Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_global _publ_contact_author_email OKUDA@MAIL.UNI-MAINZ.DE _publ_contact_author_name 'Prof Jun Okuda' _publ_contact_author_address ; Anorganische Chemie Johannes Gutenberg Univ. Duesbergweg 10-14 Mainz D-55099 GERMANY ; _publ_section_title ; Efficient Ethylene Polymerisation Catalysis by a Cationic Benzyl Hafnium Complex Containing Pyrrolide-Imine Ligands ; _journal_name_full 'J.Chem.Soc.,Dalton Trans.' _journal_coden_Cambridge 0186 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name J.Okuda S.Matsui T.P.Spaniol Y.Takagi Y.Yoshida data_sm8 _database_code_CSD 194574 _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H40 Hf N4' _chemical_formula_weight 659.19 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0030 0.0020 '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' Hf Hf -0.5830 6.1850 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0060 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M ' P 1 21/c 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 13.6020(10) _cell_length_b 9.7110(5) _cell_length_c 22.397(2) _cell_angle_alpha 90.00 _cell_angle_beta 95.228(7) _cell_angle_gamma 90.00 _cell_volume 2946.1(4) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.09 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.486 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1328 _exptl_absorpt_coefficient_mu 3.567 _exptl_absorpt_correction_type semi-empirical _exptl_absorpt_correction_T_min 0.5793 _exptl_absorpt_correction_T_max 0.6977 _exptl_absorpt_process_details ; psi-scans North A.C.T., Phillips D.C. & Mathews F.S. (1968) Acta. Cryst. A24, 351 Number of psi-scan sets used was 8 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CAD4 (Enraf-Nonius)' _diffrn_measurement_method \w-scans _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 4 _diffrn_reflns_number 12320 _diffrn_reflns_av_R_equivalents 0.0736 _diffrn_reflns_av_sigmaI/netI 0.1212 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 3.01 _diffrn_reflns_theta_max 26.96 _reflns_number_total 6401 _reflns_number_gt 3605 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD4 (Enraf Nonius)' _computing_cell_refinement 'CAD4 (Enraf Nonius)' _computing_data_reduction 'XCAD4 (Harms & Wocadlo, 1995)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1986)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1999)' _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^)+(0.0293P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6401 _refine_ls_number_parameters 427 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1253 _refine_ls_R_factor_gt 0.0525 _refine_ls_wR_factor_ref 0.0936 _refine_ls_wR_factor_gt 0.0772 _refine_ls_goodness_of_fit_ref 0.986 _refine_ls_restrained_S_all 