# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Stefan Mecking' _publ_contact_author_email STEFAN.MECKING@UNI-KONSTANZ.DE _publ_section_title ; Zirconium enolatoimine complexes in olefin polymerization ; loop_ _publ_author_name 'Stefan Mecking' 'Inigo Gottker-Schnetmann' 'Ulrich Tritschler' 'Sze-Man Yu.' # Attachment 'gs08_035_complex2a.cif' data_d:\x_ray\gs08_035\gs08_035 _database_code_depnum_ccdc_archive 'CCDC 743815' #TrackingRef 'gs08_035_complex2a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H18 Cl2 F6 N2 O2 Zr' _chemical_formula_sum 'C22 H18 Cl2 F6 N2 O2 Zr' _chemical_formula_weight 618.50 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' 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 2/c' _symmetry_Int_Tables_number 15 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 9.7961(6) _cell_length_b 14.0461(8) _cell_length_c 18.3236(12) _cell_angle_alpha 90.00 _cell_angle_beta 95.011(5) _cell_angle_gamma 90.00 _cell_volume 2511.6(3) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 30223 _cell_measurement_theta_min 2.23 _cell_measurement_theta_max 28.32 _exptl_crystal_description 'cubic fragment' _exptl_crystal_colour colourless _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.383 _exptl_crystal_size_min 0.35 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.636 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1232 _exptl_absorpt_coefficient_mu 0.717 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.6480 _exptl_absorpt_correction_T_max 0.8723 _exptl_absorpt_process_details 'STOE X-RED32' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE IPDS 2T' _diffrn_measurement_method 'rotation method' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 18366 _diffrn_reflns_av_R_equivalents 0.1265 _diffrn_reflns_av_sigmaI/netI 0.0619 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.23 _diffrn_reflns_theta_max 28.06 _reflns_number_total 3015 _reflns_number_gt 2643 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-RED' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 ' _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0224P)^2^+6.2439P] 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 refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3015 _refine_ls_number_parameters 160 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0473 _refine_ls_R_factor_gt 0.0394 _refine_ls_wR_factor_ref 0.0736 _refine_ls_wR_factor_gt 0.0710 _refine_ls_goodness_of_fit_ref 1.103 _refine_ls_restrained_S_all 1.103 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.0000 -0.00237(2) 0.2500 0.01270(8) Uani 1 2 d S . . Cl1 Cl 0.12943(6) -0.11413(4) 0.32955(3) 0.01766(12) Uani 1 1 d . . . O1 O 0.15128(15) 0.01397(11) 0.18198(8) 0.0173(3) Uani 1 1 d . . . F2 F 0.45969(15) 0.08759(12) 0.11437(8) 0.0321(4) Uani 1 1 d . . . F1 F 0.27311(17) 0.04867(14) 0.05168(8) 0.0385(4) Uani 1 1 d . . . C4 C 0.2358(2) 0.16324(16) 0.28924(11) 0.0171(4) Uani 1 1 d . . . N1 N 0.12352(19) 0.12195(13) 0.30568(9) 0.0157(4) Uani 1 1 d . . . F3 F 0.3811(2) -0.05415(12) 0.12099(11) 0.0449(5) Uani 1 1 d . . . C3 C 0.3053(2) 0.13521(17) 0.22574(12) 0.0184(4) Uani 1 1 d . . . H3A H 0.3864 0.1685 0.2165 0.022 Uiso 1 1 calc R . . C10 C -0.0751(2) 0.26479(18) 0.43234(12) 0.0215(5) Uani 1 1 d . . . H10A H -0.1324 0.3194 0.4311 0.026 Uiso 1 1 calc R . . C6 C 0.0657(2) 0.15493(16) 0.37173(11) 0.0163(4) Uani 1 1 d . . . C9 C -0.0466(3) 0.21510(18) 0.49743(12) 0.0237(5) Uani 1 1 d . . . H9A H -0.0853 0.2354 0.5406 0.028 Uiso 1 1 calc R . . C11 C -0.0194(2) 0.23440(16) 0.36887(12) 0.0185(4) Uani 1 1 d . . . H11A H -0.0394 0.2676 0.3241 0.022 Uiso 1 1 calc R . . C5 C 0.3018(2) 0.24252(18) 0.33473(13) 0.0233(5) Uani 1 1 d . . . H5C H 0.3971 0.2500 0.3234 0.028 Uiso 1 1 calc R . . H5B H 0.2994 0.2273 0.3868 0.028 Uiso 1 1 calc R . . H5A H 0.2518 0.3019 0.3236 0.028 Uiso 1 1 calc R . . C8 C 0.0383(3) 0.13576(18) 0.49962(12) 0.0229(5) Uani 1 1 d . . . H8A H 0.0579 0.1023 0.5444 0.027 Uiso 1 1 calc R . . C2 C 0.2622(2) 0.06500(16) 0.17899(11) 0.0164(4) Uani 1 1 d . . . C1 C 0.3443(2) 0.03681(17) 0.11616(13) 0.0206(5) Uani 1 1 d . . . C7 C 0.0944(2) 0.10522(17) 0.43693(12) 0.0200(5) Uani 1 1 d . . . H7A H 0.1522 0.0508 0.4384 0.024 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 Zr1 0.01385(14) 0.01174(14) 0.01258(13) 0.000 0.00156(9) 0.000 Cl1 0.0214(3) 0.0156(3) 0.0157(2) 0.00299(19) 0.00015(18) 0.00271(19) O1 0.0179(7) 0.0158(8) 0.0185(7) -0.0008(6) 0.0040(6) -0.0020(6) F2 0.0256(8) 0.0386(9) 0.0345(8) -0.0070(7) 0.0164(6) -0.0122(7) F1 0.0333(9) 0.0639(12) 0.0188(7) -0.0084(7) 0.0056(6) -0.0005(8) C4 0.0181(10) 0.0159(11) 0.0168(10) 0.0012(8) -0.0014(8) 0.0011(8) N1 0.0194(9) 0.0169(9) 0.0108(7) 0.0011(7) 0.0004(7) 0.0012(7) F3 0.0562(11) 0.0211(9) 0.0635(12) 0.0039(8) 0.0405(9) 0.0103(7) C3 0.0172(10) 0.0175(11) 0.0207(10) 0.0016(8) 0.0026(8) -0.0025(8) C10 0.0228(11) 0.0192(11) 0.0224(11) -0.0048(9) 0.0020(9) 0.0016(9) C6 0.0177(10) 0.0153(10) 0.0158(10) -0.0035(8) 0.0004(8) -0.0017(8) C9 0.0280(12) 0.0251(13) 0.0183(10) -0.0053(9) 0.0039(9) -0.0019(10) C11 0.0213(11) 0.0162(11) 0.0178(10) -0.0010(8) 0.0004(8) -0.0009(9) C5 0.0222(11) 0.0231(12) 0.0248(11) -0.0052(10) 0.0025(9) -0.0063(9) C8 0.0304(13) 0.0228(12) 0.0154(10) 0.0012(9) 0.0019(9) -0.0022(10) C2 0.0168(10) 0.0155(11) 0.0172(10) 0.0032(8) 0.0025(8) 0.0014(8) C1 0.0209(11) 0.0178(11) 0.0240(11) -0.0007(9) 0.0076(9) -0.0027(9) C7 0.0240(11) 0.0177(11) 0.0178(10) -0.0003(9) -0.0003(8) -0.0002(9) _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 Zr1 O1 2.0310(15) 2 ? Zr1 O1 2.0310(15) . ? Zr1 N1 2.3105(19) . ? Zr1 N1 2.3105(19) 2 ? Zr1 Cl1 2.4235(5) . ? Zr1 Cl1 2.4235(5) 2 ? O1 C2 1.307(3) . ? F2 C1 1.339(3) . ? F1 C1 1.329(3) . ? C4 N1 1.302(3) . ? C4 C3 1.452(3) . ? C4 C5 1.503(3) . ? N1 C6 1.456(3) . ? F3 C1 1.328(3) . ? C3 C2 1.350(3) . ? C10 C9 1.389(3) . ? C10 C11 1.394(3) . ? C6 C7 1.391(3) . ? C6 C11 1.391(3) . ? C9 C8 1.389(4) . ? C8 C7 1.385(3) . ? C2 C1 1.514(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Zr1 O1 167.02(9) 2 . ? O1 Zr1 N1 91.47(6) 2 . ? O1 Zr1 N1 78.67(6) . . ? O1 Zr1 N1 78.67(6) 2 2 ? O1 Zr1 N1 91.47(6) . 