Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name _publ_author_address 'Christoph Marschner' ; Institut fur Anorganische Chemie Technische Universitaet Graz Stremayrgasse 16 A-8010 Graz Austria ; 'Dieter Frank' ; Institut fur Anorganische Chemie Technische Universitaet Graz Stremayrgasse 16 A-8010 Graz Austria ; 'Judith Baumgartner' ; Institut fur Anorganische Chemie Technische Universitaet Graz Stremayrgasse 16 A-8010 Graz Austria ; _publ_contact_author_name 'Prof Christoph Marschner' _publ_contact_author_address ; Institut fur Anorganische Chemie Technische Universitat Graz Stremayrgasse 16 Graz A-8010 AUSTRIA ; _publ_contact_author_phone '+43 316 873 8209' _publ_contact_author_fax '+43 316 873 8701' _publ_contact_author_email 'marschner@anorg.tu-graz.ac.at' _publ_requested_journal 'Chem. Commun.' _publ_requested_coeditor_name ? _publ_contact_letter ; ? ; #============================================================================== # 2. TITLE AND AUTHOR LIST _publ_section_title ; First successful reaction of a silyl anion with haffnium tetrachloride ; data_5jneu _database_code_CSD 177992 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C6 H16 Cl4 Hf N2' _chemical_formula_weight 436.50 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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Hf' 'Hf' -0.5830 6.1852 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M Pna2(1) 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' _cell_length_a 14.797(5) _cell_length_b 7.552(3) _cell_length_c 12.000(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1341.0(8) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plates _exptl_crystal_colour yellow _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.162 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 824 _exptl_absorpt_coefficient_mu 8.540 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _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 'Bruker P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time 10 _diffrn_standards_decay_% ? _diffrn_reflns_number 5609 _diffrn_reflns_av_R_equivalents 0.0505 _diffrn_reflns_av_sigmaI/netI 0.0588 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.75 _diffrn_reflns_theta_max 23.27 _reflns_number_total 1907 _reflns_number_gt 1479 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0240P)^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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.067(16) _refine_ls_number_reflns 1907 _refine_ls_number_parameters 122 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0450 _refine_ls_R_factor_gt 0.0329 _refine_ls_wR_factor_ref 0.0598 _refine_ls_wR_factor_gt 0.0574 _refine_ls_goodness_of_fit_ref 0.848 _refine_ls_restrained_S_all 0.847 _refine_ls_shift/su_max 0.032 _refine_ls_shift/su_mean 0.005 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 0.13270(3) -0.20033(5) 0.71993(7) 0.05965(16) Uani 1 1 d . . . Cl1 Cl 0.2421(2) -0.4270(4) 0.7068(6) 0.0969(12) Uani 1 1 d . . . Cl2 Cl 0.0713(3) -0.3253(5) 0.8856(3) 0.1043(13) Uani 1 1 d . . . Cl3 Cl 0.0119(3) -0.3116(6) 0.6113(4) 0.1236(16) Uani 1 1 d . . . Cl4 Cl 0.1925(3) -0.0520(6) 0.5607(3) 0.0991(14) Uani 1 1 d . . . N1 N 0.2355(8) -0.0388(17) 0.8322(11) 0.079(4) Uani 1 1 d . . . N2 N 0.0534(8) 0.0651(13) 0.7588(8) 0.074(3) Uani 1 1 d . . . C1 C 0.3120(14) 0.027(3) 0.7757(14) 0.198(12) Uani 1 1 d . . . H15A H 0.3499 0.0898 0.8273 0.297 Uiso 1 1 calc R . . H15B H 0.2930 0.1056 0.7175 0.297 Uiso 1 1 calc R . . H15C H 0.3452 -0.0700 0.7441 0.297 Uiso 1 1 calc R . . C2 C 0.2690(12) -0.136(2) 0.9286(11) 0.138(7) Uani 1 1 d . . . H12A H 0.2946 -0.2465 0.9045 0.207 Uiso 1 1 calc R . . H12B H 0.2200 -0.1588 0.9790 0.207 Uiso 1 1 calc R . . H12C H 0.3145 -0.0673 0.9657 0.207 Uiso 1 1 calc R . . C3 C 0.1779(14) 0.117(2) 0.8770(17) 0.155(9) Uani 1 1 d . . . H18A H 0.1493 0.0783 0.9456 0.186 Uiso 1 1 calc R . . H18B H 0.2187 0.2127 0.8961 0.186 Uiso 1 1 calc R . . C4 C 0.1125(10) 0.184(2) 0.8095(17) 0.119(7) Uani 1 1 d . . . H10A H 0.1420 0.2513 0.7511 0.142 Uiso 1 1 calc R . . H10B H 0.0768 0.2662 0.8530 0.142 Uiso 1 1 calc R . . C5 C 0.0207(14) 0.154(3) 0.6592(13) 0.159(10) Uani 1 1 d . . . H11A H 0.0006 0.2708 0.6781 0.239 Uiso 1 1 calc R . . H11B H -0.0287 0.0877 0.6282 0.239 Uiso 1 1 calc R . . H11C H 0.0686 0.1612 0.6055 0.239 Uiso 1 1 calc R . . C6 C -0.0294(10) 0.038(2) 0.8318(13) 0.111(5) Uani 1 1 d . . . H16A H -0.0111 -0.0071 0.9030 0.167 Uiso 1 1 calc R . . H16B H -0.0695 -0.0447 0.7967 0.167 Uiso 1 1 calc R . . H16C H -0.0599 0.1492 0.8417 0.167 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 