0.986 _refine_ls_shift/su_max 0.177 _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 Hf Hf 0.19935(2) 0.12684(4) 0.147278(15) 0.03485(10) Uani 1 1 d . . . N1 N 0.1259(5) -0.0683(7) 0.1203(3) 0.0424(17) Uani 1 1 d . . . N2 N 0.2119(5) -0.0169(7) 0.2322(3) 0.0360(15) Uani 1 1 d . . . N3 N 0.2701(5) 0.3224(7) 0.1755(3) 0.0374(17) Uani 1 1 d . . . N4 N 0.3699(4) 0.0999(7) 0.1379(3) 0.0364(16) Uani 1 1 d . A . C1 C 0.0701(6) -0.1186(12) 0.0720(4) 0.049(2) Uani 1 1 d . . . H1 H 0.064(6) -0.075(8) 0.039(3) 0.05(3) Uiso 1 1 d . . . C2 C 0.0305(8) -0.2452(11) 0.0843(6) 0.067(3) Uani 1 1 d . . . H2 H 0.004(6) -0.292(8) 0.060(3) 0.04(3) Uiso 1 1 d . . . C3 C 0.0615(7) -0.2717(10) 0.1433(5) 0.054(3) Uani 1 1 d . . . H3 H 0.049(5) -0.331(7) 0.166(3) 0.02(2) Uiso 1 1 d . . . C4A C 0.129(2) -0.157(3) 0.1589(14) 0.056(10) Uiso 0.50 1 d P . . C4B C 0.1140(16) -0.165(2) 0.1659(9) 0.018(5) Uiso 0.50 1 d P . . C5 C 0.1637(6) -0.1313(12) 0.2208(4) 0.047(2) Uani 1 1 d . . . H5 H 0.155(6) -0.186(8) 0.240(3) 0.04(3) Uiso 1 1 d . . . C6 C 0.2541(6) 0.0074(9) 0.2959(4) 0.046(2) Uani 1 1 d . . . C7 C 0.1689(7) 0.0432(11) 0.3330(4) 0.067(3) Uani 1 1 d . . . H7A H 0.1942 0.0622 0.3735 0.100 Uiso 1 1 calc R . . H7B H 0.1238 -0.0330 0.3324 0.100 Uiso 1 1 calc R . . H7C H 0.1349 0.1229 0.3162 0.100 Uiso 1 1 calc R . . C8 C 0.3094(6) -0.1190(11) 0.3223(3) 0.058(2) Uani 1 1 d . . . H8A H 0.3565 -0.1488 0.2956 0.087 Uiso 1 1 calc R . . H8B H 0.2633 -0.1919 0.3274 0.087 Uiso 1 1 calc R . . H8C H 0.3433 -0.0957 0.3604 0.087 Uiso 1 1 calc R . . C9 C 0.3244(6) 0.1280(11) 0.2961(3) 0.053(2) Uani 1 1 d . . . H9A H 0.2906 0.2062 0.2779 0.080 Uiso 1 1 calc R . . H9B H 0.3791 0.1043 0.2739 0.080 Uiso 1 1 calc R . . H9C H 0.3482 0.1500 0.3366 0.080 Uiso 1 1 calc R . . C10 C 0.2453(8) 0.4509(12) 0.1938(4) 0.055(3) Uani 1 1 d . . . H10 H 0.184(5) 0.463(8) 0.204(3) 0.03(2) Uiso 1 1 d . . . C11 C 0.3218(12) 0.5368(14) 0.1924(7) 0.086(5) Uani 1 1 d . . . H11 H 0.318(5) 0.582(6) 0.207(3) 0.00(2) Uiso 1 1 d . . . C12 C 0.3999(8) 0.4670(12) 0.1733(6) 0.067(3) Uani 1 1 d . . . H12 H 0.452(5) 0.497(8) 0.175(3) 0.02(2) Uiso 1 1 d . . . C13 C 0.3670(6) 0.3329(8) 0.1629(4) 0.041(2) Uani 1 1 d . . . C14 C 0.4155(7) 0.2151(10) 0.1443(4) 0.044(2) Uani 1 1 d . . . H14 H 0.488(6) 0.231(9) 0.141(4) 0.07(3) Uiso 1 1 d . . . C15 C 0.4257(6) -0.0244(10) 0.1204(4) 0.047(2) Uani 1 1 d . . . C16A C 0.4751(17) -0.086(3) 0.1784(10) 0.087(8) Uiso 0.50 1 d P A 1 H16A H 0.5299 -0.0293 0.1931 0.130 Uiso 0.50 1 calc PR A 1 H16B H 0.4983 -0.1771 0.1707 0.130 Uiso 0.50 1 calc PR A 1 H16C H 0.4282 -0.0904 0.2079 0.130 Uiso 0.50 1 calc PR A 1 C17A C 0.3561(16) -0.128(3) 0.0933(10) 0.086(7) Uiso 0.50 1 d P A 1 H17A H 0.3075 -0.1480 0.1206 0.129 Uiso 0.50 1 calc PR A 1 H17B H 0.3913 -0.2102 0.0852 0.129 Uiso 0.50 1 calc PR A 1 H17C H 0.3240 -0.0921 0.0566 0.129 Uiso 0.50 1 calc PR A 1 C18A C 0.5043(15) 0.015(2) 0.0790(9) 0.063(6) Uiso 0.50 1 d P A 1 H18A H 0.4743 0.0667 0.0457 0.094 Uiso 0.50 1 calc PR A 1 H18B H 0.5336 -0.0672 0.0645 0.094 Uiso 0.50 1 calc PR A 1 H18C H 0.5543 0.0696 0.1007 0.094 Uiso 0.50 1 calc PR A 1 C16B C 0.4228(17) -0.126(3) 0.1700(9) 0.075(6) Uiso 0.50 1 d P A 2 H16D H 0.4435 -0.0821 0.2075 0.112 Uiso 0.50 1 calc PR A 2 H16E H 0.4663 -0.2012 0.1635 0.112 Uiso 0.50 1 calc PR A 2 H16F H 0.3567 -0.1598 0.1710 0.112 Uiso 0.50 1 calc PR A 2 C17B C 0.3691(13) -0.085(2) 0.0648(8) 0.053(5) Uiso 0.50 1 d P A 2 H17D H 0.3092 -0.1263 0.0756 0.079 Uiso 0.50 1 calc PR A 2 H17E H 0.4090 -0.1532 0.0476 0.079 Uiso 0.50 1 calc PR A 2 H17F H 0.3535 -0.0129 0.0360 0.079 Uiso 0.50 1 calc PR A 2 C18B C 0.5325(16) -0.003(2) 0.1102(10) 0.072(7) Uiso 0.50 1 d P A 2 H18D H 0.5377 0.0717 0.0824 0.108 Uiso 0.50 1 calc PR A 2 H18E H 0.5585 -0.0852 0.0941 0.108 Uiso 0.50 1 calc PR A 2 H18F H 0.5695 0.0194 0.1475 0.108 Uiso 0.50 1 calc PR A 2 C19 C 0.1754(8) 0.1758(12) 0.0487(4) 0.057(3) Uani 1 1 d . . . H19A H 0.101(7) 0.198(10) 0.042(4) 0.08(3) Uiso 1 1 d . . . H19B H 0.197(4) 0.108(6) 0.030(2) 0.000(16) Uiso 1 1 d . . . C20 C 0.2292(7) 0.2988(10) 0.0278(4) 0.046(2) Uani 1 1 d . . . C21 C 0.3162(8) 0.2893(11) 0.0003(4) 0.056(3) Uani 1 1 d . . . H21 H 0.339(6) 0.185(9) -0.008(4) 0.06(3) Uiso 1 1 d . . . C22 C 0.3662(10) 0.4057(15) -0.0166(5) 0.075(4) Uani 1 1 d . . . H22 H 0.424(8) 0.392(13) -0.029(5) 0.10(4) Uiso 1 1 d . . . C23 C 0.3336(12) 0.5321(15) -0.0064(5) 0.083(4) Uani 1 1 d . . . H23 H 0.369(6) 0.615(11) -0.018(3) 0.07(3) Uiso 1 1 d . . . C24 C 0.2443(15) 0.5443(15) 0.0218(6) 0.094(5) Uani 1 1 d . . . H24 H 0.230(8) 0.618(12) 0.021(5) 0.08(4) Uiso 1 1 d . . . C25 C 0.1965(9) 0.4311(12) 0.0369(5) 0.062(3) Uani 1 1 d . . . H25 H 0.135(7) 0.435(9) 0.054(4) 0.07(3) Uiso 1 1 d . . . C26 C 0.0619(7) 0.2347(11) 0.1739(5) 0.047(2) Uani 1 1 d . . . H26A H 0.059(5) 0.321(7) 0.158(3) 0.03(2) Uiso 1 1 d . . . H26B H 0.077(6) 0.247(8) 0.212(3) 0.04(3) Uiso 1 1 d . . . C27 C -0.0324(6) 0.1657(9) 0.1528(4) 0.042(2) Uani 1 1 d . . . C28 C -0.0689(7) 0.0568(10) 0.1843(4) 0.049(2) Uani 1 1 d . . . H28 H -0.030(5) 0.032(7) 0.226(3) 0.025(18) Uiso 1 1 d . . . C29 C -0.1500(8) -0.0160(12) 0.1618(5) 0.065(3) Uani 1 1 d . . . H29 H -0.170(5) -0.102(9) 0.187(3) 0.05(2) Uiso 1 1 d . . . C30 C -0.2001(8) 0.0224(14) 0.1097(6) 0.072(4) Uani 1 1 d . . . H30 H -0.247(5) -0.025(7) 0.095(3) 0.021(19) Uiso 1 1 d . . . C31 C -0.1688(7) 0.1308(16) 0.0779(5) 0.068(3) Uani 1 1 d . . . H31 H -0.208(7) 0.160(11) 0.046(4) 0.09(4) Uiso 1 1 d . . . C32 C -0.0852(7) 0.2048(11) 0.0993(4) 0.055(2) Uani 1 1 d . . . H32 H -0.057(7) 