2 ? N1 Zr1 N1 81.81(9) . 2 ? O1 Zr1 Cl1 94.33(4) 2 . ? O1 Zr1 Cl1 94.06(5) . . ? N1 Zr1 Cl1 89.87(5) . . ? N1 Zr1 Cl1 168.92(4) 2 . ? O1 Zr1 Cl1 94.06(5) 2 2 ? O1 Zr1 Cl1 94.33(4) . 2 ? N1 Zr1 Cl1 168.92(4) . 2 ? N1 Zr1 Cl1 89.87(5) 2 2 ? Cl1 Zr1 Cl1 99.26(3) . 2 ? C2 O1 Zr1 137.86(14) . . ? N1 C4 C3 121.9(2) . . ? N1 C4 C5 122.2(2) . . ? C3 C4 C5 115.9(2) . . ? C4 N1 C6 116.65(19) . . ? C4 N1 Zr1 130.92(15) . . ? C6 N1 Zr1 112.37(13) . . ? C2 C3 C4 124.3(2) . . ? C9 C10 C11 119.9(2) . . ? C7 C6 C11 120.7(2) . . ? C7 C6 N1 119.3(2) . . ? C11 C6 N1 119.95(19) . . ? C10 C9 C8 120.2(2) . . ? C6 C11 C10 119.4(2) . . ? C7 C8 C9 120.3(2) . . ? O1 C2 C3 126.1(2) . . ? O1 C2 C1 112.80(19) . . ? C3 C2 C1 121.1(2) . . ? F3 C1 F1 107.3(2) . . ? F3 C1 F2 106.8(2) . . ? F1 C1 F2 106.86(19) . . ? F3 C1 C2 111.09(19) . . ? F1 C1 C2 111.75(19) . . ? F2 C1 C2 112.65(19) . . ? C8 C7 C6 119.4(2) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O1 Zr1 O1 C2 45.8(2) 2 . . . ? N1 Zr1 O1 C2 4.6(2) . . . . ? N1 Zr1 O1 C2 86.0(2) 2 . . . ? Cl1 Zr1 O1 C2 -84.4(2) . . . . ? Cl1 Zr1 O1 C2 176.0(2) 2 . . . ? C3 C4 N1 C6 178.53(19) . . . . ? C5 C4 N1 C6 -1.3(3) . . . . ? C3 C4 N1 Zr1 1.5(3) . . . . ? C5 C4 N1 Zr1 -178.37(16) . . . . ? O1 Zr1 N1 C4 -174.08(19) 2 . . . ? O1 Zr1 N1 C4 -2.58(19) . . . . ? N1 Zr1 N1 C4 -95.8(2) 2 . . . ? Cl1 Zr1 N1 C4 91.59(19) . . . . ? Cl1 Zr1 N1 C4 -54.1(4) 2 . . . ? O1 Zr1 N1 C6 8.78(14) 2 . . . ? O1 Zr1 N1 C6 -179.72(15) . . . . ? N1 Zr1 N1 C6 87.11(14) 2 . . . ? Cl1 Zr1 N1 C6 -85.55(13) . . . . ? Cl1 Zr1 N1 C6 128.8(2) 2 . . . ? N1 C4 C3 C2 -0.5(4) . . . . ? C5 C4 C3 C2 179.3(2) . . . . ? C4 N1 C6 C7 -96.7(3) . . . . ? Zr1 N1 C6 C7 80.9(2) . . . . ? C4 N1 C6 C11 84.5(3) . . . . ? Zr1 N1 C6 C11 -97.9(2) . . . . ? C11 C10 C9 C8 0.6(4) . . . . ? C7 C6 C11 C10 0.6(3) . . . . ? N1 C6 C11 C10 179.5(2) . . . . ? C9 C10 C11 C6 -0.8(3) . . . . ? C10 C9 C8 C7 -0.4(4) . . . . ? Zr1 O1 C2 C3 -5.5(4) . . . . ? Zr1 O1 C2 C1 173.63(15) . . . . ? C4 C3 C2 O1 2.1(4) . . . . ? C4 C3 C2 C1 -176.9(2) . . . . ? O1 C2 C1 F3 -58.6(3) . . . . ? C3 C2 C1 F3 120.6(2) . . . . ? O1 C2 C1 F1 61.3(3) . . . . ? C3 C2 C1 F1 -119.5(2) . . . . ? O1 C2 C1 F2 -178.39(19) . . . . ? C3 C2 C1 F2 0.8(3) . . . . ? C9 C8 C7 C6 0.3(4) . . . . ? C11 C6 C7 C8 -0.4(3) . . . . ? N1 C6 C7 C8 -179.2(2) . . . . ? _diffrn_measured_fraction_theta_max 0.986 _diffrn_reflns_theta_full 28.06 _diffrn_measured_fraction_theta_full 0.986 _refine_diff_density_max 0.452 _refine_diff_density_min -0.497 _refine_diff_density_rms 0.103 # Attachment 'gs08_037_ligand_1d.cif' data_d:\x_ray\gs08_037 _database_code_depnum_ccdc_archive 'CCDC 743816' #TrackingRef 'gs08_037_ligand_1d.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H22 F3 N O' _chemical_formula_sum 'C17 H22 F3 N O' _chemical_formula_weight 313.36 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' 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 2/c' _symmetry_Int_Tables_number 15 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 19.4589(11) _cell_length_b 16.3091(10) _cell_length_c 11.5997(6) _cell_angle_alpha 90.00 _cell_angle_beta 112.240(4) _cell_angle_gamma 90.00 _cell_volume 3407.4(3) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 22610 _cell_measurement_theta_min 1.68 _cell_measurement_theta_max 27.76 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.400 _exptl_crystal_size_mid 0.367 _exptl_crystal_size_min 0.300 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.222 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1328 _exptl_absorpt_coefficient_mu 0.098 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.8674 _exptl_absorpt_correction_T_max 0.9867 _exptl_absorpt_process_details 'STOE X-RED32' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE IPDS 2T' _diffrn_measurement_method 'rotation method' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 26306 _diffrn_reflns_av_R_equivalents 0.1250 _diffrn_reflns_av_sigmaI/netI 0.0975 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.68 _diffrn_reflns_theta_max 27.45 _reflns_number_total 3859 _reflns_number_gt 2937 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-RED' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0670P)^2^+0.6314P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3859 _refine_ls_number_parameters 230 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0681 _refine_ls_R_factor_gt 0.0455 _refine_ls_wR_factor_ref 0.1216 _refine_ls_wR_factor_gt 0.1135 _refine_ls_goodness_of_fit_ref 1.066 _refine_ls_restrained_S_all 1.066 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group F2 F 0.00709(5) 0.15737(6) 0.05868(10) 0.0438(3) Uani 1 1 d . . . F1 F -0.02136(5) 0.12511(7) -0.13274(10) 0.0491(3) Uani 1 1 d . . . O1 O 0.15251(6) 0.10828(6) 0.11059(10) 0.0337(3) Uani 1 1 d . . . N1 N 0.21248(7) -0.03065(7) 0.07727(12) 0.0270(3) Uani 1 1 d . . . H20 H 0.2102(10) 0.0133(12) 0.1210(17) 0.036(5) Uiso 1 1 d . . . F3 F 0.05583(6) 0.22274(6) -0.05097(12) 0.0520(3) Uani 1 1 d . . . C4 C 0.15314(8) -0.03927(8) -0.02703(13) 0.0263(3) Uani 1 1 d . . . C7 C 0.26930(8) -0.15712(8) 0.18833(14) 0.0263(3) Uani 1 1 d . C . C6 C 0.27483(8) -0.08569(8) 0.12437(14) 0.0263(3) Uani 1 1 d . . . C3 C 0.09642(8) 0.01904(9) -0.06047(14) 0.0274(3) Uani 1 1 d . . . H3A H 0.0540 0.0113 -0.1348 0.033 Uiso 1 1 calc R . . C9 C 0.39855(8) -0.18346(9) 