Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Peter Scott' _publ_contact_author_address ; Department of Chemistry University of Warwick COVENTRY CV4 7AL UNITED KINGDOM ; _publ_contact_author_email PETER.SCOTT@WARWICK.AC.UK _publ_section_title ; Group 4 Salicyloxazolines are Potent Polymerisation Catalysts ; loop_ _publ_author_name 'P. Scott' 'M. Bochmann' 'Robyn K. J. Bott' 'Max Hammond' 'Peter N. Horton' ; S.J.Lancaster ; data_04src0532 _database_code_depnum_ccdc_archive 'CCDC 268639' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H40 Cl2 N2 O4 Zr' _chemical_formula_weight 654.76 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' 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 C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 15.947(3) _cell_length_b 8.3503(17) _cell_length_c 22.819(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.41(3) _cell_angle_gamma 90.00 _cell_volume 3038.6(11) _cell_formula_units_Z 4 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 3540 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.431 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1360 _exptl_absorpt_coefficient_mu 0.575 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9239 _exptl_absorpt_correction_T_max 0.9718 _exptl_absorpt_process_details 'SADABS V2.10 (Sheldrick, G.M., 2003)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker-Nonius FR591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker-Nonius KappaCCD Area Detector' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_decay_% negligible _diffrn_reflns_number 15884 _diffrn_reflns_av_R_equivalents 0.0383 _diffrn_reflns_av_sigmaI/netI 0.0376 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 3.11 _diffrn_reflns_theta_max 27.50 _reflns_number_total 3478 _reflns_number_gt 2997 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement 'DENZO, COLLECT' _computing_data_reduction 'DENZO, COLLECT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 1990)' _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^)+(0.0294P)^2^+3.8864P] 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 SHELXL _refine_ls_extinction_coef 0.0016(2) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3478 _refine_ls_number_parameters 183 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0400 _refine_ls_R_factor_gt 0.0303 _refine_ls_wR_factor_ref 0.0739 _refine_ls_wR_factor_gt 0.0698 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.041 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.59879(11) 0.0130(2) 0.63152(8) 0.0185(4) Uani 1 1 d . . . C2 C 0.61258(12) 0.0912(2) 0.57725(8) 0.0215(4) Uani 1 1 d . . . C3 C 0.56261(12) 0.2404(2) 0.55913(8) 0.0239(4) Uani 1 1 d . . . C4 C 0.46763(13) 0.2096(3) 0.55913(9) 0.0307(5) Uani 1 1 d . . . H4A H 0.4550 0.1152 0.5351 0.046 Uiso 1 1 calc R . . H4B H 0.4384 0.3030 0.5429 0.046 