H24B 109.4 . . ? H24A C24 H24B 108.0 . . ? C24 C25 H25A 109.4 . . ? C20 C25 H25A 109.4 . . ? C24 C25 H25B 109.4 . . ? C20 C25 H25B 109.4 . . ? H25A C25 H25B 108.0 . . ? C26 C27 H27 120.0 . . ? C28 C27 H27 120.0 . . ? C27 C28 H28 119.6 . . ? C29 C28 H28 119.6 . . ? C29 C30 H30 119.1 . . ? C31 C30 H30 119.1 . . ? C26 C31 H31 120.2 . . ? C30 C31 H31 120.2 . . ? C33 C32 H32A 108.1 . . ? C29 C32 H32A 108.1 . . ? C33 C32 H32B 108.1 . . ? C29 C32 H32B 108.1 . . ? H32A C32 H32B 107.3 . . ? C32 C33 H33A 110.3 . . ? C74 C33 H33A 116.0 . . ? C34 C33 H33A 110.3 . . ? C32 C33 H33B 110.3 . . ? C74 C33 H33B 84.4 . . ? C34 C33 H33B 110.3 . . ? H33A C33 H33B 108.5 . . ? C35 C34 H34A 108.6 . . ? C33 C34 H34A 108.6 . . ? C35 C34 H34B 108.6 . . ? C33 C34 H34B 108.6 . . ? H34A C34 H34B 107.6 . . ? C36 C35 H35A 104.2 . . ? C34 C35 H35A 104.2 . . ? C36 C35 H35B 104.2 . . ? C34 C35 H35B 104.2 . . ? H35A C35 H35B 105.5 . . ? C33 C74 H74A 106.8 . . ? C75 C74 H74A 106.8 . . ? C33 C74 H74B 106.8 . . ? C75 C74 H74B 106.8 . . ? H74A C74 H74B 106.6 . . ? C36 C75 H75A 110.1 . . ? C74 C75 H75A 110.1 . . ? C36 C75 H75B 110.1 . . ? C74 C75 H75B 110.1 . . ? H75A C75 H75B 108.4 . . ? C75 C36 H36A 112.9 . . ? C35 C36 H36A 109.5 . . ? C75 C36 H36B 64.2 . . ? C35 C36 H36B 109.5 . . ? H36A C36 H36B 109.5 . . ? C75 C36 H36C 136.6 . . ? C35 C36 H36C 109.5 . . ? H36A C36 H36C 109.5 . . ? H36B C36 H36C 109.5 . . ? C38 C37 H37 120.1 . . ? C45 C37 H37 120.1 . . ? C40 C39 H39 119.2 . . ? C38 C39 H39 119.2 . . ? C39 C40 H40 119.9 . . ? C46 C40 H40 119.9 . . ? C42 C41 H41 119.3 . . ? C46 C41 H41 119.3 . . ? C41 C42 H42 119.2 . . ? C43 C42 H42 119.2 . . ? C44 C43 H43 120.7 . . ? C42 C43 H43 120.7 . . ? C43 C44 H44 119.6 . . ? C45 C44 H44 119.6 . . ? C48 C47 H47A 109.5 . . ? C38 C47 H47A 109.5 . . ? C48 C47 H47B 109.5 . . ? C38 C47 H47B 109.5 . . ? H47A C47 H47B 108.1 . . ? N49 C48 H48A 109.0 . . ? C47 C48 H48A 109.0 . . ? N49 C48 H48B 109.0 . . ? C47 C48 H48B 109.0 . . ? H48A C48 H48B 107.8 . . ? C57 C56 H56 108.4 . . ? C50 C56 H56 108.4 . . ? C61 C56 H56 108.4 . . ? C56 C57 H57A 109.6 . . ? C58 C57 H57A 109.6 . . ? C56 C57 H57B 109.6 . . ? C58 C57 H57B 109.6 . . ? H57A C57 H57B 108.2 . . ? C59 C60 H60A 109.1 . . ? C61 C60 H60A 109.1 . . ? C59 C60 H60B 109.1 . . ? C61 C60 H60B 109.1 . . ? H60A C60 H60B 107.8 . . ? C60 C61 H61A 109.5 . . ? C56 C61 H61A 109.5 . . ? C60 C61 H61B 109.5 . . ? C56 C61 H61B 109.5 . . ? H61A C61 H61B 108.1 . . ? C64 C63 H63 119.9 . . ? C62 C63 H63 119.9 . . ? C85 C64 H64 113.2 . . ? C63 C64 H64 119.5 . . ? C65 C64 H64 119.5 . . ? C67 C66 H66 118.8 . . ? C65 C66 H66 118.8 . . ? C85 C66 H66 118.8 . . ? C66 C67 H67 120.0 . . ? C62 C67 H67 120.0 . . ? C69 C68 H68A 109.1 . . ? C65 C68 H68A 109.1 . . ? C69 C68 H68B 109.1 . . ? C65 C68 H68B 109.1 . . ? H68A C68 H68B 107.9 . . ? C68 C69 H69A 107.4 . . ? C70 C69 H69A 107.4 . . ? C68 C69 H69B 107.4 . . ? C70 C69 H69B 107.4 . . ? H69A C69 H69B 106.9 . . ? C71 C70 H70A 109.2 . . ? C69 C70 H70A 109.2 . . ? C71 C70 H70B 109.2 . . ? C69 C70 H70B 109.2 . . ? H70A C70 H70B 107.9 . . ? C70 C71 H71A 114.1 . . ? C72 C71 H71A 114.1 . . ? C70 C71 H71B 114.2 . . ? C72 C71 H71B 114.2 . . ? H71A C71 H71B 111.3 . . ? C71 C72 H72A 109.5 . . ? C71 C72 H72B 109.5 . . ? H72A C72 H72B 109.5 . . ? C71 C72 H72C 109.5 . . ? H72A C72 H72C 109.5 . . ? H72B C72 H72C 109.5 . . ? C89 C88 H88A 107.1 . . ? C85 C88 H88A 107.1 . . ? C89 C88 H88B 107.1 . . ? C85 C88 H88B 107.1 . . ? H88A C88 H88B 106.8 . . ? C88 C89 H89A 108.9 . . ? C90 C89 H89A 108.9 . . ? C88 C89 H89B 108.9 . . ? C90 C89 H89B 108.9 . . ? H89A C89 H89B 107.7 . . ? C91 C90 H90A 111.1 . . ? C89 C90 H90A 111.1 . . ? C91 C90 H90B 111.1 . . ? C89 C90 H90B 111.1 . . ? H90A C90 H90B 109.1 . . ? C90 C91 H91A 113.0 . . ? C92 C91 H91A 113.0 . . ? C90 C91 H91B 113.0 . . ? C92 C91 H91B 113.0 . . ? H91A C91 H91B 110.4 . . ? C91 C92 H92A 109.5 . . ? C91 C92 H92B 109.5 . . ? H92A C92 H92B 109.5 . . ? C91 C92 H92C 109.5 . . ? H92A C92 H92C 109.5 . . ? H92B C92 H92C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C9 C1 C2 C3 -0.5(7) . . . . ? C9 C1 C2 C11 178.1(4) . . . . ? C1 C2 C3 C4 -1.0(7) . . . . ? C11 C2 C3 C4 -179.6(5) . . . . ? C2 C3 C4 C10 2.2(7) . . . . ? C10 C5 C6 C7 -2.2(10) . . . . ? C5 C6 C7 C8 4.2(11) . . . . ? C6 C7 C8 C9 -4.3(9) . . . . ? C2 C1 C9 C10 0.8(7) . . . . ? C2 C1 C9 C8 -178.0(5) . . . . ? C7 C8 C9 C10 2.4(8) . . . . ? C7 C8 C9 C1 -178.8(5) . . . . ? C1 C9 C10 C4 0.4(7) . . . . ? C8 C9 C10 C4 179.3(5) . . . . ? C1 C9 C10 C5 -179.3(5) . . . . ? C8 C9 C10 C5 -0.5(7) . . . . ? C3 C4 C10 C9 -1.9(7) . . . . ? C3 C4 C10 C5 177.8(5) . . . . ? C6 C5 C10 C9 0.4(8) . . . . ? C6 C5 C10 C4 -179.3(6) . . . . ? C1 C2 C11 C12 -106.2(5) . . . . ? C3 C2 C11 C12 72.4(6) . . . . ? C14 N13 C12 C11 91.2(5) . . . . ? C26 N13 C12 C11 -87.8(5) . . . . ? C2 C11 C12 N13 178.5(4) . . . . ? C26 N13 C14 O15 -174.4(4) . . . . ? C12 N13 C14 O15 6.7(7) . . . . ? C26 N13 C14 C20 4.6(6) . . . . ? C12 N13 C14 C20 -174.3(4) . . . . ? O15 C14 C20 C21 -27.8(6) . . . . ? N13 C14 C20 C21 153.2(4) . . . . ? O15 C14 C20 C25 95.6(5) . . . . ? N13 C14 C20 C25 -83.4(5) . . . . ? C14 C20 C21 C22 178.1(4) . . . . ? C25 C20 C21 C22 54.3(5) . . . . ? C20 C21 C22 F17 179.5(4) . . . . ? C20 C21 C22 F16 64.3(5) . . . . ? C20 C21 C22 C23 -55.5(5) . . . . ? F17 C22 C23 O19 61.1(4) . . . . ? F16 C22 C23 O19 174.3(3) . . . . ? C21 C22 C23 O19 -65.0(4) . . . . ? F17 C22 C23 O18 -60.0(4) . . . . ? F16 C22 C23 O18 53.2(4) . . . . ? C21 