0.22872(14) 0.0288(3) Uani 1 1 d . C . H9A H 0.4415 -0.2164 0.2661 0.035 Uiso 1 1 calc R . . C12 C 0.19798(8) -0.18361(9) 0.20210(15) 0.0295(3) Uani 1 1 d . . . H12A H 0.1578 -0.1444 0.1542 0.035 Uiso 1 1 calc R A 1 C2 C 0.10023(8) 0.08839(9) 0.01213(14) 0.0270(3) Uani 1 1 d . . . C10 C 0.40184(8) -0.11415(9) 0.16208(15) 0.0301(3) Uani 1 1 d . . . H10A H 0.4469 -0.1010 0.1523 0.036 Uiso 1 1 calc R . . C11 C 0.34046(8) -0.06361(9) 0.10932(14) 0.0293(3) Uani 1 1 d . B . C5 C 0.14830(9) -0.11191(10) -0.10826(15) 0.0337(3) Uani 1 1 d . . . H5A H 0.1306 -0.1595 -0.0758 0.040 Uiso 1 1 calc R . . H5B H 0.1975 -0.1237 -0.1090 0.040 Uiso 1 1 calc R . . H5C H 0.1136 -0.1001 -0.1932 0.040 Uiso 1 1 calc R . . C8 C 0.33289(8) -0.20491(9) 0.24113(14) 0.0275(3) Uani 1 1 d . . . H8A H 0.3312 -0.2529 0.2863 0.033 Uiso 1 1 calc R C . C1 C 0.03497(8) 0.14814(9) -0.02988(16) 0.0328(3) Uani 1 1 d . . . C15 C 0.34520(9) 0.01313(10) 0.03855(18) 0.0384(4) Uani 1 1 d . . . H15A H 0.2942 0.0212 -0.0258 0.046 Uiso 0.610(6) 1 calc PR B 1 H15B H 0.2990 0.0492 0.0281 0.053(15) Uiso 0.390(6) 1 d PR B 2 C14 C 0.17491(9) -0.26957(10) 0.14838(18) 0.0378(4) Uani 1 1 d . C 1 H14A H 0.2110 -0.3098 0.1996 0.045 Uiso 1 1 calc R C 1 H14B H 0.1733 -0.2715 0.0629 0.045 Uiso 1 1 calc R C 1 H14C H 0.1257 -0.2825 0.1482 0.045 Uiso 1 1 calc R C 1 C13 C 0.20588(10) -0.18171(12) 0.33806(17) 0.0416(4) Uani 1 1 d . C 1 H13A H 0.2163 -0.1255 0.3698 0.050 Uiso 1 1 calc R C 1 H13B H 0.2468 -0.2177 0.3874 0.050 Uiso 1 1 calc R C 1 H13C H 0.1596 -0.2007 0.3443 0.050 Uiso 1 1 calc R C 1 C17 C 0.3970(3) 0.0024(2) -0.0364(4) 0.0468(9) Uani 0.610(6) 1 d P B 1 H17A H 0.3840 -0.0484 -0.0851 0.056 Uiso 0.610(6) 1 calc PR B 1 H17B H 0.4489 -0.0003 0.0218 0.056 Uiso 0.610(6) 1 calc PR B 1 H17C H 0.3905 0.0491 -0.0927 0.056 Uiso 0.610(6) 1 calc PR B 1 C16 C 0.3613(2) 0.08666(16) 0.1124(3) 0.0432(10) Uani 0.610(6) 1 d P B 1 H16A H 0.4101 0.0817 0.1799 0.052 Uiso 0.610(6) 1 calc PR B 1 H16B H 0.3233 0.0947 0.1478 0.052 Uiso 0.610(6) 1 calc PR B 1 H16C H 0.3613 0.1337 0.0599 0.052 Uiso 0.610(6) 1 calc PR B 1 C18 C 0.4175(3) 0.0685(3) 0.1334(5) 0.0478(17) Uani 0.390(6) 1 d P B 2 H18A H 0.4640 0.0414 0.1412 0.057 Uiso 0.390(6) 1 calc PR B 2 H18B H 0.4146 0.0727 0.2157 0.057 Uiso 0.390(6) 1 calc PR B 2 H18C H 0.4159 0.1235 0.0985 0.057 Uiso 0.390(6) 1 calc PR B 2 C19 C 0.3543(4) -0.0022(3) -0.0711(5) 0.0433(14) Uani 0.390(6) 1 d P B 2 H19C H 0.3590 0.0498 -0.1097 0.052 Uiso 0.390(6) 1 calc PR B 2 H19B H 0.3112 -0.0324 -0.1276 0.052 Uiso 0.390(6) 1 calc PR B 2 H19A H 0.3993 -0.0350 -0.0541 0.052 Uiso 0.390(6) 1 calc PR B 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 F2 0.0428(5) 0.0453(6) 0.0511(6) -0.0046(5) 0.0265(5) 0.0083(4) F1 0.0339(5) 0.0573(7) 0.0449(6) -0.0057(5) 0.0022(4) 0.0178(4) O1 0.0353(6) 0.0281(5) 0.0322(6) -0.0055(4) 0.0066(5) 0.0031(4) N1 0.0266(6) 0.0228(6) 0.0286(7) -0.0016(5) 0.0070(5) 0.0034(5) F3 0.0474(6) 0.0315(5) 0.0818(8) 0.0190(5) 0.0296(6) 0.0105(4) C4 0.0275(7) 0.0259(7) 0.0250(7) -0.0004(6) 0.0096(6) -0.0003(5) C7 0.0266(7) 0.0237(6) 0.0280(7) -0.0029(6) 0.0096(6) -0.0001(5) C6 0.0253(7) 0.0232(7) 0.0275(7) -0.0008(6) 0.0069(6) 0.0025(5) C3 0.0257(7) 0.0275(7) 0.0260(7) 0.0003(6) 0.0063(6) 0.0019(5) C9 0.0262(7) 0.0277(7) 0.0306(8) 0.0014(6) 0.0087(6) 0.0050(5) C12 0.0272(7) 0.0262(7) 0.0359(8) -0.0010(6) 0.0130(6) -0.0004(5) C2 0.0272(7) 0.0259(7) 0.0284(8) 0.0018(6) 0.0112(6) 0.0015(5) C10 0.0257(7) 0.0312(7) 0.0341(8) 0.0015(6) 0.0122(6) -0.0005(6) C11 0.0309(7) 0.0257(7) 0.0309(8) 0.0016(6) 0.0112(6) -0.0001(6) C5 0.0337(8) 0.0319(8) 0.0319(8) -0.0063(6) 0.0082(6) 0.0042(6) C8 0.0305(7) 0.0234(6) 0.0285(7) 0.0015(6) 0.0110(6) 0.0009(5) C1 0.0309(7) 0.0308(7) 0.0378(9) 0.0011(7) 0.0141(7) 0.0040(6) C15 0.0362(8) 0.0318(8) 0.0493(10) 0.0123(7) 0.0186(7) 0.0038(6) C14 0.0355(8) 0.0314(8) 0.0475(10) -0.0063(7) 0.0169(7) -0.0073(6) C13 0.0406(9) 0.0491(10) 0.0408(10) -0.0075(8) 0.0219(8) -0.0060(7) C17 0.055(2) 0.0428(17) 0.051(2) 0.0134(16) 0.030(2) 0.0016(18) C16 0.056(2) 0.0271(13) 0.0437(18) 0.0011(12) 0.0159(15) -0.0078(13) C18 0.057(4) 0.038(2) 0.046(3) 0.005(2) 0.016(2) -0.018(2) C19 0.060(4) 0.039(2) 0.033(3) 0.009(2) 0.020(3) -0.004(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 F2 C1 1.3393(19) . ? F1 C1 1.3327(19) . ? O1 C2 1.2510(18) . ? N1 C4 1.3263(19) . ? N1 C6 1.4404(18) . ? F3 C1 1.3342(18) . ? C4 C3 1.3961(19) . ? C4 C5 1.494(2) . ? C7 C8 1.393(2) . ? C7 C6 1.407(2) . ? C7 C12 1.5186(19) . ? C6 C11 1.400(2) . ? C3 C2 1.395(2) . ? C9 C8 1.384(2) . ? C9 C10 1.385(2) . ? C12 C13 1.526(2) . ? C12 C14 1.531(2) . ? C2 C1 1.527(2) . ? C10 C11 1.388(2) . ? C11 C15 1.519(2) . ? C15 C19 1.372(6) . ? C15 C16 1.438(3) . ? C15 C17 1.571(4) . ? C15 C18 1.683(5) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C4 N1 C6 126.69(13) . . ? N1 C4 C3 120.33(13) . . ? N1 C4 C5 118.99(13) . . ? C3 C4 C5 120.68(13) . . ? C8 C7 C6 117.56(13) . . ? C8 C7 C12 119.32(13) . . ? C6 C7 C12 123.11(12) . . ? C11 C6 C7 122.29(13) . . ? C11 C6 N1 118.01(12) . . ? C7 C6 N1 119.63(12) . . ? C2 C3 C4 121.92(13) . . ? C8 C9 C10 120.27(13) . . ? C7 C12 C13 111.37(13) . . ? C7 C12 C14 110.89(12) . . ? C13 C12 C14 109.79(14) . . ? O1 C2 C3 126.89(13) . . ? O1 C2 C1 114.62(13) . . ? C3 C2 C1 118.49(13) . . ? C9 C10 C11 121.13(13) . . ? C10 C11 C6 117.75(13) . . ? C10 C11 C15 120.63(13) . . ? C6 C11 C15 121.62(13) . . ? C9 C8 C7 120.95(14) . . ? F1 C1 F3 107.28(14) . . ? F1 C1 F2 106.49(12) . . ? F3 C1 F2 106.13(13) . . ? F1 C1 C2 114.12(13) . . ? F3 C1 C2 111.49(12) . . ? F2 C1 C2 110.88(13) . . ? C19 C15 C16 129.0(3) . . ? C19 C15 C11 114.0(3) . . ? C16 C15 C11 114.15(18) . . ? C19 C15 C17 29.7(3) . . ? C16 C15 C17 112.5(2) . . ? C11 C15 C17 112.97(17) . . ? C19 