Uiso 1 1 calc R . . H4C H 0.4489 0.1908 0.5994 0.046 Uiso 1 1 calc R . . C5 C 0.58536(15) 0.2940(3) 0.49676(9) 0.0365(5) Uani 1 1 d . . . H5A H 0.6453 0.3192 0.4952 0.055 Uiso 1 1 calc R . . H5B H 0.5527 0.3894 0.4863 0.055 Uiso 1 1 calc R . . H5C H 0.5726 0.2076 0.4690 0.055 Uiso 1 1 calc R . . C6 C 0.58434(14) 0.3776(3) 0.60135(10) 0.0315(5) Uani 1 1 d . . . H6A H 0.5688 0.3473 0.6413 0.047 Uiso 1 1 calc R . . H6B H 0.5534 0.4741 0.5897 0.047 Uiso 1 1 calc R . . H6C H 0.6447 0.3991 0.5999 0.047 Uiso 1 1 calc R . . C7 C 0.67766(13) 0.0310(3) 0.54336(9) 0.0268(4) Uani 1 1 d . . . H7 H 0.6880 0.0793 0.5064 0.032 Uiso 1 1 calc R . . C8 C 0.72812(13) -0.0958(3) 0.56074(9) 0.0294(5) Uani 1 1 d . . . H8 H 0.7712 -0.1331 0.5357 0.035 Uiso 1 1 calc R . . C9 C 0.71601(12) -0.1677(3) 0.61414(9) 0.0255(4) Uani 1 1 d . . . H9 H 0.7510 -0.2536 0.6265 0.031 Uiso 1 1 calc R . . C10 C 0.65103(11) -0.1124(2) 0.65041(8) 0.0200(4) Uani 1 1 d . . . C11 C 0.35521(11) -0.1779(2) 0.79050(8) 0.0189(4) Uani 1 1 d . . . C12 C 0.30610(13) -0.3366(2) 0.71815(9) 0.0261(4) Uani 1 1 d . . . H12A H 0.2507 -0.3157 0.6999 0.031 Uiso 1 1 calc R . . H12B H 0.3216 -0.4498 0.7111 0.031 Uiso 1 1 calc R . . C13 C 0.37294(12) -0.2229(2) 0.69324(8) 0.0210(4) Uani 1 1 d . . . C14 C 0.44575(12) -0.3168(2) 0.66778(9) 0.0251(4) Uani 1 1 d . . . H14A H 0.4866 -0.2424 0.6511 0.038 Uiso 1 1 calc R . . H14B H 0.4249 -0.3887 0.6370 0.038 Uiso 1 1 calc R . . H14C H 0.4727 -0.3799 0.6988 0.038 Uiso 1 1 calc R . . C15 C 0.33401(14) -0.1101(3) 0.64810(9) 0.0298(5) Uani 1 1 d . . . H15A H 0.2897 -0.0468 0.6666 0.045 Uiso 1 1 calc R . . H15B H 0.3100 -0.1727 0.6158 0.045 Uiso 1 1 calc R . . H15C H 0.3773 -0.0381 0.6329 0.045 Uiso 1 1 calc R . . N1 N 0.39976(9) -0.12814(18) 0.74626(7) 0.0186(3) Uani 1 1 d . . . O1 O 0.53635(8) 0.05831(15) 0.66663(5) 0.0198(3) Uani 1 1 d . . . O2 O 0.30448(8) -0.30216(16) 0.78031(6) 0.0251(3) Uani 1 1 d . . . Cl1 Cl 0.39361(3) 0.26758(6) 0.72300(2) 0.02869(14) Uani 1 1 d . . . Zr1 Zr 0.5000 0.07329(3) 0.7500 0.01610(10) Uani 1 2 d S . . 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 0.0139(9) 0.0206(10) 0.0211(9) -0.0033(7) 0.0000(7) -0.0013(7) C2 0.0178(9) 0.0248(10) 0.0219(9) -0.0014(7) -0.0008(7) -0.0005(8) C3 0.0220(10) 0.0263(11) 0.0235(10) 0.0038(8) 0.0025(8) 0.0015(8) C4 0.0227(11) 0.0361(13) 0.0331(11) 0.0081(9) -0.0033(9) 0.0031(9) C5 0.0405(13) 0.0381(13) 0.0309(11) 0.0121(9) 0.0084(10) 0.0101(10) C6 0.0301(12) 0.0259(11) 0.0385(12) 0.0009(9) 0.0025(9) 0.0027(9) C7 0.0243(11) 0.0336(12) 0.0227(10) -0.0003(8) 0.0040(8) 0.0020(9) C8 0.0245(11) 0.0371(12) 0.0267(10) -0.0037(9) 0.0072(8) 0.0070(9) C9 0.0201(10) 0.0277(11) 0.0288(10) -0.0030(8) 0.0009(8) 0.0064(8) C10 0.0160(9) 0.0205(10) 0.0236(9) -0.0022(7) -0.0012(7) 0.0013(7) C11 0.0127(8) 0.0149(9) 0.0290(10) 0.0014(7) -0.0019(7) 0.0003(7) C12 0.0244(10) 