C22 C23 O18 173.9(3) . . . . ? F17 C22 C23 C24 -178.6(3) . . . . ? F16 C22 C23 C24 -65.3(4) . . . . ? C21 C22 C23 C24 55.4(5) . . . . ? O19 C23 C24 C25 61.5(5) . . . . ? O18 C23 C24 C25 -175.4(4) . . . . ? C22 C23 C24 C25 -55.6(5) . . . . ? C23 C24 C25 C20 57.9(5) . . . . ? C21 C20 C25 C24 -56.7(5) . . . . ? C14 C20 C25 C24 -179.6(4) . . . . ? C14 N13 C26 C27 101.0(5) . . . . ? C12 N13 C26 C27 -80.0(5) . . . . ? C14 N13 C26 C31 -83.4(6) . . . . ? C12 N13 C26 C31 95.6(5) . . . . ? C31 C26 C27 C28 -0.5(7) . . . . ? N13 C26 C27 C28 175.2(5) . . . . ? C26 C27 C28 C29 -0.7(9) . . . . ? C27 C28 C29 C30 3.2(9) . . . . ? C27 C28 C29 C32 -176.4(6) . . . . ? C28 C29 C30 C31 -4.6(9) . . . . ? C32 C29 C30 C31 174.9(6) . . . . ? C27 C26 C31 C30 -0.9(7) . . . . ? N13 C26 C31 C30 -176.5(4) . . . . ? C29 C30 C31 C26 3.6(9) . . . . ? C30 C29 C32 C33 66.5(10) . . . . ? C28 C29 C32 C33 -113.9(8) . . . . ? C29 C32 C33 C74 -162.0(11) . . . . ? C29 C32 C33 C34 174.8(9) . . . . ? C32 C33 C34 C35 -175.0(12) . . . . ? C74 C33 C34 C35 53(2) . . . . ? C33 C34 C35 C36 -124.2(19) . . . . ? C32 C33 C74 C75 162.7(14) . . . . ? C34 C33 C74 C75 -139(3) . . . . ? C33 C74 C75 C36 156.8(16) . . . . ? C74 C75 C36 C35 -42.5(14) . . . . ? C34 C35 C36 C75 81(2) . . . . ? C45 C37 C38 C39 -1.4(7) . . . . ? C45 C37 C38 C47 178.8(4) . . . . ? C37 C38 C39 C40 -0.3(7) . . . . ? C47 C38 C39 C40 179.5(5) . . . . ? C38 C39 C40 C46 2.0(8) . . . . ? C46 C41 C42 C43 -1.6(10) . . . . ? C41 C42 C43 C44 -0.4(10) . . . . ? C42 C43 C44 C45 0.4(9) . . . . ? C43 C44 C45 C46 1.6(8) . . . . ? C43 C44 C45 C37 178.2(5) . . . . ? C38 C37 C45 C44 -175.3(5) . . . . ? C38 C37 C45 C46 1.4(7) . . . . ? C39 C40 C46 C45 -2.0(8) . . . . ? C39 C40 C46 C41 178.5(5) . . . . ? C44 C45 C46 C40 177.0(5) . . . . ? C37 C45 C46 C40 0.3(7) . . . . ? C44 C45 C46 C41 -3.4(7) . . . . ? C37 C45 C46 C41 179.9(5) . . . . ? C42 C41 C46 C40 -177.0(6) . . . . ? C42 C41 C46 C45 3.5(8) . . . . ? C37 C38 C47 C48 73.6(6) . . . . ? C39 C38 C47 C48 -106.1(5) . . . . ? C50 N49 C48 C47 87.6(5) . . . . ? C62 N49 C48 C47 -88.3(5) . . . . ? C38 C47 C48 N49 175.6(4) . . . . ? C62 N49 C50 O51 172.2(4) . . . . ? C48 N49 C50 O51 -3.5(6) . . . . ? C62 N49 C50 C56 -11.0(6) . . . . ? C48 N49 C50 C56 173.3(4) . . . . ? O51 C50 C56 C57 -22.7(6) . . . . ? N49 C50 C56 C57 160.5(4) . . . . ? O51 C50 C56 C61 99.5(5) . . . . ? N49 C50 C56 C61 -77.3(5) . . . . ? C50 C56 C57 C58 179.5(3) . . . . ? C61 C56 C57 C58 57.8(4) . . . . ? C56 C57 C58 F53 65.1(5) . . . . ? C56 C57 C58 F52 179.8(4) . . . . ? C56 C57 C58 C59 -56.6(4) . . . . ? F53 C58 C59 O54 169.7(3) . . . . ? F52 C58 C59 O54 55.5(4) . . . . ? C57 C58 C59 O54 -68.8(4) . . . . ? F53 C58 C59 O55 49.6(4) . . . . ? F52 