C15 C18 109.5(3) . . ? C16 C15 C18 39.1(2) . . ? C11 C15 C18 107.2(2) . . ? C17 C15 C18 82.5(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 C6 N1 C4 C3 179.45(13) . . . . ? C6 N1 C4 C5 -1.0(2) . . . . ? C8 C7 C6 C11 2.2(2) . . . . ? C12 C7 C6 C11 -177.97(14) . . . . ? C8 C7 C6 N1 -174.78(13) . . . . ? C12 C7 C6 N1 5.1(2) . . . . ? C4 N1 C6 C11 102.50(17) . . . . ? C4 N1 C6 C7 -80.4(2) . . . . ? N1 C4 C3 C2 1.1(2) . . . . ? C5 C4 C3 C2 -178.53(14) . . . . ? C8 C7 C12 C13 64.72(18) . . . . ? C6 C7 C12 C13 -115.13(17) . . . . ? C8 C7 C12 C14 -57.87(19) . . . . ? C6 C7 C12 C14 122.29(16) . . . . ? C4 C3 C2 O1 1.5(2) . . . . ? C4 C3 C2 C1 -178.71(13) . . . . ? C8 C9 C10 C11 1.8(2) . . . . ? C9 C10 C11 C6 -0.8(2) . . . . ? C9 C10 C11 C15 178.82(15) . . . . ? C7 C6 C11 C10 -1.2(2) . . . . ? N1 C6 C11 C10 175.84(13) . . . . ? C7 C6 C11 C15 179.18(14) . . . . ? N1 C6 C11 C15 -3.8(2) . . . . ? C10 C9 C8 C7 -0.7(2) . . . . ? C6 C7 C8 C9 -1.2(2) . . . . ? C12 C7 C8 C9 178.91(14) . . . . ? O1 C2 C1 F1 -178.07(13) . . . . ? C3 C2 C1 F1 2.1(2) . . . . ? O1 C2 C1 F3 60.20(18) . . . . ? C3 C2 C1 F3 -119.61(16) . . . . ? O1 C2 C1 F2 -57.83(17) . . . . ? C3 C2 C1 F2 122.37(15) . . . . ? C10 C11 C15 C19 67.7(4) . . . . ? C6 C11 C15 C19 -112.7(4) . . . . ? C10 C11 C15 C16 -94.9(2) . . . . ? C6 C11 C15 C16 84.7(2) . . . . ? C10 C11 C15 C17 35.3(3) . . . . ? C6 C11 C15 C17 -145.1(2) . . . . ? C10 C11 C15 C18 -53.7(3) . . . . ? C6 C11 C15 C18 126.0(3) . . . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.45 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.255 _refine_diff_density_min -0.268 _refine_diff_density_rms 0.061 # Attachment 'gs09_013_complex_2d.cif' data_g:\x_ray\gs09_013 _database_code_depnum_ccdc_archive 'CCDC 743817' #TrackingRef 'gs09_013_complex_2d.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C34 H42 Cl2 F6 N2 O2 Zr' _chemical_formula_sum 'C34 H42 Cl2 F6 N2 O2 Zr' _chemical_formula_weight 786.82 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' 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.652(3) _cell_length_b 11.781(2) _cell_length_c 13.684(2) _cell_angle_alpha 74.216(12) _cell_angle_beta 82.723(17) _cell_angle_gamma 86.135(17) _cell_volume 1791.9(6) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 3096 _cell_measurement_theta_min 2.04 _cell_measurement_theta_max 27.72 _exptl_crystal_description fragment _exptl_crystal_colour colourless _exptl_crystal_size_max 0.300 _exptl_crystal_size_mid 0.227 _exptl_crystal_size_min 0.150 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.458 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 808 _exptl_absorpt_coefficient_mu 0.520 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.8674 _exptl_absorpt_correction_T_max 0.9478 _exptl_absorpt_process_details 'STOE X-RED32' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE IPDS 2T' _diffrn_measurement_method 'rotation method' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 28369 _diffrn_reflns_av_R_equivalents 0.0922 _diffrn_reflns_av_sigmaI/netI 0.0787 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.56 _diffrn_reflns_theta_max 27.43 _reflns_number_total 8067 _reflns_number_gt 6610 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-RED' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0613P)^2^+0.0000P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 8067 _refine_ls_number_parameters 434 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0516 _refine_ls_R_factor_gt 0.0364 _refine_ls_wR_factor_ref 0.0949 _refine_ls_wR_factor_gt 0.0828 _refine_ls_goodness_of_fit_ref 1.020 _refine_ls_restrained_S_all 1.020 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.790036(18) 0.727068(19) 0.743560(16) 0.01727(7) Uani 1 1 d . . . Cl2 Cl 0.75193(6) 0.60485(5) 0.91473(4) 0.03041(14) Uani 1 1 d . . . Cl1 Cl 0.93539(5) 0.59314(6) 0.69457(5) 0.03382(15) Uani 1 1 d . . . O1 O 0.64725(13) 0.83111(15) 0.76843(12) 0.0234(3) Uani 1 1 d . . . O2 O 0.82349(14) 0.85553(14) 0.60866(12) 0.0223(3) Uani 1 1 d . . . F4 F 0.82983(14) 0.97243(14) 0.41331(10) 0.0327(3) Uani 1 1 d . . . F3 F 0.45954(16) 0.97171(17) 0.82552(14) 0.0513(5) Uani 1 1 d . . . F5 F 0.70148(12) 1.06805(15) 0.48983(11) 0.0364(4) Uani 1 1 d . . . F6 F 0.87212(13) 1.13435(13) 0.44199(10) 0.0315(3) Uani 1 1 d . . . N2 N 0.90063(15) 0.85452(16) 0.79353(13) 0.0171(4) Uani 1 1 d . . . N1 N 0.65862(16) 0.66475(16) 0.65502(14) 0.0197(4) Uani 1 1 d . . . C24 C 0.86196(19) 0.8340(2) 0.97880(16) 0.0208(4) Uani 1 1 d . . . C23 C 0.93440(18) 0.80866(19) 0.89681(16) 0.0182(4) Uani 1 1 d . . . C4 C 0.56724(19) 0.7245(2) 0.62000(17) 0.0213(4) Uani 1 1 d . . . C29 C 0.7558(2) 0.9173(2) 0.96545(18) 0.0246(5) Uani 1 1 d . . . H29A H 0.7481 0.9466 0.8907 0.029 Uiso 1 1 calc R . . C22 C 0.9901(2) 1.0399(2) 0.79078(17) 0.0250(5) Uani 1 1 d . . . H22A H 1.0095 0.9949 0.8585 0.030 Uiso 1 1 calc R . . H22B H 0.9406 1.1087 0.7972 0.030 Uiso 1 1 calc R . . H22C H 1.0613 1.0663 0.7463 0.030 Uiso 1 1 calc R . . C33 C 1.1566(2) 0.5866(2) 0.8370(2) 0.0329(6) Uani 1 1 d . . . H33A H 1.0886 0.5374 0.8573 0.039 Uiso 1 1 calc R . . H33B H 1.2087 0.5640 0.8905 0.039 Uiso 1 1 calc R . . H33C H 1.1972 0.5753 0.7729 0.039 Uiso 1 1 calc R . . C27 C 1.0597(2) 0.6852(2) 1.01087(17) 0.0242(5) Uani 1 1 d . . . H27A H 1.1266 0.6349 1.0226 0.029 Uiso 1 1 calc R . . C32 C 1.11826(19) 0.7161(2) 0.82177(17) 0.0234(5) Uani 1 1 d . . . H32A H 1.0775 0.7410 0.7589 0.028 Uiso 1 1 calc R . . C19 C 0.84892(18) 0.9660(2) 0.58480(16) 0.0190(4) Uani 1 1 d . . . C20 C 0.8961(2) 1.0206(2) 0.64364(16) 0.0212(4) Uani 1 1 d . . . H20A H 0.9103 1.1023 0.6170 0.025 Uiso 1 1 calc R . . C5 C 0.4896(2) 0.6831(2) 0.5574(2) 0.0290(5) Uani 1 1 d . . . H5A H 0.5160 0.6042 0.5516 0.035 