0.286(10) 0.078(4) 0.09(4) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Hf 0.03302(15) 0.03369(16) 0.03825(15) 0.0010(2) 0.00541(11) -0.0025(2) N1 0.042(4) 0.033(4) 0.054(4) -0.009(4) 0.011(3) -0.009(3) N2 0.039(4) 0.029(4) 0.040(4) 0.003(3) 0.002(3) -0.001(3) N3 0.037(4) 0.032(4) 0.042(4) -0.002(3) -0.002(3) 0.002(3) N4 0.034(3) 0.036(5) 0.040(4) -0.001(3) 0.009(3) -0.001(3) C1 0.052(5) 0.045(6) 0.049(5) -0.006(6) 0.000(4) -0.002(6) C2 0.060(7) 0.048(7) 0.092(9) -0.020(7) -0.005(6) -0.017(6) C3 0.057(6) 0.041(6) 0.065(7) 0.012(5) 0.010(5) -0.009(5) C5 0.042(5) 0.044(5) 0.058(6) 0.018(6) 0.015(4) 0.007(6) C6 0.044(5) 0.053(6) 0.040(5) 0.005(4) 0.007(4) 0.004(5) C7 0.061(6) 0.085(8) 0.055(6) 0.005(6) 0.014(5) 0.021(6) C8 0.060(5) 0.064(6) 0.049(5) 0.007(6) -0.005(4) 0.009(6) C9 0.051(5) 0.063(6) 0.044(4) 0.003(6) -0.007(4) -0.003(6) C10 0.050(6) 0.065(7) 0.050(6) -0.016(5) 0.004(5) 0.001(6) C11 0.095(11) 0.050(8) 0.112(12) -0.039(8) 0.012(8) -0.012(8) C12 0.042(6) 0.045(7) 0.113(10) -0.010(6) 0.005(6) -0.014(6) C13 0.040(5) 0.037(6) 0.044(5) 0.002(4) -0.008(4) -0.005(4) C14 0.039(6) 0.042(6) 0.051(6) 0.004(5) 0.009(4) -0.001(5) C15 0.034(5) 0.047(6) 0.061(6) -0.011(5) 0.007(4) 0.005(4) C19 0.055(7) 0.065(8) 0.053(6) 0.000(5) 0.013(5) 0.004(6) C20 0.051(6) 0.051(6) 0.037(5) 0.001(5) 0.000(4) -0.006(5) C21 0.069(7) 0.052(7) 0.048(6) 0.000(5) 0.009(5) -0.007(6) C22 0.086(9) 0.096(12) 0.045(6) 0.010(6) 0.014(6) -0.030(8) C23 0.132(13) 0.064(9) 0.051(7) 0.012(7) 0.003(7) -0.039(9) C24 0.169(17) 0.053(10) 0.058(8) 0.014(7) -0.005(9) -0.001(11) C25 0.083(9) 0.057(7) 0.047(6) 0.009(5) 0.011(6) 0.003(7) C26 0.042(5) 0.044(6) 0.055(6) -0.008(5) -0.001(5) 0.002(5) C27 0.037(5) 0.047(6) 0.042(5) -0.005(4) 0.011(4) 0.003(4) C28 0.048(5) 0.061(6) 0.039(5) -0.001(5) 0.011(4) 0.008(5) C29 0.054(6) 0.067(8) 0.078(8) -0.008(6) 0.031(6) -0.015(6) C30 0.041(6) 0.085(9) 0.092(9) -0.032(8) 0.009(6) -0.020(6) C31 0.043(5) 0.092(9) 0.065(6) -0.017(8) -0.007(5) 0.016(8) C32 0.049(6) 0.061(7) 0.055(6) -0.007(5) 0.008(5) 0.007(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Hf N3 2.196(6) . ? Hf N1 2.201(6) . ? Hf C19 2.252(10) . ? Hf C26 2.270(9) . ? Hf N2 2.354(6) . ? Hf N4 2.363(6) . ? N1 C4A 1.22(3) . ? N1 C1 1.355(10) . ? N1 C4B 1.40(2) . ? N2 C5 1.303(12) . ? N2 C6 1.506(10) . ? N3 C10 1.365(11) . ? N3 C13 1.377(10) . ? N4 C14 1.281(11) . ? N4 C15 1.497(10) . ? C1 C2 1.380(14) . ? C1 H1 0.85(7) . ? C2 C3 1.374(14) . ? C2 H2 0.77(7) . ? C3 C4B 1.34(2) . ? C3 C4A 1.47(3) . ? C3 H3 0.80(6) . ? C4A C5 1.44(3) . ? C4B C5 1.39(2) . ? C5 H5 0.71(7) . ? C6 C9 1.511(11) . ? C6 C7 1.527(11) . ? C6 C8 1.530(12) . ? C7 H7A 0.9600 . ? C7 H7B 0.9600 . ? C7 H7C 0.9600 . ? C8 H8A 0.9600 . ? C8 H8B 0.9600 . ? C8 H8C 0.9600 . ? C9 H9A 0.9600 . ? C9 H9B 0.9600 . ? C9 H9C 0.9600 . ? C10 C11 1.337(17) . ? C10 H10 0.89(7) . ? C11 C12 1.361(17) . ? C11 H11 0.56(6) . ? C12 C13 1.390(13) . ? C12 H12 0.77(7) . ? C13 C14 1.403(11) . ? C14 H14 1.01(8) . ? C15 C17A 1.47(2) . ? C15 C16B 1.49(2) . ? C15 C18B 1.51(2) . ? C15 C17B 1.522(19) . ? C15 C18A 1.53(2) . ? C15 C16A 1.53(2) . ? C16A H16A 0.9600 . ? C16A H16B 0.9600 . ? C16A H16C 0.9600 . ? C17A H17A 0.9600 . ? C17A H17B 0.9600 . ? C17A H17C 0.9600 . ? C18A H18A 0.9600 . ? C18A H18B 0.9600 . ? C18A H18C 0.9600 . ? C16B H16D 0.9600 . ? C16B H16E 0.9600 . ? C16B H16F 0.9600 . ? C17B H17D 0.9600 . ? C17B H17E 0.9600 . ? C17B H17F 0.9600 . ? C18B H18D 0.9600 . ? C18B H18E 0.9600 . ? C18B H18F 0.9600 . ? C19 C20 1.498(13) . ? C19 H19A 1.04(9) . ? C19 H19B 0.85(6) . ? C20 C25 1.381(13) . ? C20 C21 1.386(12) . ? C21 C22 1.390(14) . ? C21 H21 1.08(8) . ? C22 C23 1.332(17) . ? C22 H22 0.87(10) . ? C23 C24 1.42(2) . ? C23 H23 0.98(10) . ? C24 C25 1.337(17) . ? C24 H24 0.74(11) . ? C25 H25 0.95(8) . ? C26 C27 1.485(12) . ? C26 H26A 0.92(7) . ? C26 H26B 0.86(7) . ? C27 C28 1.387(11) . ? C27 C32 1.394(12) . ? C28 C29 1.367(13) . ? C28 H28 1.05(6) . ? C29 C30 1.349(15) . ? C29 H29 1.05(8) . ? C30 C31 1.362(16) . ? C30 H30 0.83(7) . ? C31 C32 1.393(14) . ? C31 H31 0.90(10) . ? C32 H32 1.02(10) . ? 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 N3 Hf N1 178.7(3) . . ? N3 Hf C19 96.9(3) . . ? N1 Hf C19 83.8(3) . . ? N3 Hf C26 82.8(3) . . ? N1 Hf C26 96.0(3) . . ? C19 Hf C26 96.4(4) . . ? N3 Hf N2 106.4(2) . . ? N1 Hf N2 73.1(3) . . ? C19 Hf N2 155.6(3) . . ? C26 Hf N2 93.6(3) . . ? N3 Hf N4 73.3(2) . . ? N1 Hf N4 107.8(2) . . ? C19 Hf N4 89.5(3) . . ? C26 Hf N4 156.0(3) . . ? N2 Hf N4 90.4(2) . . ? C4A N1 C1 107.1(16) . . ? C4A N1 C4B 9(2) . . ? C1 N1 C4B 104.3(10) . . ? C4A N1 Hf 115.3(15) . . ? C1 N1 Hf 137.4(7) . . ? C4B N1 Hf 116.9(9) . . ? C5 N2 C6 117.5(7) . . ? C5 N2 Hf 110.4(6) . . ? C6 N2 Hf 131.7(5) . . ? C10 N3 C13 105.1(7) . . ? C10 N3 Hf 139.7(6) . . ? C13 N3 Hf 114.1(5) . . ? C14 N4 C15 118.8(7) . . ? C14 N4 Hf 111.3(6) . . ? C15 N4 Hf 129.6(5) . . ? N1 C1 C2 111.2(9) . . ? N1 C1 H1 121(6) . . ? C2 C1 H1 127(6) . . ? C3 C2 C1 105.5(9) . . ? C3 C2 H2 130(6) . . ? C1 C2 H2 124(6) . . ? C4B C3 C2 109.1(12) . . ? C4B C3 C4A 10.3(18) . . ? C2 C3 C4A 102.7(15) . . ? C4B C3 H3 117(5) . . ? C2 C3 H3 133(5) . . ? C4A C3 H3 124(5) . . ? N1 C4A C5 123(2) . . ? N1 C4A C3 113(2) . . ? C5 C4A C3 120(2) . . ? C3 C4B C5 136.1(18) . . ? C3 C4B N1 109.6(15) . . ? C5 C4B N1 114.2(15) . . ? N2 C5 C4B 124.8(12) . . ? N2 C5 C4A 116.8(15) . . ? C4B C5 C4A 11.3(17) . . ? N2 C5 H5 129(7) . . ? C4B C5 H5 106(7) . . ? C4A C5 H5 114(7) . . ? N2 C6 C9 108.1(6) . . ? N2 C6 C7 107.9(7) . . ? C9 C6 C7 109.5(8) . . ? N2 C6 C8 111.8(7) . . ? C9 