Hf 0.0766(3) 0.0427(2) 0.0597(2) -0.0057(5) 0.0036(6) -0.0032(2) Cl1 0.110(2) 0.0590(17) 0.122(3) -0.012(3) 0.005(4) 0.0173(15) Cl2 0.156(4) 0.070(3) 0.086(2) 0.012(2) 0.043(3) -0.001(3) Cl3 0.137(4) 0.108(3) 0.125(3) -0.020(3) -0.039(3) -0.031(3) Cl4 0.135(4) 0.082(3) 0.081(3) 0.015(2) 0.033(3) 0.006(3) N1 0.081(9) 0.053(8) 0.103(10) -0.014(7) -0.025(8) -0.013(7) N2 0.082(8) 0.054(6) 0.086(9) 0.006(6) 0.011(6) 0.013(6) C1 0.21(2) 0.21(2) 0.17(2) 0.041(14) -0.058(16) -0.167(19) C2 0.167(17) 0.142(15) 0.105(13) -0.039(11) -0.088(13) 0.039(12) C3 0.20(2) 0.094(14) 0.172(18) -0.067(13) -0.107(17) 0.034(14) C4 0.108(13) 0.061(10) 0.187(18) -0.056(12) -0.009(11) 0.010(10) C5 0.21(2) 0.152(19) 0.113(15) 0.029(13) 0.046(15) 0.113(18) C6 0.091(11) 0.098(13) 0.145(14) 0.008(11) 0.042(11) 0.030(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 Hf Cl1 2.361(3) . ? Hf Cl3 2.367(4) . ? Hf N2 2.369(9) . ? Hf N1 2.370(11) . ? Hf Cl2 2.381(3) . ? Hf Cl4 2.385(4) . ? N1 C1 1.409(18) . ? N1 C2 1.457(17) . ? N1 C3 1.548(19) . ? N2 C4 1.392(16) . ? N2 C5 1.453(16) . ? N2 C6 1.519(15) . ? C1 H15A 0.9600 . ? C1 H15B 0.9600 . ? C1 H15C 0.9600 . ? C2 H12A 0.9600 . ? C2 H12B 0.9600 . ? C2 H12C 0.9600 . ? C3 C4 1.36(2) . ? C3 H18A 0.9700 . ? C3 H18B 0.9700 . ? C4 H10A 0.9700 . ? C4 H10B 0.9700 . ? C5 H11A 0.9600 . ? C5 H11B 0.9600 . ? C5 H11C 0.9600 . ? C6 H16A 0.9600 . ? C6 H16B 0.9600 . ? C6 H16C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag Cl1 Hf Cl3 102.94(18) . . ? Cl1 Hf N2 165.0(3) . . ? Cl3 Hf N2 92.0(3) . . ? Cl1 Hf N1 88.3(3) . . ? Cl3 Hf N1 168.7(3) . . ? N2 Hf N1 76.7(4) . . ? Cl1 Hf Cl2 91.72(18) . . ? Cl3 Hf Cl2 91.76(18) . . ? N2 Hf Cl2 89.0(3) . . ? N1 Hf Cl2 88.5(4) . . ? Cl1 Hf Cl4 91.89(19) . . ? Cl3 Hf Cl4 90.34(18) . . ? N2 Hf Cl4 86.8(3) . . ? N1 Hf Cl4 88.6(4) . . ? Cl2 Hf Cl4 175.32(14) . . ? C1 N1 C2 106.6(12) . . ? C1 N1 C3 110.0(14) . . ? C2 N1 C3 107.1(13) . . ? C1 N1 Hf 115.1(10) . . ? C2 N1 Hf 114.2(10) . . ? C3 N1 Hf 103.6(8) . . ? C4 N2 C5 105.8(14) . . ? C4 N2 C6 110.0(11) . . ? C5 N2 C6 105.5(11) . . ? C4 N2 Hf 108.6(9) . . ? C5 N2 Hf 113.1(7) . . ? C6 N2 Hf 113.5(8) . . ? N1 C1 H15A 109.5 . . ? N1 C1 H15B 109.5 . . ? H15A C1 H15B 109.5 . . ? N1 C1 H15C 109.5 . . ? H15A C1 H15C 109.5 . . ? H15B C1 H15C 109.5 . . ? N1 C2 H12A 109.5 . . ? N1 C2 H12B 109.5 . . ? H12A C2 H12B 109.5 . . ? N1 C2 H12C 109.5 . . ? H12A C2 H12C 109.5 . . ? H12B C2 H12C 109.5 . . ? C4 C3 N1 117.8(14) . . ? C4 C3 H18A 107.9 . . ? N1 C3 H18A 107.9 . . ? C4 C3 H18B 107.9 . . ? N1 C3 H18B 107.9 . . ? H18A C3 H18B 107.2 . . ? C3 C4 N2 118.0(15) . . ? C3 C4 H10A 107.8 . . ? N2 C4 H10A 107.8 . . ? C3 C4 H10B 107.8 . . ? N2 C4 H10B 107.8 . . ? H10A C4 H10B 107.1 . . ? N2 C5 H11A 109.5 . . ? N2 C5 H11B 109.5 . . ? H11A C5 H11B 109.5 . . ? N2 C5 H11C 109.5 . . ? H11A C5 H11C 109.5 . . ? H11B C5 H11C 109.5 . . ? N2 C6 H16A 109.5 . . ? N2 C6 H16B 109.5 . . ? H16A C6 H16B 109.5 . . ? N2 C6 H16C 109.5 . . ? H16A C6 H16C 109.5 . . ? H16B C6 H16C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag Cl1 Hf N1 C1 69.6(13) . . . . ? Cl3 Hf N1 C1 -107.0(19) . . . . ? N2 Hf N1 C1 -109.3(13) . . . . ? Cl2 Hf N1 C1 161.4(13) . . . . ? Cl4 Hf N1 C1 -22.3(13) . . . . ? Cl1 Hf N1 C2 -54.1(10) . . . . ? Cl3 Hf N1 C2 129.3(15) . . . . ? N2 Hf N1 C2 126.9(11) . . . . ? Cl2 Hf N1 C2 37.6(10) . . . . ? Cl4 Hf N1 C2 -146.1(10) . . . . ? Cl1 Hf N1 C3 -170.3(11) . . . . ? Cl3 Hf N1 C3 13(3) . . . . ? N2 Hf N1 C3 10.7(11) . . . . ? Cl2 Hf N1 C3 -78.5(11) . . . . ? Cl4 Hf N1 C3 97.8(11) . . . . ? Cl1 Hf N2 C4 5.5(18) . . . . ? Cl3 Hf N2 C4 -170.0(11) . . . . ? N1 Hf N2 C4 9.5(11) . . . . ? Cl2 Hf N2 C4 98.2(11) . . . . ? Cl4 Hf N2 C4 -79.8(10) . . . . ? Cl1 Hf N2 C5 122.6(14) . . . . ? Cl3 Hf N2 C5 -52.9(13) . . . . ? N1 Hf N2 C5 126.7(14) . . . . ? Cl2 Hf N2 C5 -144.6(13) . . . . ? Cl4 Hf N2 C5 37.3(13) . . . . ? Cl1 Hf N2 C6 -117.1(13) . . . . ? Cl3 Hf N2 C6 67.3(9) . . . . ? N1 Hf N2 C6 -113.1(10) . . . . ? Cl2 Hf N2 C6 -24.4(9) . . . . ? Cl4 Hf N2 C6 157.6(9) . . . . ? C1 N1 C3 C4 90(2) . . . . ? C2 N1 C3 C4 -154.8(18) . . . . ? Hf N1 C3 C4 -34(2) . . . . ? N1 C3 C4 N2 49(3) . . . . ? C5 N2 C4 C3 -155.1(17) . . . . ? C6 N2 C4 C3 91.4(18) . . . . ? Hf N2 C4 C3 -33.4(19) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 23.27 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.752 _refine_diff_density_min -0.479 _refine_diff_density_rms 0.092 data_44jneu _database_code_CSD 177993 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H58 Cl3 Hf N3 Si4' _chemical_formula_weight 857.99 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' 