Uiso 1 1 calc R . . H5B H 0.4922 0.7381 0.4891 0.035 Uiso 1 1 calc R . . H5C H 0.4099 0.6800 0.5910 0.035 Uiso 1 1 calc R . . C2 C 0.56698(19) 0.8792(2) 0.71053(17) 0.0218(4) Uani 1 1 d . . . C11 C 0.7486(2) 0.5510(2) 0.5370(2) 0.0274(5) Uani 1 1 d . . . C21 C 0.92680(18) 0.9628(2) 0.74526(16) 0.0190(4) Uani 1 1 d . . . C25 C 0.8919(2) 0.7812(2) 1.07709(17) 0.0248(5) Uani 1 1 d . . . H25A H 0.8449 0.7969 1.1342 0.030 Uiso 1 1 calc R . . C3 C 0.52919(19) 0.8366(2) 0.63931(17) 0.0225(5) Uani 1 1 d . . . H3A H 0.4737 0.8831 0.5989 0.027 Uiso 1 1 calc R . . C28 C 1.03496(19) 0.7364(2) 0.91034(17) 0.0203(4) Uani 1 1 d . . . C6 C 0.68541(19) 0.5522(2) 0.63109(18) 0.0234(5) Uani 1 1 d . . . C18 C 0.8145(2) 1.0359(2) 0.48133(16) 0.0226(5) Uani 1 1 d . . . C10 C 0.7748(2) 0.4416(3) 0.5177(2) 0.0348(6) Uani 1 1 d . . . H10A H 0.8173 0.4375 0.4546 0.042 Uiso 1 1 calc R . . C15 C 0.7875(2) 0.6626(2) 0.45602(19) 0.0324(6) Uani 1 1 d . . . H15A H 0.7654 0.7315 0.4848 0.039 Uiso 1 1 calc R . . C9 C 0.7398(2) 0.3387(2) 0.5891(2) 0.0379(7) Uani 1 1 d . . . H9A H 0.7585 0.2649 0.5744 0.046 Uiso 1 1 calc R . . C8 C 0.6784(2) 0.3418(2) 0.6810(2) 0.0359(6) Uani 1 1 d . . . H8A H 0.6551 0.2701 0.7290 0.043 Uiso 1 1 calc R . . F1 F 0.59493(15) 1.06872(16) 0.72530(18) 0.0550(5) Uani 1 1 d . . . F2 F 0.43798(16) 1.04566(16) 0.66869(15) 0.0527(5) Uani 1 1 d . . . C7 C 0.6496(2) 0.4486(2) 0.7050(2) 0.0277(5) Uani 1 1 d . . . C26 C 0.9886(2) 0.7066(2) 1.09303(18) 0.0274(5) Uani 1 1 d . . . H26A H 1.0061 0.6700 1.1607 0.033 Uiso 1 1 calc R . . C30 C 0.6450(2) 0.8548(2) 1.0185(2) 0.0308(5) Uani 1 1 d . . . H30A H 0.6505 0.8258 1.0920 0.037 Uiso 1 1 calc R . . H30B H 0.6350 0.7882 0.9906 0.037 Uiso 1 1 calc R . . H30C H 0.5785 0.9104 1.0067 0.037 Uiso 1 1 calc R . . C1 C 0.5138(2) 0.9916(2) 0.7327(2) 0.0290(5) Uani 1 1 d . . . C12 C 0.5776(2) 0.4505(2) 0.8046(2) 0.0318(5) Uani 1 1 d . . . H12A H 0.5874 0.5284 0.8179 0.038 Uiso 1 1 calc R . . C31 C 0.7700(2) 1.0244(2) 1.0060(2) 0.0314(5) Uani 1 1 d . . . H31A H 0.8420 1.0631 0.9728 0.038 Uiso 1 1 calc R . . H31B H 0.7729 0.9981 1.0801 0.038 Uiso 1 1 calc R . . H31C H 0.7043 1.0802 0.9910 0.038 Uiso 1 1 calc R . . C34 C 1.2238(2) 0.7924(3) 0.8044(2) 0.0340(6) Uani 1 1 d . . . H34A H 1.2758 0.7800 0.7457 0.041 Uiso 1 1 calc R . . H34B H 1.2648 0.7703 0.8655 0.041 Uiso 1 1 calc R . . H34C H 1.1986 0.8757 0.7908 0.041 Uiso 1 1 calc R . . C14 C 0.6145(3) 0.3537(3) 0.8957(2) 0.0426(7) Uani 1 1 d . . . H14A H 0.6983 0.3556 0.8970 0.051 Uiso 1 1 calc R . . H14B H 0.5950 0.2766 0.8894 0.051 Uiso 1 1 calc R . . H14C H 0.5740 0.3669 0.9591 0.051 Uiso 1 1 calc R . . C17 C 0.9184(3) 0.6617(3) 0.4273(2) 0.0419(7) Uani 1 1 d . . . H17A H 0.9428 0.5919 0.4031 0.050 Uiso 1 1 calc R . . H17B H 0.9571 0.6595 0.4874 0.050 Uiso 1 1 calc R . . H17C H 0.9394 0.7331 0.3731 0.050 Uiso 1 1 calc R . . C16 C 0.7263(3) 0.6800(3) 0.3598(2) 0.0519(9) Uani 1 1 d . . . H16A H 0.6429 0.6709 0.3793 0.062 Uiso 1 1 calc R . . H16B H 0.7566 0.6209 0.3238 0.062 Uiso 1 1 calc R . . H16C H 0.7405 0.7593 0.3148 0.062 Uiso 1 1 calc R . . C13 C 0.4488(2) 0.4397(3) 0.7968(2) 0.0465(8) Uani 1 1 d . . . H13A H 0.4378 0.3665 0.7786 0.056 Uiso 1 1 calc R . . H13B H 0.4225 0.5073 0.7440 0.056 Uiso 1 1 calc R . . H13C H 0.4040 0.4383 0.8627 0.056 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 Zr1 0.01762(10) 0.01535(11) 0.02084(11) -0.00607(8) -0.00782(7) 0.00116(7) Cl2 0.0417(3) 0.0238(3) 0.0259(3) -0.0025(2) -0.0120(2) -0.0040(2) Cl1 0.0271(3) 0.0360(4) 0.0482(4) -0.0253(3) -0.0153(3) 0.0094(3) O1 0.0217(8) 0.0254(9) 0.0269(8) -0.0118(7) -0.0083(6) 0.0029(7) O2 0.0268(8) 0.0226(8) 0.0198(7) -0.0069(6) -0.0077(6) -0.0033(7) F4 0.0457(9) 0.0362(9) 0.0201(7) -0.0115(6) -0.0106(6) 0.0021(7) F3 0.0531(11) 0.0529(12) 0.0495(10) -0.0263(9) 0.0071(8) 0.0159(9) F5 0.0243(7) 0.0495(10) 0.0317(8) -0.0038(7) -0.0109(6) 0.0111(7) F6 0.0409(8) 0.0283(8) 0.0228(7) 0.0008(6) -0.0090(6) -0.0042(6) N2 0.0169(8) 0.0188(9) 0.0169(8) -0.0059(7) -0.0051(7) 0.0016(7) N1 0.0211(9) 0.0157(9) 0.0237(9) -0.0057(7) -0.0073(7) 0.0003(7) C24 0.0229(11) 0.0206(11) 0.0203(10) -0.0065(8) -0.0040(8) -0.0039(9) C23 0.0209(10) 0.0172(11) 0.0180(10) -0.0042(8) -0.0072(8) -0.0026(8) C4 0.0209(10) 0.0198(11) 0.0232(10) -0.0036(9) -0.0067(8) -0.0015(9) C29 0.0241(11) 0.0268(13) 0.0235(11) -0.0087(9) -0.0026(9) 0.0024(9) C22 0.0332(12) 0.0220(12) 0.0225(11) -0.0067(9) -0.0089(9) -0.0058(10) C33 0.0362(14) 0.0306(14) 0.0335(13) -0.0114(11) -0.0104(11) 0.0113(11) C27 0.0263(11) 0.0224(12) 0.0253(11) -0.0045(9) -0.0124(9) 0.0008(9) C32 0.0214(10) 0.0249(12) 0.0260(11) -0.0078(9) -0.0102(9) 0.0032(9) C19 0.0167(10) 0.0205(11) 0.0193(10) -0.0047(8) -0.0038(8) 0.0031(8) C20 0.0268(11) 0.0163(11) 0.0208(10) -0.0044(8) -0.0069(8) 0.0021(9) C5 0.0284(12) 0.0261(13) 0.0369(13) -0.0104(10) -0.0171(10) 0.0021(10) C2 0.0184(10) 0.0198(11) 0.0267(11) -0.0058(9) -0.0028(8) 0.0011(9) C11 0.0270(12) 0.0246(13) 0.0369(13) -0.0147(10) -0.0157(10) 0.0054(10) C21 0.0200(10) 0.0188(11) 0.0199(10) -0.0064(8) -0.0066(8) 0.0008(8) C25 0.0327(12) 0.0250(12) 0.0183(10) -0.0065(9) -0.0043(9) -0.0058(10) C3 0.0201(10) 0.0211(12) 0.0271(11) -0.0061(9) -0.0088(9) 0.0047(9) C28 0.0213(10) 0.0189(11) 0.0231(10) -0.0066(9) -0.0083(8) -0.0017(8) C6 0.0216(10) 0.0181(11) 0.0352(12) -0.0115(9) -0.0137(9) 0.0026(9) C18 0.0244(11) 0.0252(12) 0.0194(10) -0.0062(9) -0.0080(8) 0.0022(9) C10 0.0331(13) 0.0343(15) 0.0463(15) -0.0246(12) -0.0122(11) 0.0059(11) C15 0.0442(15) 0.0298(14) 0.0262(12) -0.0133(10) -0.0074(11) 0.0077(11) C9 0.0350(14) 0.0205(13) 0.0670(19) -0.0214(13) -0.0199(13) 0.0056(11) C8 0.0310(13) 0.0197(13) 0.0582(18) -0.0085(12) -0.0131(12) -0.0015(10) F1 0.0396(9) 0.0292(9) 0.1043(16) -0.0329(10) -0.0043(10) -0.0031(7) F2 