C6 C8 109.4(7) . . ? C7 C6 C8 110.1(7) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C6 C8 H8A 109.5 . . ? C6 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C6 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C6 C9 H9A 109.5 . . ? C6 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C6 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C11 C10 N3 110.4(10) . . ? C11 C10 H10 133(5) . . ? N3 C10 H10 117(5) . . ? C10 C11 C12 109.2(11) . . ? C10 C11 H11 111(9) . . ? C12 C11 H11 134(9) . . ? C11 C12 C13 105.7(10) . . ? C11 C12 H12 123(6) . . ? C13 C12 H12 130(6) . . ? N3 C13 C12 109.5(8) . . ? N3 C13 C14 119.1(8) . . ? C12 C13 C14 131.4(9) . . ? N4 C14 C13 120.6(8) . . ? N4 C14 H14 126(5) . . ? C13 C14 H14 113(5) . . ? C17A C15 C16B 78.2(14) . . ? C17A C15 N4 109.5(11) . . ? C16B C15 N4 106.9(11) . . ? C17A C15 C18B 128.8(14) . . ? C16B C15 C18B 107.4(14) . . ? N4 C15 C18B 116.5(11) . . ? C17A C15 C17B 30.8(10) . . ? C16B C15 C17B 108.1(14) . . ? N4 C15 C17B 107.1(9) . . ? C18B C15 C17B 110.6(12) . . ? C17A C15 C18A 112.3(13) . . ? C16B C15 C18A 133.4(14) . . ? N4 C15 C18A 111.0(11) . . ? C18B C15 C18A 30.0(10) . . ? C17B C15 C18A 85.8(11) . . ? C17A C15 C16A 107.4(15) . . ? C16B C15 C16A 31.4(11) . . ? N4 C15 C16A 106.7(11) . . ? C18B C15 C16A 80.2(13) . . ? C17B C15 C16A 134.0(14) . . ? C18A C15 C16A 109.7(13) . . ? C15 C16A H16A 109.5 . . ? C15 C16A H16B 109.5 . . ? C15 C16A H16C 109.5 . . ? C15 C17A H17A 109.5 . . ? C15 C17A H17B 109.5 . . ? C15 C17A H17C 109.5 . . ? C15 C18A H18A 109.5 . . ? C15 C18A H18B 109.5 . . ? C15 C18A H18C 109.5 . . ? C15 C16B H16D 109.5 . . ? C15 C16B H16E 109.5 . . ? H16D C16B H16E 109.5 . . ? C15 C16B H16F 109.5 . . ? H16D C16B H16F 109.5 . . ? H16E C16B H16F 109.5 . . ? C15 C17B H17D 109.5 . . ? C15 C17B H17E 109.5 . . ? H17D C17B H17E 109.5 . . ? C15 C17B H17F 109.5 . . ? H17D C17B H17F 109.5 . . ? H17E C17B H17F 109.5 . . ? C15 C18B H18D 109.5 . . ? C15 C18B H18E 109.5 . . ? H18D C18B H18E 109.5 . . ? C15 C18B H18F 109.5 . . ? H18D C18B H18F 109.5 . . ? H18E C18B H18F 109.5 . . ? C20 C19 Hf 116.3(7) . . ? C20 C19 H19A 107(5) . . ? Hf C19 H19A 103(5) . . ? C20 C19 H19B 105(4) . . ? Hf C19 H19B 107(4) . . ? H19A C19 H19B 118(7) . . ? C25 C20 C21 115.3(10) . . ? C25 C20 C19 121.5(9) . . ? C21 C20 C19 123.2(10) . . ? C20 C21 C22 121.7(12) . . ? C20 C21 H21 114(5) . . ? C22 C21 H21 124(5) . . ? C23 C22 C21 121.6(13) . . ? C23 C22 H22 121(9) . . ? C21 C22 H22 117(9) . . ? C22 C23 C24 117.6(14) . . ? C22 C23 H23 122(5) . . ? C24 C23 H23 120(5) . . ? C25 C24 C23 119.9(15) . . ? C25 C24 H24 132(10) . . ? C23 C24 H24 108(10) . . ? C24 C25 C20 123.8(13) . . ? C24 C25 H25 123(6) . . ? C20 C25 H25 114(6) . . ? C27 C26 Hf 114.6(6) . . ? C27 C26 H26A 107(4) . . ? Hf C26 