0.0248(11) 0.0293(10) -0.0086(8) 0.0050(8) -0.0062(8) C13 0.0177(9) 0.0205(10) 0.0247(9) -0.0043(7) 0.0006(7) -0.0009(7) C14 0.0202(10) 0.0266(11) 0.0284(10) -0.0075(8) 0.0033(8) -0.0023(8) C15 0.0277(11) 0.0319(12) 0.0296(11) -0.0029(9) -0.0069(9) 0.0015(9) N1 0.0142(8) 0.0162(8) 0.0253(8) -0.0017(6) 0.0006(6) 0.0007(6) O1 0.0157(6) 0.0212(7) 0.0226(7) 0.0007(5) 0.0029(5) 0.0033(5) O2 0.0223(7) 0.0235(7) 0.0294(7) -0.0022(6) 0.0016(6) -0.0091(6) Cl1 0.0202(3) 0.0248(3) 0.0411(3) 0.0075(2) 0.0046(2) 0.00667(19) Zr1 0.01239(14) 0.01466(15) 0.02128(14) 0.000 0.00271(9) 0.000 _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 O1 1.337(2) . ? C1 C10 1.404(3) . ? C1 C2 1.419(3) . ? C2 C7 1.393(3) . ? C2 C3 1.534(3) . ? C3 C4 1.536(3) . ? C3 C6 1.536(3) . ? C3 C5 1.538(3) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C5 H5C 0.9800 . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C6 H6C 0.9800 . ? C7 C8 1.386(3) . ? C7 H7 0.9500 . ? C8 C9 1.373(3) . ? C8 H8 0.9500 . ? C9 C10 1.409(3) . ? C9 H9 0.9500 . ? C10 C11 1.460(3) 2_656 ? C11 N1 1.306(2) . ? C11 O2 1.335(2) . ? C11 C10 1.460(3) 2_656 ? C12 O2 1.448(2) . ? C12 C13 1.539(3) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 N1 1.505(2) . ? C13 C14 1.520(3) . ? C13 C15 1.525(3) . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? N1 Zr1 2.3217(16) . ? O1 Zr1 1.9965(13) . ? Cl1 Zr1 2.4239(6) . ? Zr1 O1 1.9965(13) 2_656 ? Zr1 N1 2.3216(16) 2_656 ? Zr1 Cl1 2.4239(6) 2_656 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 C1 C10 118.04(16) . . ? O1 C1 C2 120.91(17) . . ? C10 C1 C2 121.05(16) . . ? C7 C2 C1 116.07(18) . . ? C7 C2 C3 122.09(17) . . ? C1 C2 C3 121.71(16) . . ? C2 C3 C4 111.98(17) . . ? C2 C3 C6 108.82(16) . . ? C4 C3 C6 110.06(17) . . ? C2 C3 C5 111.13(16) . . ? C4 C3 C5 106.73(17) . . ? C6 C3 C5 108.02(18) . . ? C3 C4 H4A 109.5 . . ? C3 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C3 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C3 C5 H5A 109.5 . . ? C3 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C3 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? C3 C6 H6A 109.5 . . ? C3 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C3 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? C8 C7 C2 123.39(18) . . ? C8 C7 H7 118.3 . . ? C2 C7 H7 118.3 . . ? C9 C8 C7 120.18(18) . . ? C9 C8 H8 119.9 . . ? C7 C8 H8 119.9 . . ? C8 C9 C10 119.12(19) . . ? C8 C9 H9 120.4 . . ? C10 C9 H9 120.4 . . ? C1 C10 C9 120.12(17) . . ? C1 C10 C11 121.28(16) . 2_656 ? C9 C10 C11 118.36(17) . 2_656 ? N1 C11 O2 116.42(16) . . ? N1 C11 C10 129.46(17) . 2_656 ? O2 C11 C10 114.04(15) . 