0.0598(11) 0.0392(10) 0.0701(12) -0.0281(9) -0.0360(10) 0.0319(9) C7 0.0228(11) 0.0196(12) 0.0439(14) -0.0085(10) -0.0157(10) 0.0002(9) C26 0.0378(13) 0.0255(13) 0.0203(11) -0.0035(9) -0.0122(10) -0.0048(10) C30 0.0270(12) 0.0348(15) 0.0335(13) -0.0153(11) 0.0008(10) -0.0031(10) C1 0.0248(11) 0.0274(13) 0.0379(13) -0.0140(11) -0.0058(10) 0.0042(10) C12 0.0297(13) 0.0254(13) 0.0378(14) -0.0009(11) -0.0085(10) -0.0047(10) C31 0.0341(13) 0.0256(13) 0.0361(13) -0.0126(11) -0.0010(10) 0.0007(11) C34 0.0258(12) 0.0459(17) 0.0330(13) -0.0140(12) -0.0020(10) -0.0075(11) C14 0.0419(15) 0.0353(16) 0.0463(16) 0.0038(13) -0.0176(13) -0.0088(13) C17 0.0443(16) 0.0401(17) 0.0391(15) -0.0074(13) -0.0027(12) -0.0021(13) C16 0.058(2) 0.068(2) 0.0311(15) -0.0171(15) -0.0136(14) 0.0172(17) C13 0.0303(14) 0.055(2) 0.0441(16) 0.0067(14) -0.0091(12) -0.0007(13) _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 Zr1 O1 2.0481(16) . ? Zr1 O2 2.0560(16) . ? Zr1 N2 2.3293(18) . ? Zr1 N1 2.3361(18) . ? Zr1 Cl1 2.3948(8) . ? Zr1 Cl2 2.3967(8) . ? O1 C2 1.302(3) . ? O2 C19 1.298(3) . ? F4 C18 1.333(3) . ? F3 C1 1.313(3) . ? F5 C18 1.345(3) . ? F6 C18 1.326(3) . ? N2 C21 1.304(3) . ? N2 C23 1.463(3) . ? N1 C4 1.305(3) . ? N1 C6 1.455(3) . ? C24 C25 1.397(3) . ? C24 C23 1.403(3) . ? C24 C29 1.524(3) . ? C23 C28 1.403(3) . ? C4 C3 1.445(3) . ? C4 C5 1.508(3) . ? C29 C30 1.528(3) . ? C29 C31 1.536(3) . ? C22 C21 1.507(3) . ? C33 C32 1.526(3) . ? C27 C26 1.380(4) . ? C27 C28 1.401(3) . ? C32 C28 1.515(3) . ? C32 C34 1.528(3) . ? C19 C20 1.344(3) . ? C19 C18 1.519(3) . ? C20 C21 1.450(3) . ? C2 C3 1.342(3) . ? C2 C1 1.513(3) . ? C11 C10 1.392(4) . ? C11 C6 1.403(4) . ? C11 C15 1.524(4) . ? C25 C26 1.383(4) . ? C6 C7 1.405(4) . ? C10 C9 1.383(4) . ? C15 C17 1.526(4) . ? C15 C16 1.535(4) . ? C9 C8 1.375(4) . ? C8 C7 1.394(4) . ? F1 C1 1.331(3) . ? F2 C1 1.330(3) . ? C7 C12 1.512(4) . ? C12 C14 1.528(4) . ? C12 C13 1.534(4) . ? 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 Zr1 O2 84.94(7) . . ? O1 Zr1 N2 88.25(6) . . ? O2 Zr1 N2 78.64(6) . . ? O1 Zr1 N1 79.05(6) . . ? O2 Zr1 N1 83.77(6) . . ? N2 Zr1 N1 159.14(6) . . ? O1 Zr1 Cl1 169.23(5) . . ? O2 Zr1 Cl1 93.16(5) . . ? N2 Zr1 Cl1 101.80(5) . . ? N1 Zr1 Cl1 90.20(5) . . ? O1 Zr1 Cl2 89.64(5) . . ? O2 Zr1 Cl2 169.95(5) . . ? N2 Zr1 Cl2 92.77(5) . . ? N1 Zr1 Cl2 103.53(5) . . ? Cl1 Zr1 Cl2 93.70(3) . . ? C2 O1 Zr1 131.14(14) . . ? C19 O2 Zr1 134.76(14) . . ? C21 N2 C23 117.17(17) . . ? C21 N2 Zr1 128.36(14) . . ? C23 N2 Zr1 114.19(13) . . ? C4 N1 C6 117.06(18) . . ? C4 N1 Zr1 126.03(15) . . ? C6 N1 Zr1 116.78(13) . . ? C25 C24 C23 117.2(2) . . ? C25 C24 C29 119.3(2) . . ? C23 C24 C29 123.49(19) . . ? C28 C23 C24 122.66(19) . . ? C28 C23 N2 118.58(19) . . ? C24 C23 N2 118.69(19) . . ? N1 C4 C3 123.1(2) . . ? N1 C4 C5 123.7(2) . . ? C3 C4 C5 113.23(19) . . ? C24 C29 C30 111.8(2) . . ? C24 C29 C31 110.79(19) . . ? C30 C29 C31 109.8(2) . . ? C26 C27 C28 121.2(2) . . ? C28 C32 C33 112.5(2) . . ? C28 C32 C34 110.44(19) . . ? C33 C32 C34 110.1(2) . . ? O2 C19 C20 126.3(2) . . ? O2 C19 C18 113.47(18) . . ? C20 C19 C18 120.1(2) . . ? C19 C20 C21 124.2(2) . . ? O1 C2 C3 126.2(2) . . ? O1 C2 C1 113.0(2) . . ? C3 C2 C1 120.8(2) . . ? C10 C11 C6 117.3(2) . . ? C10 C11 C15 119.4(2) . . ? C6 C11 C15 123.3(2) . . ? N2 C21 C20 123.11(19) . . ? N2 C21 C22 122.98(19) . . ? C20 C21 C22 113.9(2) . . ? C26 C25 C24 121.5(2) . . ? C2 C3 C4 124.4(2) . . ? C27 C28 C23 117.3(2) . . ? C27 C28 C32 119.8(2) . . ? C23 C28 C32 122.86(19) . . ? C11 C6 C7 122.8(2) . . ? C11 C6 N1 118.9(2) . . ? C7 C6 N1 118.3(2) . . ? F6 C18 F4 107.85(18) . . ? F6 C18 F5 106.70(19) . . ? F4 C18 F5 106.76(18) . . ? F6 C18 C19 113.19(18) . . ? F4 C18 C19 111.91(19) . . ? F5 C18 C19 110.09(18) . . ? C9 C10 C11 120.8(3) . . ? C11 C15 C17 112.1(2) . . ? C11 C15 C16 111.0(2) . . ? C17 C15 C16 109.7(2) . . ? C8 C9 C10 120.9(2) . . ? C9 C8 C7 121.0(3) . . ? C8 C7 C6 117.2(3) . . ? C8 C7 C12 120.2(2) . . ? C6 C7 C12 122.6(2) . . ? C27 C26 C25 120.1(2) . . ? F3 C1 F2 107.1(2) . . ? F3 C1 F1 107.0(2) . . ? F2 C1 F1 106.7(2) . . ? F3 C1 C2 111.7(2) . . ? F2 C1 C2 113.2(2) . . ? F1 C1 C2 110.8(2) . . ? C7 C12 C14 113.1(2) . . ? C7 C12 C13 110.7(2) . . ? C14 C12 C13 109.3(2) . . ? 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 O2 Zr1 O1 C2 50.1(2) . . . . ? N2 Zr1 O1 C2 128.9(2) . . . . ? N1 Zr1 O1 C2 -34.5(2) . . . . ? Cl1 Zr1 O1 C2 -30.2(4) . . . . ? Cl2 Zr1 O1 C2 -138.4(2) . . . . ? O1 Zr1 O2 C19 64.88(19) . . . . ? N2 Zr1 O2 C19 -24.35(19) . . . . ? N1 Zr1 O2 C19 144.4(2) . . . . ? Cl1 Zr1 O2 C19 -125.75(19) . . . . ? Cl2 Zr1 O2 C19 7.3(4) . . . . ? O1 Zr1 N2 C21 -70.07(18) . . . . ? O2 Zr1 N2 C21 15.12(18) . . . . ? N1 Zr1 N2 C21 -17.9(3) . . . . ? Cl1 Zr1 N2 C21 106.01(18) . . . . ? Cl2 Zr1 N2 C21 -159.63(18) . . . . ? O1 Zr1 N2 C23 103.55(14) . . . . ? O2 Zr1 N2 C23 -171.26(15) . . . . ? N1 Zr1 N2 C23 155.68(17) . . . . ? Cl1 Zr1 N2 C23 -80.37(14) . . . . ? Cl2 Zr1 N2 C23 13.99(14) . . . . ? O1 Zr1 N1 C4 22.11(19) . . . . ? O2 Zr1 N1 C4 -63.92(19) . . . . ? N2 Zr1 N1 C4 -31.4(3) . . . . ? Cl1 Zr1 N1 C4 -157.08(19) . . . . ? Cl2 Zr1 N1 C4 109.07(18) . . . . ? O1 Zr1 N1 C6 -162.12(17) . . . . ? O2 Zr1 N1 C6 111.85(16) . . . . ? N2 Zr1 N1 C6 144.39(18) . . . . ? Cl1 Zr1 N1 C6 18.69(16) . . . . ? Cl2 Zr1 N1 C6 -75.16(16) . . . . ? C25 C24 C23 C28 -1.7(3) . . . . ? C29 C24 C23 C28 176.8(2) . . . . ? C25 C24 C23 N2 175.1(2) . . . . ? C29 C24 C23 N2 -6.4(3) . . . . ? C21 N2 C23 C28 -99.8(2) . . . . ? Zr1 N2 C23 C28 85.8(2) . . . . ? C21 N2 C23 C24 83.3(3) . . . . ? Zr1 N2 C23 C24 -91.1(2) . . . . ? C6 N1 C4 C3 178.9(2) . . . . ? Zr1 N1 C4 C3 -5.3(3) . . . . ? C6 N1 C4 C5 0.2(3) . . . . ? Zr1 N1 C4 C5 175.94(17) . . . . ? C25 C24 C29 