'Si' 'Si' 0.0817 0.0704 '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' 'Hf' 'Hf' -0.5830 6.1852 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorombic _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, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 11.625(2) _cell_length_b 12.164(2) _cell_length_c 29.975(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4238.8(15) _cell_formula_units_Z 4 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plates _exptl_crystal_colour orange _exptl_crystal_size_max 0.39 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.26 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.344 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1752 _exptl_absorpt_coefficient_mu 2.785 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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 'Bruker P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time 10 _diffrn_standards_decay_% ? _diffrn_reflns_number 25824 _diffrn_reflns_av_R_equivalents 0.0401 _diffrn_reflns_av_sigmaI/netI 0.0371 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_theta_min 1.81 _diffrn_reflns_theta_max 23.26 _reflns_number_total 6067 _reflns_number_gt 5665 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0538P)^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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.002(9) _refine_ls_number_reflns 6067 _refine_ls_number_parameters 355 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0331 _refine_ls_R_factor_gt 0.0305 _refine_ls_wR_factor_ref 0.0797 _refine_ls_wR_factor_gt 0.0786 _refine_ls_goodness_of_fit_ref 0.982 _refine_ls_restrained_S_all 0.982 _refine_ls_shift/su_max 0.300 _refine_ls_shift/su_mean 0.022 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 Hf1 Hf 0.37250(2) -0.14331(2) 0.907909(8) 0.04619(9) Uani 1 1 d . . . Cl1 Cl 0.31002(17) -0.25559(15) 0.84529(6) 0.0707(5) Uani 1 1 d . . . Cl2 Cl 0.45781(18) -0.06036(16) 0.97361(5) 0.0702(5) Uani 1 1 d . . . Cl3 Cl 0.17910(17) -0.15279(17) 0.94005(8) 0.0840(6) Uani 1 1 d . . . Si1 Si 0.23329(13) 0.14863(15) 0.87520(5) 0.0461(4) Uani 1 1 d . . . Si2 Si 0.20251(17) 0.21441(15) 0.94884(6) 0.0577(5) Uani 1 1 d . . . Si3 Si 0.05666(16) 0.08124(19) 0.84614(8) 0.0693(6) Uani 1 1 d . . . Si4 Si 0.29276(17) 0.29886(16) 0.82978(7) 0.0577(5) Uani 1 1 d . . . N1 N 0.3841(6) -0.3203(4) 0.95148(18) 0.0665(15) Uani 1 1 d . . . N2 N 0.5649(5) -0.2196(5) 0.89251(19) 0.0657(16) Uani 1 1 d . . . N3 N 0.4258(4) -0.0084(4) 0.86485(15) 0.0433(12) Uani 1 1 d . . . C1 C 0.2902(10) -0.4006(7) 0.9398(4) 0.119(4) Uani 1 1 d . . . H1A H 0.2761 -0.3982 0.9083 0.179 Uiso 1 1 calc R . . H1B H 0.2212 -0.3812 0.9556 0.179 Uiso 1 1 calc R . . H1C H 0.3135 -0.4734 0.9482 0.179 Uiso 1 1 calc R . . C2 C 0.3807(9) -0.3082(7) 0.9997(2) 0.101(3) Uani 1 1 d . . . H2A H 0.3909 -0.3787 1.0135 0.152 Uiso 1 1 calc R . . H2B H 0.3078 -0.2780 1.0085 0.152 Uiso 1 1 calc R . . H2C H 0.4413 -0.2597 1.0091 0.152 Uiso 1 1 calc R . . C3 C 0.4977(9) -0.3705(9) 0.9393(4) 0.120(4) Uani 1 1 d . . . H3A H 0.5319 -0.3961 0.9669 0.145 Uiso 1 1 calc R . . H3B H 0.4806 -0.4356 0.9218 0.145 Uiso 1 1 calc R . . C4 C 0.5738(10) -0.3209(10) 0.9192(6) 0.197(8) Uani 1 1 d . . . H4A H 0.6074 -0.3748 0.8992 0.237 Uiso 1 1 calc R . . H4B H 0.6320 -0.3053 0.9415 0.237 Uiso 1 1 calc R . . C5 C 0.6615(6) -0.1510(8) 0.9065(3) 0.093(3) Uani 1 1 d . . . H5A H 0.7300 -0.1949 0.9081 0.140 Uiso 1 1 calc R . . H5B H 0.6456 -0.1202 0.9353 0.140 Uiso 1 1 calc R . . H5C H 0.6725 -0.0927 0.8853 0.140 Uiso 1 1 calc R . . C6 C 0.5848(8) -0.2509(10) 0.8462(3) 0.125(4) Uani 1 1 d . . . H6A H 0.6658 -0.2601 0.8412 0.188 Uiso 1 1 calc R . . H6B H 0.5558 -0.1944 0.8268 0.188 Uiso 1 1 calc R . . H6C H 0.5458 -0.3188 0.8400 0.188 Uiso 1 1 calc R . . C7 C 0.3292(5) 0.0207(5) 0.88099(18) 0.0381(13) Uani 1 1 d . . . C8 C 0.5040(5) 0.0491(5) 0.8356(2) 0.0461(14) Uani 1 1 d . . . C9 C 0.4976(5) 0.0281(6) 0.7899(2) 0.0596(18) Uani 1 1 d . . . C10 C 0.5792(6) 0.0773(7) 0.7622(2) 0.069(2) Uani 1 1 d . . . H10 H 0.5768 0.0647 0.7316 0.083 Uiso 1 1 calc R . . C11 C 0.6626(6) 0.1439(7) 0.7797(3) 0.0716(19) Uani 1 1 d . . . H11 H 0.7167 0.1761 0.7608 0.086 Uiso 1 1 calc R . . C12 C 0.6673(6) 0.1638(6) 0.8250(3) 0.075(2) Uani 1 1 d . . . H12 H 0.7245 0.2094 0.8364 0.090 Uiso 1 1 calc R . . C13 C 0.5870(5) 0.1163(5) 0.8542(2) 0.0548(17) Uani 1 1 d . . . C14 C 0.5931(6) 0.1455(6) 0.9024(2) 0.0702(18) Uani 1 1 d . . . H14A H 0.5205 0.1300 0.9163 0.105 Uiso 1 1 calc R . . H14B H 0.6102 0.2223 0.9054 0.105 Uiso 1 1 calc R . . H14C H 0.6523 0.1030 0.9165 0.105 Uiso 1 1 calc R . . C15 C 0.4086(6) -0.0456(7) 0.7702(2) 0.078(2) Uani 1 1 d . . . H15A H 0.3335 -0.0163 0.7762 0.117 Uiso 1 1 calc R . . H15B H 0.4150 -0.1175 0.7832 0.117 Uiso 1 1 calc R . . H15C H 0.4200 -0.0505 0.7386 0.117 Uiso 1 1 calc R . . C16 C 0.3385(7) 0.2622(8) 0.9745(3) 0.092(3) Uani 1 1 d . . . H16A H 0.3742 0.3154 0.9554 0.138 Uiso 1 1 calc R . . H16B H 0.3893 0.2008 0.9785 0.138 Uiso 1 1 calc R . . H16C H 0.3224 0.2951 1.0029 0.138 Uiso 1 1 calc R . . C17 C 0.1363(8) 0.1101(6) 0.9873(2) 0.083(2) Uani 1 1 d . . . H17A H 0.1812 0.0439 0.9868 0.124 Uiso 1 1 calc R . . H17B H 0.0593 0.0942 0.9777 0.124 Uiso 1 1 calc R . . H17C H 0.1346 0.1390 1.0171 0.124 Uiso 1 1 calc R . . C18 C 0.1013(7) 0.3338(6) 0.9459(3) 0.089(3) Uani 1 1 d . . . H18A H 0.0870 0.3610 0.9755 0.134 Uiso 1 1 calc R . . H18B H 0.0301 0.3105 0.9327 0.134 Uiso 1 1 calc R . . H18C H 0.1347 0.3910 0.9281 0.134 Uiso 1 1 calc R . . C19 C 0.0838(8) -0.0396(8) 0.8080(4) 0.116(4) Uani 1 1 d . . . H19A H 0.0123 -0.0636 0.7952 0.174 Uiso 1 1 calc R . . H19B H 0.1174 -0.0987 0.8248 0.174 Uiso 1 1 calc R . . H19C H 0.1354 -0.0180 0.7846 0.174 Uiso 1 1 calc R . . C20 C -0.0472(7) 0.0436(10) 0.8888(3) 0.115(4) Uani 1 1 d . . . H20A H -0.0684 0.1078 0.9055 0.172 Uiso 1 1 calc R . . H20B H -0.0137 -0.0098 0.9085 0.172 Uiso 1 1 calc R . . H20C H -0.1144 0.0130 0.8749 0.172 Uiso 1 1 calc R . . C21 C -0.0123(7) 0.1886(9) 0.8111(4) 0.107(3) Uani 1 1 d . . . H21A H 0.0418 0.2146 0.7893 0.161 Uiso 1 1 calc R . . H21B H -0.0362 0.2488 0.8296 0.161 Uiso 1 1 calc R . . H21C H -0.0781 0.1580 0.7962 0.161 Uiso 1 1 calc R . . C22 C 0.1804(8) 0.4115(6) 0.8311(3) 0.093(3) Uani 1 1 d . . . H22A H 0.1646 0.4314 0.8615 0.139 Uiso 1 1 calc R . . H22B H 0.1110 0.3857 0.8172 0.139 Uiso 1 1 calc R . . H22C H 0.2085 0.4746 0.8153 0.139 Uiso 1 1 calc R . . C23 C 0.3129(7) 0.2602(6) 0.7700(2) 0.078(2) Uani 1 1 d . . . H23A H 0.3313 0.3246 0.7530 0.118 Uiso 1 1 calc R . . H23B H 0.2433 0.2280 0.7588 0.118 Uiso 1 1 calc R . . H23C H 0.3746 0.2080 0.7676 0.118 Uiso 1 1 calc R . . C24 C 0.4303(7) 0.3626(7) 0.8496(3) 0.079(2) Uani 1 1 d . . . H24A H 0.4942 0.3198 0.8391 0.118 Uiso 1 1 calc R . . H24B H 0.4310 0.3644 0.8816 0.118 Uiso 1 1 calc R . . H24C H 0.4362 0.4361 0.8382 0.118 Uiso 1 1 calc R . . C65 C 0.9177(8) 0.5810(9) 0.8960(3) 0.101(3) Uiso 1 1 d . . . H65 H 0.9557 0.6150 0.9196 0.121 Uiso 1 1 calc R . . C67 C 0.7786(12) 0.4354(12) 0.8907(5) 0.148(5) Uiso 1 1 d . . . H69 H 0.7325 0.3822 0.9041 0.178 Uiso 1 1 calc R . . C66 C 0.8548(12) 0.5050(12) 0.9105(5) 0.154(5) Uiso 1 1 d . . . H68 H 0.8617 0.4941 0.9411 0.185 Uiso 1 1 calc R . . C68 C 0.7863(14) 0.4635(14) 0.8447(5) 0.174(6) Uiso 1 1 d . . . H70 H 0.7393 0.4261 0.8247 0.209 Uiso 1 1 calc R . . C70 C 0.9618(16) 0.6514(17) 0.8392(6) 0.221(8) Uiso 1 1 d . . . H72 H 1.0069 0.7060 0.8264 0.265 Uiso 1 1 calc R . . C69 C 0.8602(12) 0.5439(11) 0.8276(4) 0.148(4) Uiso 1 1 d . . . H71 H 0.8540 0.5399 0.7967 0.178 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 Hf1 0.04867(14) 0.03887(14) 0.05105(14) -0.00134(12) 0.00516(12) 0.00321(12) Cl1 0.0800(12) 0.0578(11) 0.0744(12) -0.0126(9) -0.0128(10) -0.0036(9) Cl2 0.0989(14) 0.0644(11) 0.0474(9) -0.0063(8) 0.0002(9) -0.0047(10) Cl3 0.0678(11) 0.0636(12) 0.1205(16) 0.0173(12) 0.0359(11) 0.0027(10) Si1 0.0408(8) 0.0432(9) 0.0541(9) 0.0035(9) 0.0061(7) 0.0034(8) Si2 0.0614(12) 0.0504(11) 0.0612(11) 0.0000(9) 0.0136(9) 0.0091(9) Si3 0.0418(10) 0.0782(14) 0.0879(14) 0.0118(12) -0.0061(10) -0.0027(10) Si4 0.0613(12) 0.0487(11) 0.0630(12) 0.0088(9) 0.0080(10) 0.0054(9) N1 0.086(4) 0.048(3) 0.065(3) 0.002(2) 0.005(3) -0.002(3) N2 0.066(4) 0.057(4) 0.074(4) 0.003(3) 0.009(3) 0.016(3) N3 0.039(3) 0.045(3) 0.045(3) -0.002(2) 0.002(2) -0.002(2) C1 0.174(11) 0.057(5) 0.127(8) 0.017(5) -0.042(8) -0.016(6) C2 0.158(9) 0.078(5) 0.069(5) 0.021(4) 0.014(6) -0.006(6) C3 0.125(8) 0.094(7) 0.143(9) 0.063(7) 0.041(7) 0.052(7) C4 0.114(9) 0.125(9) 0.35(2) 0.150(12) 0.118(11) 0.078(7) C5 0.051(4) 0.123(7) 0.106(6) -0.022(7) -0.005(4) 0.008(4) C6 0.072(6) 0.203(12) 0.101(7) -0.064(8) 0.004(5) 0.060(7) C7 0.040(3) 0.037(3) 0.037(3) 0.000(3) -0.003(3) 0.002(3) C8 0.039(3) 0.048(4) 0.051(4) -0.001(3) 0.005(3) 0.005(3) C9 0.041(4) 0.071(5) 0.067(4) 0.004(4) 0.003(3) 0.006(3) C10 0.061(4) 0.090(5) 0.056(4) 0.013(4) 0.016(3) 0.012(4) C11 0.053(4) 0.083(5) 0.079(5) 0.013(5) 0.026(3) -0.001(4) C12 0.065(5) 0.067(5) 0.093(6) 0.000(4) 0.011(4) -0.002(4) C13 0.048(4) 0.047(4) 0.069(4) -0.001(3) 0.008(3) 0.003(3) C14 0.070(4) 0.068(4) 0.073(4) 0.000(4) 0.003(3) -0.015(4) C15 0.072(5) 0.110(6) 0.053(4) 0.001(4) -0.003(3) -0.016(4) C16 