2_656 ? O2 C12 C13 104.85(15) . . ? O2 C12 H12A 110.8 . . ? C13 C12 H12A 110.8 . . ? O2 C12 H12B 110.8 . . ? C13 C12 H12B 110.8 . . ? H12A C12 H12B 108.9 . . ? N1 C13 C14 111.41(15) . . ? N1 C13 C15 109.29(15) . . ? C14 C13 C15 111.66(17) . . ? N1 C13 C12 102.77(14) . . ? C14 C13 C12 110.82(16) . . ? C15 C13 C12 110.55(17) . . ? C13 C14 H14A 109.5 . . ? C13 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C13 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C13 C15 H15A 109.5 . . ? C13 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C13 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C11 N1 C13 107.51(15) . . ? C11 N1 Zr1 125.47(13) . . ? C13 N1 Zr1 127.01(11) . . ? C1 O1 Zr1 144.21(12) . . ? C11 O2 C12 108.07(14) . . ? O1 Zr1 O1 172.81(7) . 2_656 ? O1 Zr1 N1 97.13(6) . . ? O1 Zr1 N1 77.59(6) 2_656 . ? O1 Zr1 N1 77.59(5) . 2_656 ? O1 Zr1 N1 97.13(6) 2_656 2_656 ? N1 Zr1 N1 87.15(8) . 2_656 ? O1 Zr1 Cl1 94.40(4) . 2_656 ? O1 Zr1 Cl1 90.41(4) 2_656 2_656 ? N1 Zr1 Cl1 167.11(4) . 2_656 ? N1 Zr1 Cl1 89.72(4) 2_656 2_656 ? O1 Zr1 Cl1 90.41(4) . . ? O1 Zr1 Cl1 94.40(4) 2_656 . ? N1 Zr1 Cl1 89.72(4) . . ? N1 Zr1 Cl1 167.11(4) 2_656 . ? Cl1 Zr1 Cl1 95.97(3) 2_656 . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.317 _refine_diff_density_min -0.434 _refine_diff_density_rms 0.067 data_s92 _database_code_depnum_ccdc_archive 'CCDC 268638' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Dr. S. J. Lancaster ; _chemical_name_common 'Dr. S. J. Lancaster' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H28 Cl2 N2 O4 Zr' _chemical_formula_weight 570.60 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' 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 Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 11.4174(18) _cell_length_b 13.9809(9) _cell_length_c 15.0376(17) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2400.4(5) _cell_formula_units_Z 4 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 3187 _cell_measurement_theta_min 2.910 _cell_measurement_theta_max 27.485 _exptl_crystal_description Plate _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.579 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1168 _exptl_absorpt_coefficient_mu 0.715 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7631 _exptl_absorpt_correction_T_max 0.9720 _exptl_absorpt_process_details 'SORTAV Blessing (1997)' _exptl_special_details ; PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Nonius FR591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius KappaCCD Area Detector' _diffrn_measurement_method '\f and \w scans to fill Ewald Sphere' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 26703 _diffrn_reflns_av_R_equivalents 0.0502 _diffrn_reflns_av_sigmaI/netI 0.0408 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.08 _diffrn_reflns_theta_max 27.48 _reflns_number_total 5479 _reflns_number_gt 4876 _reflns_threshold_expression >2sigma(I) _computing_data_collection ' DENZO (Otwinowski and Minor, 1997)' _computing_cell_refinement ' DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998)' _computing_data_reduction ' DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997a)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997b)' _computing_molecular_graphics 'PLATON (Spek, 1990)' _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^)+(0.0298P)^2^+0.5006P] 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 SHELXL _refine_ls_extinction_coef 0.0023(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.04(3) _refine_ls_number_reflns 5479 _refine_ls_number_parameters 305 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0368 _refine_ls_R_factor_gt 0.0286 _refine_ls_wR_factor_ref 0.0648 _refine_ls_wR_factor_gt 0.0618 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _refine_ls_shift/su_max 0.043 _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 Cl1 Cl 0.04371(5) 0.16030(6) 0.85320(4) 0.02345(15) Uani 1 1 d . . . Cl2 Cl 0.07363(5) 0.16261(6) 0.61966(4) 0.02473(15) Uani 1 1 d . . . Zr1 Zr 0.201408(17) 0.152074(14) 0.748309(14) 0.01421(7) Uani 1 1 d . . . C1 C 0.3863(2) 0.05298(18) 0.61429(15) 0.0163(5) Uani 1 1 d . . . C2 C 0.4987(2) 0.1545(2) 0.53969(19) 0.0332(7) Uani 1 1 d . . . H2A H 0.4824 0.1758 0.4781 0.040 Uiso 1 1 calc R . . H2B H 0.5831 0.1637 0.5522 0.040 Uiso 1 1 calc R . . C3 C 0.4245(2) 0.21006(18) 0.60572(16) 0.0207(5) Uani 1 1 d . . . C4 C 0.3450(3) 0.2787(2) 0.55760(19) 0.0331(7) Uani 1 1 d . . . H4A H 0.2952 0.2432 0.5160 0.050 Uiso 1 1 calc R . . H4B H 0.3924 0.3252 0.5246 0.050 Uiso 1 1 calc R . . H4C H 0.2957 0.3124 0.6008 0.050 Uiso 1 1 calc R . . C5 C 0.4995(3) 0.2605(2) 0.6733(2) 0.0390(8) Uani 1 1 d . . . H5A H 0.4492 0.2920 0.7174 0.058 Uiso 1 1 calc R . . H5B H 0.5480 0.3086 0.6434 0.058 Uiso 1 1 calc R . . H5C H 0.5501 0.2139 0.7032 0.058 Uiso 1 1 calc R . . C6 C 0.3451(2) -0.04305(18) 0.63310(15) 0.0161(5) Uani 1 1 d . . . C7 C 0.2613(2) -0.05970(18) 0.69800(15) 0.0156(5) Uani 1 1 d . . . C8 C 0.2216(2) -0.15249(19) 0.71512(15) 0.0198(5) Uani 1 1 d . . . C9 C 0.2651(2) -0.22542(19) 0.66391(18) 0.0228(6) Uani 1 1 d . . . H9 H 0.2383 -0.2888 0.6742 0.027 Uiso 1 1 calc R . . C10 C 0.3463(2) -0.20970(19) 0.59825(17) 0.0230(6) Uani 1 1 d . . . H10 H 0.3741 -0.2617 0.5635 0.028 Uiso 1 1 calc R . . C11 C 0.3873(2) -0.11945(18) 0.58274(17) 0.0206(5) Uani 1 1 d . . . H11 H 0.4443 -0.1087 0.5378 0.025 Uiso 1 1 calc R . . C12 C 0.1308(3) -0.1689(2) 0.78398(18) 0.0302(6) Uani 1 1 d . . . H12A H 0.1522 -0.1347 0.8385 0.045 Uiso 1 1 calc R . . H12B H 0.1250 -0.2375 0.7966 0.045 Uiso 1 1 calc R . . H12C H 0.0551 -0.1454 0.7624 0.045 Uiso 1 1 calc R . . N1 N 0.35497(17) 0.13307(15) 0.64916(13) 0.0161(5) Uani 1 1 d . . . O1 O 0.46686(16) 0.05715(12) 0.55093(11) 0.0239(4) Uani 1 1 d . . . O2 O 0.21739(13) 0.01309(10) 0.74324(12) 0.0170(3) Uani 1 1 d . . . C21 C 0.3417(2) 0.23143(18) 0.91567(15) 0.0166(5) Uani 1 1 d . . . C22 C 0.4289(2) 0.12116(18) 0.99924(16) 