C30 -61.4(3) . . . . ? C23 C24 C29 C30 120.1(2) . . . . ? C25 C24 C29 C31 61.5(3) . . . . ? C23 C24 C29 C31 -117.0(2) . . . . ? Zr1 O2 C19 C20 22.6(3) . . . . ? Zr1 O2 C19 C18 -154.45(15) . . . . ? O2 C19 C20 C21 0.1(4) . . . . ? C18 C19 C20 C21 177.0(2) . . . . ? Zr1 O1 C2 C3 29.9(4) . . . . ? Zr1 O1 C2 C1 -151.83(17) . . . . ? C23 N2 C21 C20 -178.4(2) . . . . ? Zr1 N2 C21 C20 -4.9(3) . . . . ? C23 N2 C21 C22 0.6(3) . . . . ? Zr1 N2 C21 C22 174.05(16) . . . . ? C19 C20 C21 N2 -7.2(4) . . . . ? C19 C20 C21 C22 173.7(2) . . . . ? C23 C24 C25 C26 -0.3(3) . . . . ? C29 C24 C25 C26 -178.9(2) . . . . ? O1 C2 C3 C4 4.3(4) . . . . ? C1 C2 C3 C4 -173.9(2) . . . . ? N1 C4 C3 C2 -14.4(4) . . . . ? C5 C4 C3 C2 164.4(2) . . . . ? C26 C27 C28 C23 -0.9(3) . . . . ? C26 C27 C28 C32 176.8(2) . . . . ? C24 C23 C28 C27 2.3(3) . . . . ? N2 C23 C28 C27 -174.5(2) . . . . ? C24 C23 C28 C32 -175.2(2) . . . . ? N2 C23 C28 C32 8.0(3) . . . . ? C33 C32 C28 C27 46.9(3) . . . . ? C34 C32 C28 C27 -76.5(3) . . . . ? C33 C32 C28 C23 -135.6(2) . . . . ? C34 C32 C28 C23 100.9(2) . . . . ? C10 C11 C6 C7 0.6(3) . . . . ? C15 C11 C6 C7 179.7(2) . . . . ? C10 C11 C6 N1 178.6(2) . . . . ? C15 C11 C6 N1 -2.2(3) . . . . ? C4 N1 C6 C11 84.1(3) . . . . ? Zr1 N1 C6 C11 -92.0(2) . . . . ? C4 N1 C6 C7 -97.8(2) . . . . ? Zr1 N1 C6 C7 86.1(2) . . . . ? O2 C19 C18 F6 -158.94(19) . . . . ? C20 C19 C18 F6 23.8(3) . . . . ? O2 C19 C18 F4 -36.8(3) . . . . ? C20 C19 C18 F4 145.9(2) . . . . ? O2 C19 C18 F5 81.7(2) . . . . ? C20 C19 C18 F5 -95.5(3) . . . . ? C6 C11 C10 C9 -0.2(4) . . . . ? C15 C11 C10 C9 -179.4(2) . . . . ? C10 C11 C15 C17 -57.8(3) . . . . ? C6 C11 C15 C17 123.1(2) . . . . ? C10 C11 C15 C16 65.2(3) . . . . ? C6 C11 C15 C16 -113.9(3) . . . . ? C11 C10 C9 C8 -0.1(4) . . . . ? C10 C9 C8 C7 0.0(4) . . . . ? C9 C8 C7 C6 0.4(4) . . . . ? C9 C8 C7 C12 177.4(2) . . . . ? C11 C6 C7 C8 -0.7(3) . . . . ? N1 C6 C7 C8 -178.7(2) . . . . ? C11 C6 C7 C12 -177.6(2) . . . . ? N1 C6 C7 C12 4.4(3) . . . . ? C28 C27 C26 C25 -1.1(4) . . . . ? C24 C25 C26 C27 1.7(4) . . . . ? O1 C2 C1 F3 -63.8(3) . . . . ? C3 C2 C1 F3 114.6(3) . . . . ? O1 C2 C1 F2 175.3(2) . . . . ? C3 C2 C1 F2 -6.3(4) . . . . ? O1 C2 C1 F1 55.4(3) . . . . ? C3 C2 C1 F1 -126.2(3) . . . . ? C8 C7 C12 C14 43.1(3) . . . . ? C6 C7 C12 C14 -140.1(2) . . . . ? C8 C7 C12 C13 -79.9(3) . . . . ? C6 C7 C12 C13 96.9(3) . . . . ? _diffrn_measured_fraction_theta_max 0.986 _diffrn_reflns_theta_full 27.43 _diffrn_measured_fraction_theta_full 0.986 _refine_diff_density_max 0.741 _refine_diff_density_min -0.691 _refine_diff_density_rms 0.085 # Attachment 'sy194_complex_2b.cif' data_g:\x_ray\sy\sy194\sy194 _database_code_depnum_ccdc_archive 'CCDC 743818' #TrackingRef 'sy194_complex_2b.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H14 Cl2 F10 N2 O2 Zr' _chemical_formula_sum 'C22 H14 Cl2 F10 N2 O2 Zr' _chemical_formula_weight 690.47 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' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 2/c' _symmetry_Int_Tables_number 15 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 10.3139(13) _cell_length_b 13.3171(14) _cell_length_c 19.161(2) _cell_angle_alpha 90.00 _cell_angle_beta 95.468(9) _cell_angle_gamma 90.00 _cell_volume 2619.8(5) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 30247 _cell_measurement_theta_min 1.46 _cell_measurement_theta_max 27.26 _exptl_crystal_description cube _exptl_crystal_colour colourless _exptl_crystal_size_max 0.380 _exptl_crystal_size_mid 0.360 _exptl_crystal_size_min 0.350 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.751 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1360 _exptl_absorpt_coefficient_mu 0.719 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.6981 _exptl_absorpt_correction_T_max 0.8501 _exptl_absorpt_process_details 'STOE X-RED32' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE IPDS 2T' _diffrn_measurement_method 'rotation method' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 17115 _diffrn_reflns_av_R_equivalents 0.0835 _diffrn_reflns_av_sigmaI/netI 0.0405 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.14 _diffrn_reflns_theta_max 26.84 _reflns_number_total 2789 _reflns_number_gt 2428 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE X-AREA' _computing_cell_refinement 'STOE X-AREA' _computing_data_reduction 'STOE X-RED' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 (Farrugia, 1997)' _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0328P)^2^+2.3521P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2789 _refine_ls_number_parameters 178 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0386 _refine_ls_R_factor_gt 0.0301 _refine_ls_wR_factor_ref 0.0720 _refine_ls_wR_factor_gt 0.0691 _refine_ls_goodness_of_fit_ref 1.056 _refine_ls_restrained_S_all 1.056 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.0000 0.00659(2) 0.2500 0.01129(9) Uani 1 2 d S . . Cl1 Cl 0.10700(5) 0.12761(4) 0.32843(3) 0.01932(13) Uani 1 1 d . . . F4 F -0.06328(13) -0.27945(10) 0.31111(6) 0.0225(3) Uani 1 1 d . . . O1 O 0.15017(13) -0.01645(11) 0.19125(7) 0.0160(3) Uani 1 1 d . . . F5 F 0.18008(14) -0.03872(10) 0.44438(7) 0.0273(3) Uani 1 1 d . . . C6 C 0.0556(2) -0.15467(16) 0.37490(11) 0.0160(4) Uani 1 1 d . . . F3 F 0.44420(14) -0.10472(12) 0.13529(8) 0.0351(4) Uani 1 1 d . . . F2 F 0.27484(15) -0.05263(17) 0.07394(8) 0.0485(5) Uani 1 1 d . . . C5 C 0.2877(2) -0.24125(18) 0.35122(13) 0.0261(5) Uani 1 1 d . . . H5A H 0.2283 -0.2983 0.3537 0.031 Uiso 1 1 calc R . . H5B H 0.3071 -0.2125 0.3981 0.031 Uiso 1 1 calc R . . H5C H 0.3687 -0.2641 0.3335 0.031 Uiso 1 1 calc R . . N1 N 0.11389(16) -0.12167(13) 0.31319(9) 0.0146(3) Uani 1 1 d . . . F1 F 0.38751(18) 0.04790(12) 0.14174(10) 0.0511(5) Uani 