H26A 109(4) . . ? C27 C26 H26B 120(5) . . ? Hf C26 H26B 101(5) . . ? H26A C26 H26B 105(7) . . ? C28 C27 C32 117.7(9) . . ? C28 C27 C26 121.5(8) . . ? C32 C27 C26 120.8(9) . . ? C29 C28 C27 121.5(9) . . ? C29 C28 H28 122(4) . . ? C27 C28 H28 117(4) . . ? C30 C29 C28 120.1(11) . . ? C30 C29 H29 123(4) . . ? C28 C29 H29 117(4) . . ? C29 C30 C31 120.7(11) . . ? C29 C30 H30 120(5) . . ? C31 C30 H30 119(5) . . ? C30 C31 C32 120.2(11) . . ? C30 C31 H31 118(7) . . ? C32 C31 H31 121(7) . . ? C31 C32 C27 119.7(10) . . ? C31 C32 H32 125(5) . . ? C27 C32 H32 116(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 N3 Hf N1 C4A -69(13) . . . . ? C19 Hf N1 C4A 169.3(16) . . . . ? C26 Hf N1 C4A -94.9(16) . . . . ? N2 Hf N1 C4A -3.0(16) . . . . ? N4 Hf N1 C4A 81.8(16) . . . . ? N3 Hf N1 C1 106(13) . . . . ? C19 Hf N1 C1 -15.8(8) . . . . ? C26 Hf N1 C1 80.0(8) . . . . ? N2 Hf N1 C1 171.9(8) . . . . ? N4 Hf N1 C1 -103.3(8) . . . . ? N3 Hf N1 C4B -59(13) . . . . ? C19 Hf N1 C4B 179.6(11) . . . . ? C26 Hf N1 C4B -84.6(11) . . . . ? N2 Hf N1 C4B 7.3(10) . . . . ? N4 Hf N1 C4B 92.1(10) . . . . ? N3 Hf N2 C5 174.3(6) . . . . ? N1 Hf N2 C5 -4.5(6) . . . . ? C19 Hf N2 C5 -23.3(11) . . . . ? C26 Hf N2 C5 90.7(6) . . . . ? N4 Hf N2 C5 -113.0(6) . . . . ? N3 Hf N2 C6 2.0(7) . . . . ? N1 Hf N2 C6 -176.8(7) . . . . ? C19 Hf N2 C6 164.5(8) . . . . ? C26 Hf N2 C6 -81.5(7) . . . . ? N4 Hf N2 C6 74.8(6) . . . . ? N1 Hf N3 C10 -32(13) . . . . ? C19 Hf N3 C10 89.3(10) . . . . ? C26 Hf N3 C10 -6.3(9) . . . . ? N2 Hf N3 C10 -97.9(9) . . . . ? N4 Hf N3 C10 176.7(10) . . . . ? N1 Hf N3 C13 162(13) . . . . ? C19 Hf N3 C13 -76.6(6) . . . . ? C26 Hf N3 C13 -172.2(6) . . . . ? N2 Hf N3 C13 96.1(5) . . . . ? N4 Hf N3 C13 10.8(5) . . . . ? N3 Hf N4 C14 -10.2(6) . . . . ? N1 Hf N4 C14 170.4(6) . . . . ? C19 Hf N4 C14 87.1(6) . . . . ? C26 Hf N4 C14 -17.6(11) . . . . ? N2 Hf N4 C14 -117.2(6) . . . . ? N3 Hf N4 C15 176.4(7) . . . . ? N1 Hf N4 C15 -3.0(7) . . . . ? C19 Hf N4 C15 -86.3(7) . . . . ? C26 Hf N4 C15 169.0(8) . . . . ? N2 Hf N4 C15 69.3(7) . . . . ? C4A N1 C1 C2 4.9(18) . . . . ? C4B N1 C1 C2 -4.4(13) . . . . ? Hf N1 C1 C2 -170.2(7) . . . . ? N1 C1 C2 C3 1.6(12) . . . . ? C1 C2 C3 C4B 2.1(15) . . . . ? C1 C2 C3 C4A -6.3(16) . . . . ? C1 N1 C4A C5 -166.0(19) . . . . ? C4B N1 C4A C5 -92(13) . . . . ? Hf N1 C4A C5 10(3) . . . . ? C1 N1 C4A C3 -9(2) . . . . ? C4B N1 C4A C3 65(12) . . . . ? Hf N1 C4A C3 167.1(13) . . . . ? C4B C3 C4A N1 -119(13) . . . . ? C2 C3 C4A N1 10(2) . . . . ? C4B C3 C4A C5 38(10) . . . . ? C2 C3 C4A C5 168(2) . . . . ? C2 C3 C4B C5 -179(2) . . . . ? C4A C3 C4B C5 -127(13) . . . . ? C2 C3 C4B N1 -4.9(18) . . . . ? C4A C3 C4B N1 48(11) . . . . ? C4A N1 C4B C3 -103(13) . . . . ? C1 N1 C4B C3 5.7(17) . . . . ? Hf N1 C4B C3 