0.0206(5) Uani 1 1 d . . . H22A H 0.3823 0.0951 1.0492 0.025 Uiso 1 1 calc R . . H22B H 0.5129 0.1092 1.0110 0.025 Uiso 1 1 calc R . . C23 C 0.3918(2) 0.07575(18) 0.91171(15) 0.0172(5) Uani 1 1 d . . . C24 C 0.3161(2) -0.01077(18) 0.92927(17) 0.0232(6) Uani 1 1 d . . . H24A H 0.2389 0.0100 0.9502 0.035 Uiso 1 1 calc R . . H24B H 0.3531 -0.0508 0.9748 0.035 Uiso 1 1 calc R . . H24C H 0.3072 -0.0476 0.8743 0.035 Uiso 1 1 calc R . . C25 C 0.4958(2) 0.0506(2) 0.85436(16) 0.0233(6) Uani 1 1 d . . . H25A H 0.4684 0.0255 0.7972 0.035 Uiso 1 1 calc R . . H25B H 0.5434 0.0020 0.8844 0.035 Uiso 1 1 calc R . . H25C H 0.5433 0.1080 0.8442 0.035 Uiso 1 1 calc R . . C26 C 0.2968(2) 0.32694(17) 0.90173(15) 0.0174(5) Uani 1 1 d . . . C27 C 0.2494(2) 0.35376(19) 0.82055(16) 0.0187(5) Uani 1 1 d . . . C28 C 0.2121(2) 0.44740(19) 0.80684(17) 0.0218(5) Uani 1 1 d . . . C29 C 0.2174(2) 0.51030(18) 0.87624(18) 0.0251(6) Uani 1 1 d . . . H29 H 0.1896 0.5738 0.8681 0.030 Uiso 1 1 calc R . . C30 C 0.2619(2) 0.48402(19) 0.95778(18) 0.0256(6) Uani 1 1 d . . . H30 H 0.2638 0.5289 1.0052 0.031 Uiso 1 1 calc R . . C31 C 0.3034(2) 0.39295(18) 0.97041(16) 0.0205(5) Uani 1 1 d . . . H31 H 0.3365 0.3752 1.0260 0.025 Uiso 1 1 calc R . . C32 C 0.1669(3) 0.47632(19) 0.71787(18) 0.0299(7) Uani 1 1 d . . . H32A H 0.1165 0.5327 0.7243 0.045 Uiso 1 1 calc R . . H32B H 0.1216 0.4236 0.6921 0.045 Uiso 1 1 calc R . . H32C H 0.2329 0.4917 0.6787 0.045 Uiso 1 1 calc R . . N21 N 0.32531(16) 0.15572(16) 0.86884(11) 0.0140(4) Uani 1 1 d . . . O21 O 0.40699(15) 0.22166(12) 0.98810(10) 0.0195(4) Uani 1 1 d . . . O22 O 0.23911(14) 0.29033(11) 0.75525(13) 0.0199(3) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.0182(3) 0.0339(4) 0.0182(3) -0.0043(3) 0.0034(2) 0.0013(3) Cl2 0.0219(3) 0.0349(4) 0.0174(3) -0.0047(3) -0.0050(2) 0.0071(3) Zr1 0.01485(11) 0.01478(11) 0.01301(10) -0.00147(11) -0.00026(10) 0.00136(8) C1 0.0128(12) 0.0245(14) 0.0117(11) 0.0009(10) 0.0004(10) 0.0027(10) C2 0.0333(16) 0.0227(15) 0.0436(16) 0.0090(14) 0.0192(13) 0.0001(13) C3 0.0205(13) 0.0172(13) 0.0244(12) 0.0045(10) 0.0048(11) -0.0038(10) C4 0.0348(17) 0.0326(17) 0.0318(15) 0.0203(13) 0.0113(13) 0.0104(13) C5 0.0369(18) 0.048(2) 0.0322(16) 0.0061(14) -0.0007(14) -0.0217(15) C6 0.0144(12) 0.0192(13) 0.0147(11) -0.0029(9) -0.0025(9) 0.0014(10) C7 0.0146(12) 0.0180(13) 0.0143(11) -0.0008(9) -0.0020(9) 0.0013(10) C8 0.0202(13) 0.0194(13) 0.0198(10) 0.0018(10) -0.0025(9) 0.0021(11) C9 0.0226(14) 0.0174(14) 0.0286(14) -0.0031(11) -0.0080(11) -0.0019(10) C10 0.0202(14) 0.0228(15) 0.0260(14) -0.0086(11) -0.0034(11) 0.0061(11) C11 0.0168(13) 0.0233(14) 0.0218(12) -0.0025(10) 0.0003(10) 0.0029(10) C12 0.0367(16) 0.0241(15) 0.0297(13) -0.0001(12) 0.0077(12) -0.0083(13) N1 0.0146(10) 0.0167(12) 0.0171(9) 0.0021(8) 0.0005(8) -0.0004(8) O1 0.0252(9) 0.0211(10) 0.0253(9) 0.0013(8) 0.0122(8) 