1 1 d . . . C10 C 0.0313(2) -0.13875(18) 0.49950(11) 0.0240(5) Uani 1 1 d . . . H10A H 0.0542 -0.1061 0.5430 0.029 Uiso 1 1 calc R . . C4 C 0.2249(2) -0.16287(15) 0.30277(11) 0.0159(4) Uani 1 1 d . . . C3 C 0.2965(2) -0.13637(16) 0.24420(11) 0.0182(4) Uani 1 1 d . . . H3A H 0.3771 -0.1695 0.2404 0.022 Uiso 1 1 calc R . . C2 C 0.25803(19) -0.06881(15) 0.19484(10) 0.0148(4) Uani 1 1 d . . . C11 C 0.0872(2) -0.11037(17) 0.44008(11) 0.0204(4) Uani 1 1 d . . . C1 C 0.3415(2) -0.04479(17) 0.13593(12) 0.0203(4) Uani 1 1 d . . . C7 C -0.0340(2) -0.23252(16) 0.37287(11) 0.0179(4) Uani 1 1 d . . . C9 C -0.0593(2) -0.21616(19) 0.49423(12) 0.0256(5) Uani 1 1 d . . . H9A H -0.0994 -0.2364 0.5346 0.031 Uiso 1 1 calc R . . C8 C -0.0919(2) -0.26418(18) 0.43110(12) 0.0236(5) Uani 1 1 d . . . H8A H -0.1529 -0.3178 0.4278 0.028 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 Zr1 0.01040(14) 0.01229(14) 0.01155(13) 0.000 0.00292(9) 0.000 Cl1 0.0201(3) 0.0193(3) 0.0185(2) -0.00388(19) 0.00148(19) -0.00388(18) F4 0.0269(7) 0.0237(7) 0.0165(6) 0.0007(5) 0.0008(5) -0.0057(5) O1 0.0134(7) 0.0180(7) 0.0170(7) 0.0017(5) 0.0035(5) 0.0021(5) F5 0.0352(8) 0.0276(7) 0.0184(6) -0.0033(5) -0.0015(6) -0.0096(6) C6 0.0155(10) 0.0187(10) 0.0142(9) 0.0022(8) 0.0030(8) 0.0034(8) F3 0.0287(8) 0.0444(9) 0.0357(8) 0.0102(7) 0.0208(6) 0.0182(6) F2 0.0279(8) 0.1005(15) 0.0178(7) 0.0121(8) 0.0061(6) -0.0015(9) C5 0.0202(11) 0.0278(12) 0.0311(12) 0.0103(10) 0.0066(9) 0.0076(9) N1 0.0159(9) 0.0169(9) 0.0111(8) -0.0008(6) 0.0022(7) -0.0009(6) F1 0.0588(11) 0.0260(8) 0.0773(13) -0.0060(8) 0.0523(10) -0.0131(7) C10 0.0309(13) 0.0288(12) 0.0125(10) 0.0004(9) 0.0028(9) 0.0057(9) C4 0.0166(10) 0.0148(10) 0.0161(10) -0.0007(8) 0.0000(8) -0.0016(7) C3 0.0128(10) 0.0196(10) 0.0229(11) -0.0010(8) 0.0052(8) 0.0030(8) C2 0.0130(9) 0.0164(10) 0.0157(10) -0.0042(8) 0.0043(7) -0.0015(7) C11 0.0233(11) 0.0199(10) 0.0179(10) 0.0006(8) 0.0018(8) 0.0022(8) C1 0.0166(10) 0.0210(11) 0.0245(11) 0.0024(9) 0.0082(8) 0.0032(8) C7 0.0186(10) 0.0199(10) 0.0150(9) 0.0019(8) 0.0014(8) 0.0025(8) C9 0.0257(12) 0.0346(13) 0.0177(11) 0.0095(9) 0.0090(9) 0.0050(10) C8 0.0209(11) 0.0270(12) 0.0235(11) 0.0071(9) 0.0056(9) -0.0008(9) _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 Zr1 O1 2.0230(14) . ? Zr1 O1 2.0230(14) 2 ? Zr1 N1 2.3435(17) 2 ? Zr1 N1 2.3435(17) . ? Zr1 Cl1 2.3994(6) 2 ? Zr1 Cl1 2.3995(6) . ? F4 C7 1.347(2) . ? O1 C2 1.309(2) . ? F5 C11 1.349(3) . ? C6 C7 1.387(3) . ? C6 C11 1.391(3) . ? C6 N1 1.445(3) . ? F3 C1 1.327(2) . ? F2 C1 1.319(3) . ? C5 C4 1.502(3) . ? N1 C4 1.302(3) . ? F1 C1 1.323(3) . ? C10 C11 1.377(3) . ? C10 C9 1.389(3) . ? C4 C3 1.445(3) . ? C3 C2 1.338(3) . ? C2 C1 1.518(3) . ? C7 C8 1.381(3) . ? C9 C8 1.381(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Zr1 O1 162.55(8) . 2 ? O1 Zr1 N1 88.55(6) . 2 ? O1 Zr1 N1 78.71(6) 2 2 ? O1 Zr1 N1 78.71(6) . . ? O1 Zr1 N1 88.55(6) 2 . ? N1 Zr1 N1 86.42(8) 2 . ? O1 Zr1 Cl1 94.83(4) . 2 ? O1 Zr1 Cl1 96.86(4) 2 2 ? N1 Zr1 Cl1 89.31(4) 2 2 ? N1 Zr1 Cl1 172.34(4) . 2 ? O1 Zr1 Cl1 96.86(4) . . ? O1 Zr1 Cl1 94.83(4) 2 . ? N1 Zr1 Cl1 172.34(4) 2 . ? N1 Zr1 Cl1 89.31(4) . . ? Cl1 Zr1 Cl1 95.61(3) 2 . ? C2 O1 Zr1 138.02(13) . . ? C7 C6 C11 116.14(19) . . ? C7 C6 N1 122.17(18) . . ? C11 C6 N1 121.68(19) . . ? C4 N1 C6 115.96(17) . . ? C4 N1 Zr1 129.25(14) . . ? C6 N1 Zr1 114.66(13) . . ? C11 C10 C9 118.4(2) . . ? N1 C4 C3 122.56(19) . . ? N1 C4 C5 122.13(19) . . ? C3 C4 C5 115.31(18) . . ? C2 C3 C4 125.06(19) . . ? O1 C2 C3 126.05(19) . . ? O1 C2 C1 112.84(18) . . ? C3 C2 C1 121.11(19) . . ? F5 C11 C10 119.6(2) . . ? F5 C11 C6 117.34(19) . . ? C10 C11 C6 123.0(2) . . ? F2 C1 F1 107.6(2) . . ? F2 C1 F3 106.99(19) . . ? F1 C1 F3 106.36(18) . . ? F2 C1 C2 111.67(18) . . ? F1 C1 C2 110.99(18) . . ? F3 C1 C2 112.96(18) . . ? F4 C7 C8 119.4(2) . . ? F4 C7 C6 117.66(18) . . ? C8 C7 C6 123.0(2) . . ? C8 C9 C10 120.9(2) . . ? C7 C8 C9 118.6(2) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O1 Zr1 O1 C2 -50.58(19) 2 . . . ? N1 Zr1 O1 C2 -93.38(19) 2 . . . ? N1 Zr1 O1 C2 -6.74(19) . . . . ? Cl1 Zr1 O1 C2 177.43(19) 2 . . . ? Cl1 Zr1 O1 C2 81.18(19) . . . . ? C7 C6 N1 C4 -93.1(2) . . . . ? C11 C6 N1 C4 86.4(2) . . . . ? C7 C6 N1 Zr1 90.6(2) . . . . ? C11 C6 N1 Zr1 -89.9(2) . . . . ? O1 Zr1 N1 C4 5.07(17) . . . . ? O1 Zr1 N1 C4 173.07(18) 2 . . . ? N1 Zr1 N1 C4 94.30(18) 2 . . . ? Cl1 Zr1 N1 C4 38.0(4) 2 . . . ? Cl1 Zr1 N1 C4 -92.07(17) . . . . ? O1 Zr1 N1 C6 -179.23(14) . . . . ? O1 Zr1 N1 C6 -11.23(14) 2 . . . ? N1 Zr1 N1 C6 -90.00(14) 2 . . . ? Cl1 Zr1 N1 C6 -146.3(3) 2 . . . ? Cl1 Zr1 N1 C6 83.63(13) . . . . ? C6 N1 C4 C3 -178.77(18) . . . . ? Zr1 N1 C4 C3 -3.1(3) . . . . ? C6 N1 C4 C5 1.0(3) . . . . ? Zr1 N1 C4 C5 176.65(15) . . . . ? N1 C4 C3 C2 -0.5(3) . . . . ? C5 C4 C3 C2 179.8(2) . . . . ? Zr1 O1 C2 C3 6.1(3) . . . . ? Zr1 O1 C2 C1 -173.20(14) . . . . ? C4 C3 C2 O1 -0.4(3) . . . . ? C4 C3 C2 C1 178.9(2) . . . . ? C9 C10 C11 F5 -176.8(2) . . . . ? C9 C10 C11 C6 1.0(3) . . . . ? C7 C6 C11 F5 176.01(18) . . . . ? N1 C6 C11 F5 -3.5(3) . . . . ? C7 C6 C11 C10 -1.9(3) . . . . ? N1 C6 C11 C10 178.6(2) . . . . ? O1 C2 C1 F2 -52.9(3) . . . . ? C3 C2 C1 F2 127.7(2) . . . . ? O1 C2 C1 F1 67.1(2) . . . . ? C3 C2 C1 F1 -112.3(2) . . . . ? O1 C2 C1 F3 -173.59(18) . . . . ? C3 C2 C1 F3 7.1(3) . . . . ? C11 C6 C7 F4 -177.65(18) . . . . ? N1 C6 C7 F4 1.9(3) . . . . ? C11 C6 C7 C8 1.3(3) . . . . ? N1 C6 C7 C8 -179.2(2) . . . . ? C11 C10 C9 C8 0.5(3) . . . . ? F4 C7 C8 C9 179.04(19) . . . . ? C6 C7 C8 C9 0.1(3) . . . . ? C10 C9 C8 C7 -1.0(3) . . . . ? _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 26.84 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 0.360 _refine_diff_density_min -0.812 _refine_diff_density_rms 0.077