C58 C59 O55 -64.6(4) . . . . ? C57 C58 C59 O55 171.1(3) . . . . ? F53 C58 C59 C60 -68.2(4) . . . . ? F52 C58 C59 C60 177.6(3) . . . . ? C57 C58 C59 C60 53.2(4) . . . . ? O54 C59 C60 C61 65.2(5) . . . . ? O55 C59 C60 C61 -172.6(4) . . . . ? C58 C59 C60 C61 -52.4(5) . . . . ? C59 C60 C61 C56 56.4(5) . . . . ? C57 C56 C61 C60 -58.1(4) . . . . ? C50 C56 C61 C60 178.2(3) . . . . ? C50 N49 C62 C67 106.3(5) . . . . ? C48 N49 C62 C67 -78.0(5) . . . . ? C50 N49 C62 C63 -73.6(6) . . . . ? C48 N49 C62 C63 102.1(5) . . . . ? C67 C62 C63 C64 -1.5(8) . . . . ? N49 C62 C63 C64 178.4(5) . . . . ? C62 C63 C64 C85 23.8(14) . . . . ? C62 C63 C64 C65 -8.3(11) . . . . ? C85 C64 C65 C66 -77.7(17) . . . . ? C63 C64 C65 C66 18.1(12) . . . . ? C85 C64 C65 C68 94.1(19) . . . . ? C63 C64 C65 C68 -170.1(9) . . . . ? C63 C64 C85 C88 -179.7(17) . . . . ? C65 C64 C85 C88 -79(2) . . . . ? C63 C64 C85 C66 -39.9(16) . . . . ? C65 C64 C85 C66 60.9(15) . . . . ? C64 C65 C66 C67 -19.5(13) . . . . ? C68 C65 C66 C67 168.5(9) . . . . ? C64 C65 C66 C85 63.4(15) . . . . ? C68 C65 C66 C85 -108.6(19) . . . . ? C64 C85 C66 C67 37.1(15) . . . . ? C88 C85 C66 C67 -176.0(12) . . . . ? C64 C85 C66 C65 -74.3(17) . . . . ? C88 C85 C66 C65 72.6(19) . . . . ? C65 C66 C67 C62 11.0(11) . . . . ? C85 C66 C67 C62 -17.9(11) . . . . ? C63 C62 C67 C66 0.4(8) . . . . ? N49 C62 C67 C66 -179.5(5) . . . . ? C66 C65 C68 C69 89(2) . . . . ? C64 C65 C68 C69 -82(2) . . . . ? C65 C68 C69 C70 -177(2) . . . . ? C68 C69 C70 C71 -56(4) . . . . ? C69 C70 C71 C72 -175(3) . . . . ? C64 C85 C88 C89 19(4) . . . . ? C66 C85 C88 C89 -122(2) . . . . ? C85 C88 C89 C90 -165(2) . . . . ? C88 C89 C90 C91 -165(3) . . . . ? C89 C90 C91 C92 -179(3) . . . . ? _diffrn_measured_fraction_theta_max 0.975 _diffrn_measured_fraction_theta_full 0.975 _refine_diff_density_max 0.475 _refine_diff_density_min -0.237 _refine_diff_density_rms 0.048 _publ_section_references ; Mackay, S., Gilmore, C. J.,Edwards, C., Stewart, N. & Shankland, K. (1999). maXus Computer Program for the Solution and Refinement of Crystal Structures. Bruker Nonius, The Netherlands, MacScience, Japan & The University of Glasgow. Johnson, C. K. (1976). ORTEP-II. A Fortran Thermal-Ellipsoid Plot Program. Report ORNL-5138. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Otwinowski, Z. and Minor, W, (1997). In Methods in Enzymology, 276, edited by C.W. Carter, Jr. & R.M. Sweet pp. 307-326, New York:Academic Press. Altomare, A., Burla, M.C., Camalli, M., Cascarano, G.L., Giacovazzo, C., Guagliardi, A., Moliterni, A.G.G & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119. Sheldrick, G. M. (1997). SHELXL97. Program for the Refinement of Crystal Structures. University of G\"ottingen, Germany. ;