175.0(10) . . . . ? C4A N1 C4B C5 73(13) . . . . ? C1 N1 C4B C5 -178.5(13) . . . . ? Hf N1 C4B C5 -9.2(19) . . . . ? C6 N2 C5 C4B 174.8(12) . . . . ? Hf N2 C5 C4B 1.4(15) . . . . ? C6 N2 C5 C4A -175.9(15) . . . . ? Hf N2 C5 C4A 10.6(16) . . . . ? C3 C4B C5 N2 179.3(18) . . . . ? N1 C4B C5 N2 5(2) . . . . ? C3 C4B C5 C4A 132(12) . . . . ? N1 C4B C5 C4A -43(10) . . . . ? N1 C4A C5 N2 -15(3) . . . . ? C3 C4A C5 N2 -170.2(17) . . . . ? N1 C4A C5 C4B 122(12) . . . . ? C3 C4A C5 C4B -33(9) . . . . ? C5 N2 C6 C9 167.8(7) . . . . ? Hf N2 C6 C9 -20.4(9) . . . . ? C5 N2 C6 C7 -73.9(10) . . . . ? Hf N2 C6 C7 97.9(8) . . . . ? C5 N2 C6 C8 47.3(10) . . . . ? Hf N2 C6 C8 -140.9(6) . . . . ? C13 N3 C10 C11 0.3(12) . . . . ? Hf N3 C10 C11 -166.4(9) . . . . ? N3 C10 C11 C12 -0.3(16) . . . . ? C10 C11 C12 C13 0.0(16) . . . . ? C10 N3 C13 C12 -0.3(11) . . . . ? Hf N3 C13 C12 170.3(7) . . . . ? C10 N3 C13 C14 178.2(8) . . . . ? Hf N3 C13 C14 -11.1(9) . . . . ? C11 C12 C13 N3 0.2(14) . . . . ? C11 C12 C13 C14 -178.1(11) . . . . ? C15 N4 C14 C13 -177.5(8) . . . . ? Hf N4 C14 C13 8.2(10) . . . . ? N3 C13 C14 N4 1.4(13) . . . . ? C12 C13 C14 N4 179.6(11) . . . . ? C14 N4 C15 C17A -158.2(12) . . . . ? Hf N4 C15 C17A 14.8(14) . . . . ? C14 N4 C15 C16B 118.6(12) . . . . ? Hf N4 C15 C16B -68.4(12) . . . . ? C14 N4 C15 C18B -1.4(15) . . . . ? Hf N4 C15 C18B 171.6(10) . . . . ? C14 N4 C15 C17B -125.8(11) . . . . ? Hf N4 C15 C17B 47.2(11) . . . . ? C14 N4 C15 C18A -33.7(13) . . . . ? Hf N4 C15 C18A 139.3(10) . . . . ? C14 N4 C15 C16A 85.8(13) . . . . ? Hf N4 C15 C16A -101.2(12) . . . . ? N3 Hf C19 C20 13.1(8) . . . . ? N1 Hf C19 C20 -168.0(8) . . . . ? C26 Hf C19 C20 96.6(8) . . . . ? N2 Hf C19 C20 -150.0(6) . . . . ? N4 Hf C19 C20 -60.1(8) . . . . ? Hf C19 C20 C25 -77.8(11) . . . . ? Hf C19 C20 C21 99.7(10) . . . . ? C25 C20 C21 C22 0.2(14) . . . . ? C19 C20 C21 C22 -177.5(10) . . . . ? C20 C21 C22 C23 0.8(17) . . . . ? C21 C22 C23 C24 -0.9(19) . . . . ? C22 C23 C24 C25 0(2) . . . . ? C23 C24 C25 C20 1(2) . . . . ? C21 C20 C25 C24 -1.1(17) . . . . ? C19 C20 C25 C24 176.6(11) . . . . ? N3 Hf C26 C27 166.4(8) . . . . ? N1 Hf C26 C27 -14.1(8) . . . . ? C19 Hf C26 C27 70.2(8) . . . . ? N2 Hf C26 C27 -87.5(7) . . . . ? N4 Hf C26 C27 173.6(5) . . . . ? Hf C26 C27 C28 83.0(9) . . . . ? Hf C26 C27 C32 -94.3(9) . . . . ? C32 C27 C28 C29 4.3(13) . . . . ? C26 C27 C28 C29 -173.1(9) . . . . ? C27 C28 C29 C30 -4.0(15) . . . . ? C28 C29 C30 C31 2.2(16) . . . . ? C29 C30 C31 C32 -0.9(17) . . . . ? C30 C31 C32 C27 1.3(15) . . . . ? C28 C27 C32 C31 -2.9(13) . . . . ? C26 C27 C32 C31 174.5(8) . . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.96 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 1.699 _refine_diff_density_min -0.696 _refine_diff_density_rms 0.144