0.0001(8) O2 0.0201(8) 0.0136(8) 0.0172(8) -0.0033(7) 0.0041(9) -0.0001(6) C21 0.0124(12) 0.0217(14) 0.0156(11) 0.0025(10) 0.0011(10) -0.0013(10) C22 0.0244(13) 0.0191(13) 0.0184(11) 0.0027(10) -0.0041(11) 0.0017(11) C23 0.0191(14) 0.0187(13) 0.0139(11) 0.0013(10) -0.0010(10) 0.0022(10) C24 0.0291(15) 0.0204(13) 0.0202(12) 0.0040(10) -0.0022(11) 0.0013(11) C25 0.0221(14) 0.0268(15) 0.0211(13) -0.0008(11) -0.0005(11) 0.0080(11) C26 0.0150(11) 0.0175(12) 0.0197(11) -0.0019(9) 0.0033(10) -0.0016(10) C27 0.0155(11) 0.0178(13) 0.0227(12) -0.0023(11) 0.0034(10) -0.0001(10) C28 0.0182(13) 0.0179(13) 0.0292(13) 0.0017(10) 0.0021(11) -0.0004(11) C29 0.0237(15) 0.0129(13) 0.0388(15) 0.0008(11) 0.0024(12) 0.0005(11) C30 0.0271(15) 0.0182(15) 0.0315(14) -0.0090(11) 0.0021(12) 0.0002(11) C31 0.0186(12) 0.0229(13) 0.0200(11) -0.0027(10) 0.0018(11) -0.0028(11) C32 0.0357(17) 0.0190(14) 0.0351(15) 0.0071(11) -0.0074(13) 0.0012(12) N21 0.0145(9) 0.0141(10) 0.0134(9) 0.0020(9) -0.0002(7) 0.0021(9) O21 0.0204(9) 0.0204(9) 0.0176(8) 0.0002(7) -0.0040(7) 0.0006(8) O22 0.0275(9) 0.0153(8) 0.0168(8) -0.0011(8) -0.0022(9) 0.0033(6) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cl1 Zr1 2.3964(6) . ? Cl2 Zr1 2.4275(6) . ? Zr1 O2 1.9532(14) . ? Zr1 O22 1.9831(15) . ? Zr1 N21 2.2997(18) . ? Zr1 N1 2.317(2) . ? C1 N1 1.287(3) . ? C1 O1 1.325(3) . ? C1 C6 1.451(4) . ? C2 O1 1.419(3) . ? C2 C3 1.519(4) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? C3 N1 1.488(3) . ? C3 C5 1.505(4) . ? C3 C4 1.506(4) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C5 H5C 0.9800 . ? C6 C7 1.386(3) . ? C6 C11 1.395(3) . ? C7 O2 1.323(3) . ? C7 C8 1.398(4) . ? C8 C9 1.371(4) . ? C8 C12 1.484(4) . ? C9 C10 1.372(4) . ? C9 H9 0.9500 . ? C10 C11 1.366(4) . ? C10 H10 0.9500 . ? C11 H11 0.9500 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C21 N21 1.285(3) . ? C21 O21 1.327(3) . ? C21 C26 1.445(4) . ? C22 O21 1.437(3) . ? C22 C23 1.521(3) . ? C22 H22A 0.9900 . ? C22 H22B 0.9900 . ? C23 N21 1.498(3) . ? C23 C25 1.509(3) . ? C23 C24 1.510(4) . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C25 H25A 0.9800 . ? C25 H25B 0.9800 . ? C25 H25C 0.9800 . ? C26 C27 1.387(3) . ? C26 C31 1.387(3) . ? C27 O22 1.328(3) . ? C27 C28 1.392(4) . ? C28 C29 1.366(4) . ? C28 C32 1.490(4) . ? C29 C30 1.377(4) . ? C29 H29 0.9500 . ? C30 C31 1.372(4) . ? C30 H30 0.9500 . ? C31 H31 0.9500 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Zr1 O22 162.08(7) . . ? O2 Zr1 N21 89.73(7) . . ? O22 Zr1 N21 78.66(8) . . ? O2 Zr1 N1 77.88(7) . . ? O22 Zr1 N1 88.93(7) . . ? N21 Zr1 N1 92.54(7) . . ? O2 Zr1 Cl1 98.26(5) . . ? O22 Zr1 Cl1 94.69(5) . . ? N21 Zr1 Cl1 86.69(5) . . ? N1 Zr1 Cl1 176.07(6) . . ? O2 Zr1 Cl2 94.90(5) . . ? O22 Zr1 Cl2 96.50(6) . . ? N21 Zr1 Cl2 175.16(6) . . ? N1 Zr1 Cl2 87.07(5) . . ? Cl1 Zr1 Cl2 94.02(3) . . ? N1 C1 O1 116.6(2) . . ? N1 