0.098(7) 0.102(7) 0.075(5) -0.016(5) -0.006(5) -0.004(5) C17 0.107(6) 0.072(5) 0.069(4) 0.005(4) 0.028(5) 0.003(5) C18 0.091(6) 0.075(5) 0.102(6) -0.005(4) 0.030(5) 0.036(5) C19 0.099(7) 0.102(7) 0.146(9) -0.031(7) -0.047(6) -0.006(6) C20 0.055(5) 0.152(10) 0.137(8) 0.028(7) 0.004(5) -0.028(6) C21 0.054(5) 0.119(8) 0.148(9) 0.032(7) -0.019(5) 0.002(5) C22 0.101(6) 0.063(5) 0.114(7) 0.008(5) 0.022(5) 0.024(5) C23 0.095(6) 0.073(5) 0.067(5) 0.016(4) 0.008(4) -0.014(5) C24 0.091(5) 0.060(4) 0.086(5) 0.012(4) -0.002(4) -0.012(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 Hf1 N3 2.178(5) . ? Hf1 C7 2.210(6) . ? Hf1 Cl2 2.4249(18) . ? Hf1 Cl1 2.4323(18) . ? Hf1 Cl3 2.4488(18) . ? Hf1 N2 2.466(6) . ? Hf1 N1 2.522(5) . ? Si1 C7 1.922(6) . ? Si1 Si2 2.375(2) . ? Si1 Si3 2.376(3) . ? Si1 Si4 2.381(3) . ? Si2 C16 1.851(9) . ? Si2 C18 1.871(7) . ? Si2 C17 1.880(7) . ? Si3 C20 1.817(9) . ? Si3 C21 1.858(9) . ? Si3 C19 1.889(10) . ? Si4 C24 1.873(8) . ? Si4 C23 1.866(7) . ? Si4 C22 1.894(8) . ? N1 C2 1.455(9) . ? N1 C3 1.500(11) . ? N1 C1 1.505(11) . ? N2 C6 1.459(10) . ? N2 C5 1.461(9) . ? N2 C4 1.472(11) . ? N3 C7 1.274(7) . ? N3 C8 1.444(8) . ? C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C2 H2A 0.9600 . ? C2 H2B 0.9600 . ? C2 H2C 0.9600 . ? C3 C4 1.229(13) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 H5A 0.9600 . ? C5 H5B 0.9600 . ? C5 H5C 0.9600 . ? C6 H6A 0.9600 . ? C6 H6B 0.9600 . ? C6 H6C 0.9600 . ? C8 C13 1.382(9) . ? C8 C9 1.394(9) . ? C9 C10 1.396(9) . ? C9 C15 1.491(10) . ? C10 C11 1.368(11) . ? C10 H10 0.9300 . ? C11 C12 1.382(10) . ? C11 H11 0.9300 . ? C12 C13 1.404(10) . ? C12 H12 0.9300 . ? C13 C14 1.490(9) . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C15 H15A 0.9600 . ? C15 H15B 0.9600 . ? C15 H15C 0.9600 . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C17 H17A 0.9600 . ? C17 H17B 0.9600 . ? C17 H17C 0.9600 . ? C18 H18A 0.9600 . ? C18 H18B 0.9600 . ? C18 H18C 0.9600 . ? C19 H19A 0.9600 . ? C19 H19B 0.9600 . ? C19 H19C 0.9600 . ? C20 H20A 0.9600 . ? C20 H20B 0.9600 . ? C20 H20C 0.9600 . ? C21 H21A 0.9600 . ? C21 H21B 0.9600 . ? C21 H21C 0.9600 . ? C22 H22A 0.9600 . ? C22 H22B 0.9600 . ? C22 H22C 0.9600 . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C23 H23C 0.9600 . ? C24 H24A 0.9600 . ? C24 H24B 0.9600 . ? C24 H24C 0.9600 . ? C65 C66 1.256(15) . ? C65 C70 1.97(2) . ? C65 H65 0.9300 . ? C67 C66 1.362(16) . ? C67 C68 1.426(17) . ? C67 H69 0.9300 . ? C66 H68 0.9300 . ? C68 C69 1.398(18) . ? C68 H70 0.9300 . ? C70 C69 1.80(2) . ? C70 H72 0.9300 . ? C69 H71 0.9300 . ? 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 Hf1 C7 33.73(18) . . ? N3 Hf1 Cl2 92.94(14) . . ? C7 Hf1 Cl2 90.82(15) . . ? N3 Hf1 Cl1 92.92(13) . . ? C7 Hf1 Cl1 99.03(15) . . ? Cl2 Hf1 Cl1 169.27(7) . . ? N3 Hf1 Cl3 122.01(14) . . ? C7 Hf1 Cl3 88.68(16) . . ? Cl2 Hf1 Cl3 94.34(8) . . ? Cl1 Hf1 Cl3 90.17(8) . . ? N3 Hf1 N2 85.09(19) . . ? C7 Hf1 N2 118.6(2) . . ? Cl2 Hf1 N2 86.43(15) . . ? Cl1 Hf1 N2 85.12(15) . . ? Cl3 Hf1 N2 152.74(15) . . ? N3 Hf1 N1 159.2(2) . . ? C7 Hf1 N1 166.4(2) . . ? Cl2 Hf1 N1 84.99(14) . . ? Cl1 Hf1 N1 86.34(14) . . ? Cl3 Hf1 N1 78.77(16) . . ? N2 Hf1 N1 74.2(2) . . ? C7 Si1 Si2 106.04(18) . . ? C7 Si1 Si3 104.77(19) . . ? Si2 Si1 Si3 109.07(10) . . ? C7 Si1 Si4 120.30(19) . . ? Si2 Si1 Si4 108.45(10) . . ? Si3 Si1 Si4 107.82(10) . . ? C16 Si2 C18 108.2(4) . . ? C16 Si2 C17 107.8(4) . . ? C18 Si2 C17 107.1(4) . . ? C16 Si2 Si1 111.3(3) . . ? C18 Si2 Si1 108.2(3) . . ? C17 Si2 Si1 113.9(3) . . ? C20 Si3 C21 106.7(5) . . ? C20 Si3 C19 109.9(5) . . ? C21 Si3 C19 106.1(5) . . ? C20 Si3 Si1 113.8(3) . . ? C21 Si3 Si1 109.7(3) . . ? C19 Si3 Si1 110.2(3) . . ? C24 Si4 C23 107.5(4) . . ? C24 Si4 C22 106.4(4) . . ? C23 Si4 C22 106.8(4) . . ? C24 Si4 Si1 112.6(3) . . ? C23 Si4 Si1 113.0(3) . . ? C22 Si4 Si1 110.1(3) . . ? C2 N1 C3 107.9(7) . . ? C2 N1 C1 106.1(7) . . ? C3 N1 C1 108.6(8) . . ? C2 N1 Hf1 115.2(4) . . ? C3 N1 Hf1 105.6(5) . . ? C1 N1 Hf1 113.2(5) . . ? C6 N2 C5 107.5(7) . . ? C6 N2 C4 106.7(9) . . ? C5 N2 C4 105.6(9) . . ? C6 N2 Hf1 114.8(5) . . ? C5 N2 Hf1 115.4(4) . . ? C4 N2 Hf1 106.1(5) . . ? C7 N3 C8 130.7(5) . . ? C7 N3 Hf1 74.5(3) . . ? C8 N3 Hf1 154.7(4) . . ? N1 C1 H1A 109.5 . . ? N1 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? N1 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? N1 C2 H2A 109.5 . . ? N1 C2 H2B 109.4 . . ? H2A C2 H2B 109.5 . . ? N1 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? C4 C3 N1 123.6(8) . . ? C4 C3 H3A 106.5 . . ? N1 C3 H3A 106.5 . . ? C4 C3 H3B 106.4 . . ? N1 C3 H3B 106.4 . . ? H3A C3 H3B 106.5 . . ? C3 C4 N2 128.9(9) . . ? C3 C4 H4A 105.1 . . ? N2 C4 H4A 105.1 . . ? C3 C4 H4B 105.0 . . ? N2 C4 H4B 105.1 . . ? H4A C4 H4B 105.9 . . ? N2 C5 H5A 109.5 . . ? N2 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? N2 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? N2 C6 H6A 109.4 . . ? N2 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? N2 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? N3 C7 Si1 134.6(5) . . ? N3 C7 Hf1 71.8(3) . . ? Si1 C7 Hf1 153.6(3) . . ? C13 C8 C9 122.8(6) . . ? C13 C8 N3 118.7(5) . . ? C9 C8 N3 118.3(6) . . ? C8 C9 C10 118.0(7) . . ? C8 C9 C15 122.4(6) . . ? C10 C9 C15 119.5(7) . . ? C11 C10 C9 120.5(7) . . ? C11 C10 H10 119.7 . . ? C9 C10 H10 119.8 . . ? C10 C11 C12 120.5(7) . . ? C10 C11 H11 119.7 . . ? C12 C11 H11 119.7 . . ? C11 C12 C13 121.0(7) . . ? C11 C12 H12 119.5 . . ? C13 C12 H12 119.5 . . ? C8 C13 C12 117.2(6) . . ? C8 C13 C14 124.4(6) . . ? C12 C13 C14 118.4(6) . . ? 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 . . ? C9 C15 H15A 109.5 . . ? C9 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C9 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? Si2 C16 H16A 109.5 . . ? Si2 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? Si2 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? Si2 C17 H17A 109.5 . . ? Si2 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? Si2 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? Si2 C18 H18A 109.5 . . ? Si2 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? Si2 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? Si3 C19 H19A 109.5 . . ? Si3 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? Si3 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? Si3 C20 H20A 109.5 . . ? Si3 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? Si3 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? Si3 C21 H21A 109.5 . . ? Si3 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? Si3 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? Si4 C22 H22A 109.5 . . ? Si4 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? Si4 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? Si4 C23 H23A 109.5 . . ? Si4 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? Si4 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? Si4 C24 H24A 109.5 . . ? Si4 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? Si4 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C66 C65 C70 140.3(12) . . ? C66 C65 H65 109.8 . . ? C70 C65 H65 109.9 . . ? C66 C67 C68 103.3(14) . . ? C66 C67 H69 128.4 . . ? C68 C67 H69 128.2 . . ? C65 C66 C67 133.3(15) . . ? C65 C66 H68 113.3 . . ? C67 C66 H68 113.4 . . ? C69 C68 C67 124.2(16) . . ? C69 C68 H70 117.7 . . ? C67 C68 H70 118.1 . . ? C69 C70 C65 71.4(10) . . ? C69 C70 H72 144.3 . . ? C65 C70 H72 144.3 . . ? C68 C69 C70 147.3(15) . . ? C68 C69 H71 106.3 . . ? C70 C69 H71 106.3 . . ? 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 C7 Si1 Si2 C16 65.0(4) . . . . ? Si3 Si1 Si2 C16 177.3(3) . . . . ? Si4 Si1 Si2 C16 -65.5(3) . . . . ? C7 Si1 Si2 C18 -176.2(4) . . . . ? Si3 Si1 Si2 C18 -63.9(3) . . . . ? Si4 Si1 Si2 C18 53.3(3) . . . . ? C7 Si1 Si2 C17 -57.2(4) . . . . ? Si3 Si1 Si2 C17 55.2(3) . . . . ? Si4 Si1 Si2 C17 172.3(3) . . . . ? C7 Si1 Si3 C20 91.0(5) . . . . ? Si2 Si1 Si3 C20 -22.2(4) . . . . ? Si4 Si1 Si3 C20 -139.8(4) . . . . ? C7 Si1 Si3 C21 -149.5(4) . . . . ? Si2 Si1 Si3 C21 97.3(4) . . . . ? Si4 Si1 Si3 C21 -20.2(4) . . . . ? C7 Si1 Si3 C19 -33.0(4) . . . . ? Si2 Si1 Si3 C19 -146.2(4) . . . . ? Si4 Si1 Si3 C19 96.2(4) . . . . ? C7 Si1 Si4 C24 -61.3(4) . . . . ? Si2 Si1 Si4 C24 60.8(3) . . . . ? Si3 Si1 Si4 C24 178.8(3) . . . . ? C7 Si1 Si4 C23 60.8(4) . . . . ? Si2 Si1 Si4 C23 -177.1(3) . . . . ? Si3 Si1 Si4 C23 -59.1(3) . . . . ? C7 Si1 Si4 C22 -179.9(4) . . . . ? Si2 Si1 Si4 C22 -57.7(3) . . . . ? Si3 Si1 Si4 C22 60.3(3) . . . . ? N3 Hf1 N1 C2 112.2(7) . . . . ? C7 Hf1 N1 C2 -45.3(12) . . . . ? Cl2 Hf1 N1 C2 27.2(6) . . . . ? Cl1 Hf1 N1 C2 -159.2(6) . . . . ? Cl3 Hf1 N1 C2 -68.3(6) . . . . ? N2 Hf1 N1 C2 114.9(7) . . . . ? N3 Hf1 N1 C3 -6.7(9) . . . . ? C7 Hf1 N1 C3 -164.3(9) . . . . ? Cl2 Hf1 N1 C3 -91.8(6) . . . . ? Cl1 Hf1 N1 C3 81.8(6) . . . . ? Cl3 Hf1 N1 C3 172.7(6) . . . . ? N2 Hf1 N1 C3 -4.1(6) . . . . ? N3 Hf1 N1 C1 -125.4(7) . . . . ? C7 Hf1 N1 C1 77.1(10) . . . . ? Cl2 Hf1 N1 C1 149.6(6) . . . . ? Cl1 Hf1 N1 C1 -36.8(6) . . . . ? Cl3 Hf1 N1 C1 54.1(6) . . . . ? N2 Hf1 N1 C1 -122.8(6) . . . . ? N3 Hf1 N2 C6 -65.4(7) . . . . ? C7 Hf1 N2 C6 -69.6(7) . . . . ? Cl2 Hf1 N2 C6 -158.6(7) . . . . ? Cl1 Hf1 N2 C6 28.0(7) . . . . ? Cl3 Hf1 