C1 C6 129.4(2) . . ? O1 C1 C6 114.0(2) . . ? O1 C2 C3 105.6(2) . . ? O1 C2 H2A 110.6 . . ? C3 C2 H2A 110.6 . . ? O1 C2 H2B 110.6 . . ? C3 C2 H2B 110.6 . . ? H2A C2 H2B 108.7 . . ? N1 C3 C5 110.2(2) . . ? N1 C3 C4 110.5(2) . . ? C5 C3 C4 111.6(3) . . ? N1 C3 C2 102.4(2) . . ? C5 C3 C2 111.3(2) . . ? C4 C3 C2 110.4(2) . . ? C3 C4 H4A 109.5 . . ? C3 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C3 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C3 C5 H5A 109.5 . . ? C3 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C3 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? C7 C6 C11 119.5(2) . . ? C7 C6 C1 121.1(2) . . ? C11 C6 C1 119.4(2) . . ? O2 C7 C6 119.6(2) . . ? O2 C7 C8 119.8(2) . . ? C6 C7 C8 120.6(2) . . ? C9 C8 C7 118.0(2) . . ? C9 C8 C12 122.0(2) . . ? C7 C8 C12 119.9(2) . . ? C8 C9 C10 122.0(2) . . ? C8 C9 H9 119.0 . . ? C10 C9 H9 119.0 . . ? C11 C10 C9 120.2(2) . . ? C11 C10 H10 119.9 . . ? C9 C10 H10 119.9 . . ? C10 C11 C6 119.7(2) . . ? C10 C11 H11 120.1 . . ? C6 C11 H11 120.1 . . ? C8 C12 H12A 109.5 . . ? C8 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C8 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C1 N1 C3 107.6(2) . . ? C1 N1 Zr1 124.92(16) . . ? C3 N1 Zr1 127.08(15) . . ? C1 O1 C2 107.80(19) . . ? C7 O2 Zr1 145.17(15) . . ? N21 C21 O21 116.5(2) . . ? N21 C21 C26 129.1(2) . . ? O21 C21 C26 114.4(2) . . ? O21 C22 C23 105.00(19) . . ? O21 C22 H22A 110.7 . . ? C23 C22 H22A 110.7 . . ? O21 C22 H22B 110.7 . . ? C23 C22 H22B 110.7 . . ? H22A C22 H22B 108.8 . . ? N21 C23 C25 109.08(19) . . ? N21 C23 C24 112.5(2) . . ? C25 C23 C24 111.3(2) . . ? N21 C23 C22 101.65(19) . . ? C25 C23 C22 111.9(2) . . ? C24 C23 C22 110.0(2) . . ? C23 C24 H24A 109.5 . . ? C23 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C23 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C23 C25 H25A 109.5 . . ? C23 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? C23 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? C27 C26 C31 119.8(2) . . ? C27 C26 C21 121.0(2) . . ? C31 C26 C21 119.2(2) . . ? O22 C27 C26 120.3(2) . . ? O22 C27 C28 119.4(2) . . ? C26 C27 C28 120.3(2) . . ? C29 C28 C27 118.6(2) . . ? C29 C28 C32 121.8(2) . . ? C27 C28 C32 119.6(2) . . ? C28 C29 C30 121.6(2) . . ? C28 C29 H29 119.2 . . ? C30 C29 H29 119.2 . . ? C31 C30 C29 119.9(2) . . ? C31 C30 H30 120.1 . . ? C29 C30 H30 120.1 . . ? C30 C31 C26 119.7(2) . . ? C30 C31 H31 120.1 . . ? C26 C31 H31 120.1 . . ? C28 C32 H32A 109.5 . . ? C28 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C28 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C21 N21 C23 107.79(18) . . ? C21 N21 Zr1 122.65(16) . . ? C23 N21 Zr1 129.40(16) . . ? C21 O21 C22 107.10(19) . . ? C27 O22 Zr1 135.14(16) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.463 _refine_diff_density_min -0.440 _refine_diff_density_rms 0.063