N2 C6 108.8(7) . . . . ? N1 Hf1 N2 C6 115.6(7) . . . . ? N3 Hf1 N2 C5 60.6(5) . . . . ? C7 Hf1 N2 C5 56.3(6) . . . . ? Cl2 Hf1 N2 C5 -32.7(5) . . . . ? Cl1 Hf1 N2 C5 153.9(5) . . . . ? Cl3 Hf1 N2 C5 -125.2(5) . . . . ? N1 Hf1 N2 C5 -118.5(6) . . . . ? N3 Hf1 N2 C4 177.0(9) . . . . ? C7 Hf1 N2 C4 172.7(8) . . . . ? Cl2 Hf1 N2 C4 83.8(9) . . . . ? Cl1 Hf1 N2 C4 -89.6(9) . . . . ? Cl3 Hf1 N2 C4 -8.8(10) . . . . ? N1 Hf1 N2 C4 -2.0(9) . . . . ? Cl2 Hf1 N3 C7 -87.1(3) . . . . ? Cl1 Hf1 N3 C7 101.9(3) . . . . ? Cl3 Hf1 N3 C7 9.9(4) . . . . ? N2 Hf1 N3 C7 -173.2(3) . . . . ? N1 Hf1 N3 C7 -170.7(5) . . . . ? C7 Hf1 N3 C8 175.5(11) . . . . ? Cl2 Hf1 N3 C8 88.4(9) . . . . ? Cl1 Hf1 N3 C8 -82.6(9) . . . . ? Cl3 Hf1 N3 C8 -174.6(9) . . . . ? N2 Hf1 N3 C8 2.3(9) . . . . ? N1 Hf1 N3 C8 4.8(12) . . . . ? C2 N1 C3 C4 -111.3(16) . . . . ? C1 N1 C3 C4 134.2(16) . . . . ? Hf1 N1 C3 C4 12.5(17) . . . . ? N1 C3 C4 N2 -18(3) . . . . ? C6 N2 C4 C3 -111.4(19) . . . . ? C5 N2 C4 C3 134.4(19) . . . . ? Hf1 N2 C4 C3 11(2) . . . . ? C8 N3 C7 Si1 1.9(9) . . . . ? Hf1 N3 C7 Si1 179.4(5) . . . . ? C8 N3 C7 Hf1 -177.5(6) . . . . ? Si2 Si1 C7 N3 -124.3(5) . . . . ? Si3 Si1 C7 N3 120.4(5) . . . . ? Si4 Si1 C7 N3 -0.9(7) . . . . ? Si2 Si1 C7 Hf1 54.4(7) . . . . ? Si3 Si1 C7 Hf1 -60.9(7) . . . . ? Si4 Si1 C7 Hf1 177.7(5) . . . . ? Cl2 Hf1 C7 N3 94.1(3) . . . . ? Cl1 Hf1 C7 N3 -81.6(3) . . . . ? Cl3 Hf1 C7 N3 -171.6(3) . . . . ? N2 Hf1 C7 N3 7.7(4) . . . . ? N1 Hf1 C7 N3 165.9(8) . . . . ? N3 Hf1 C7 Si1 -179.0(9) . . . . ? Cl2 Hf1 C7 Si1 -84.9(7) . . . . ? Cl1 Hf1 C7 Si1 99.3(7) . . . . ? Cl3 Hf1 C7 Si1 9.4(7) . . . . ? N2 Hf1 C7 Si1 -171.3(6) . . . . ? N1 Hf1 C7 Si1 -13.1(14) . . . . ? C7 N3 C8 C13 88.8(7) . . . . ? Hf1 N3 C8 C13 -85.5(10) . . . . ? C7 N3 C8 C9 -95.8(8) . . . . ? Hf1 N3 C8 C9 89.9(10) . . . . ? C13 C8 C9 C10 0.2(10) . . . . ? N3 C8 C9 C10 -175.0(6) . . . . ? C13 C8 C9 C15 179.2(6) . . . . ? N3 C8 C9 C15 4.0(9) . . . . ? C8 C9 C10 C11 0.0(10) . . . . ? C15 C9 C10 C11 -179.0(7) . . . . ? C9 C10 C11 C12 -0.2(12) . . . . ? C10 C11 C12 C13 0.1(12) . . . . ? C9 C8 C13 C12 -0.3(9) . . . . ? N3 C8 C13 C12 174.9(6) . . . . ? C9 C8 C13 C14 176.6(6) . . . . ? N3 C8 C13 C14 -8.2(9) . . . . ? C11 C12 C13 C8 0.1(10) . . . . ? C11 C12 C13 C14 -177.0(7) . . . . ? C70 C65 C66 C67 -4(3) . . . . ? C68 C67 C66 C65 3(2) . . . . ? C66 C67 C68 C69 1(2) . . . . ? C66 C65 C70 C69 0.6(18) . . . . ? C67 C68 C69 C70 -6(3) . . . . ? C65 C70 C69 C68 5(2) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 23.26 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 1.056 _refine_diff_density_min -0.295 _refine_diff_density_rms 0.079 data_34j _database_code_CSD 177994 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C15 H43 Cl3 Hf N2 Si4' _chemical_formula_weight 648.71 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' 'Si' 'Si' 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Hf' 'Hf' -0.5830 6.1852 '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 Orthorhombic _symmetry_space_group_name_H-M Pbca loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 14.212(3) _cell_length_b 13.760(3) _cell_length_c 30.415(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 5948(2) _cell_formula_units_Z 8 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description 'thin plates' _exptl_crystal_colour orange _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.449 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2608 _exptl_absorpt_coefficient_mu 3.942 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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 'Bruker P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count 10 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 31754 _diffrn_reflns_av_R_equivalents 0.2670 _diffrn_reflns_av_sigmaI/netI 0.1876 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_theta_min 1.96 _diffrn_reflns_theta_max 23.41 _reflns_number_total 4345 _reflns_number_gt 2187 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0432P)^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 SHELXL _refine_ls_extinction_coef 0.00184(16) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 4345 _refine_ls_number_parameters 240 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1693 _refine_ls_R_factor_gt 0.0814 _refine_ls_wR_factor_ref 0.1721 _refine_ls_wR_factor_gt 0.1409 _refine_ls_goodness_of_fit_ref 0.957 _refine_ls_restrained_S_all 0.957 _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 Hf Hf 0.54082(5) 0.23159(5) 0.29670(3) 0.0480(3) Uani 1 1 d . . . Cl1 Cl 0.6483(4) 0.3625(4) 0.3013(2) 0.0822(17) Uani 1 1 d . . . Cl2 Cl 0.4200(4) 0.3316(4) 0.2686(2) 0.0806(18) Uani 1 1 d . . . Cl3 Cl 0.4361(3) 0.0965(4) 0.28946(17) 0.0656(15) Uani 1 1 d . . . Si1 Si 0.5239(3) 0.2419(4) 0.38835(18) 0.0545(15) Uani 1 1 d . . . Si2 Si 0.6611(4) 0.2444(5) 0.4332(2) 0.078(2) Uani 1 1 d . . . Si3 Si 0.4236(4) 0.1248(4) 0.4209(2) 0.0656(18) Uani 1 1 d . . . Si4 Si 0.4533(5) 0.3921(4) 0.4060(2) 0.0750(18) Uani 1 1 d . . . N1 N 0.5934(11) 0.2192(12) 0.2194(5) 0.061(4) Uani 1 1 d . . . N2 N 0.6633(10) 0.1139(10) 0.2972(6) 0.062(4) Uani 1 1 d . . . C1 C 0.7566(15) 0.3272(17) 0.4117(8) 0.127(10) Uani 1 1 d . . . H21A H 0.7766 0.3703 0.4346 0.191 Uiso 1 1 calc R . . H21B H 0.7326 0.3644 0.3874 0.191 Uiso 1 1 calc R . . H21C H 0.8091 0.2888 0.4020 0.191 Uiso 1 1 calc R . . C2 C 0.7075(16) 0.1207(16) 0.4428(7) 0.106(9) Uani 1 1 d . . . H17A H 0.7640 0.1246 0.4600 0.160 Uiso 1 1 calc R . . H17B H 0.7210 0.0903 0.4151 0.160 Uiso 1 1 calc R . . H17C H 0.6614 0.0829 0.4584 0.160 Uiso 1 1 calc R . . C3 C 0.6356(17) 0.2932(17) 0.4905(7) 0.116(9) Uani 1 1 d . . . H16A H 0.5816 0.2606 0.5024 0.175 Uiso 1 1 calc R . . H16B H 0.6234 0.3617 0.4889 0.175 Uiso 1 1 calc R . . H16C H 0.6890 0.2818 0.5092 0.175 Uiso 1 1 calc R . . C4 C 0.4493(18) -0.0005(14) 0.4048(7) 0.114(9) Uani 1 1 d . . . H11A H 0.5132 -0.0159 0.4123 0.171 Uiso 1 1 calc R . . H11B H 0.4407 -0.0076 0.3737 0.171 Uiso 1 1 calc R . . H11C H 0.4076 -0.0438 0.4200 0.171 Uiso 1 1 calc R . . C5 C 0.4259(14) 0.1254(16) 0.4823(7) 0.095(8) Uani 1 1 d . . . H12A H 0.3851 0.0754 0.4933 0.142 Uiso 1 1 calc R . . H12B H 0.4049 0.1875 0.4929 0.142 Uiso 1 1 calc R . . H12C H 0.4890 0.1137 0.4924 0.142 Uiso 1 1 calc R . . C6 C 0.2980(12) 0.1552(16) 0.4023(7) 0.091(8) Uani 1 1 d . . . H15A H 0.2874 0.1289 0.3735 0.137 Uiso 1 1 calc R . . H15B H 0.2901 0.2244 0.4015 0.137 Uiso 1 1 calc R . . H15C H 0.2538 0.1274 0.4226 0.137 Uiso 1 1 calc R . . C7 C 0.5404(19) 0.4929(13) 0.4025(8) 0.136(11) Uani 1 1 d . . . H14A H 0.5102 0.5533 0.4096 0.204 Uiso 1 1 calc R . . H14B H 0.5652 0.4963 0.3731 0.204 Uiso 1 1 calc R . . H14C H 0.5908 0.4813 0.4228 0.204 Uiso 1 1 calc R . . C8 C 0.3501(17) 0.4249(16) 0.3690(9) 0.132(11) Uani 1 1 d . . . H20A H 0.3341 0.4921 0.3731 0.198 Uiso 1 1 calc R . . H20B H 0.2969 0.3850 0.3763 0.198 Uiso 1 1 calc R . . H20C H 0.3672 0.4142 0.3388 0.198 Uiso 1 1 calc R . . C9 C 0.4011(17) 0.3965(16) 0.4622(7) 0.103(9) Uani 1 1 d . . . H13A H 0.3788 0.4610 0.4681 0.155 Uiso 1 1 calc R . . H13B H 0.4481 0.3791 0.4835 0.155 Uiso 1 1 calc R . . H13C H 0.3496 0.3516 0.4639 0.155 Uiso 1 1 calc R . . C10 C 0.5224(13) 0.1682(17) 0.1915(7) 0.092(8) Uani 1 1 d . . . H63A H 0.4663 0.2068 0.1896 0.138 Uiso 1 1 calc R . . H63B H 0.5076 0.1063 0.2043 0.138 Uiso 1 1 calc R . . H63C H 0.5476 0.1586 0.1625 0.138 Uiso 1 1 calc R . . C11 C 0.6137(15) 0.3102(14) 0.1967(6) 0.082(7) Uani 1 1 d . . . H62A H 0.6502 0.3516 0.2156 0.123 Uiso 1 1 calc R . . H62B H 0.5557 0.3420 0.1893 0.123 Uiso 1 1 calc R . . H62C H 0.6486 0.2969 0.1704 0.123 Uiso 1 1 calc R . . C12 C 0.6813(13) 0.1589(15) 0.2177(6) 0.070(6) Uani 1 1 d . . . H18A H 0.7352 0.1994 0.2245 0.083 Uiso 1 1 calc R . . H18B H 0.6895 0.1334 0.1882 0.083 Uiso 1 1 calc R . . C13 C 0.6762(13) 0.0742(14) 0.2507(6) 0.064(6) Uani 1 1 d . . . H19A H 0.6238 0.0320 0.2432 0.077 Uiso 1 1 calc R . . H19B H 0.7336 0.0362 0.2491 0.077 Uiso 1 1 calc R . . C14 C 0.7556(14) 0.1573(17) 0.3126(8) 0.106(9) Uani 1 1 d . . . H9A H 0.8064 0.1149 0.3047 0.160 Uiso 1 1 calc R . . H9B H 0.7542 0.1651 0.3440 0.160 Uiso 1 1 calc R . . H9C H 0.7646 0.2196 0.2990 0.160 Uiso 1 1 calc R . . C15 C 0.6387(14) 0.0258(12) 0.3257(6) 0.071(7) Uani 1 1 d . . . H4A H 0.6947 -0.0109 0.3316 0.106 Uiso 1 1 calc R . . H4B H 0.5943 -0.0144 0.3104 0.106 Uiso 1 1 calc R . . H4C H 0.6116 0.0474 0.3529 0.106 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 Hf 0.0376(5) 0.0450(5) 0.0614(6) -0.0031(5) 0.0016(5) 0.0005(4) Cl1 0.085(4) 0.071(4) 0.090(5) -0.012(3) 0.005(4) -0.029(3) Cl2 0.080(4) 0.071(4) 0.091(5) 0.012(3) 0.009(3) 0.031(3) Cl3 0.039(3) 0.083(3) 0.075(4) -0.005(3) -0.006(3) -0.011(2) Si1 0.046(3) 0.049(3) 0.068(4) -0.004(3) -0.010(3) -0.004(3) Si2 0.067(4) 0.088(5) 0.081(5) -0.004(4) -0.018(3) -0.008(4) Si3 0.064(4) 0.064(4) 0.069(5) 0.002(3) 0.011(3) -0.014(3) Si4 0.077(4) 0.068(4) 0.081(5) -0.016(3) 0.004(4) 0.010(4) N1 0.056(11) 0.077(12) 0.051(11) 0.005(9) 0.008(8) -0.013(10) N2 0.061(11) 0.054(10) 0.072(13) -0.005(11) 0.005(10) -0.002(8) C1 0.084(19) 0.16(2) 0.14(3) -0.02(2) -0.054(18) -0.037(19) C2 0.11(2) 0.12(2) 0.10(2) 0.006(15) -0.075(16) 0.009(16) C3 0.13(2) 0.14(2) 0.082(19) -0.030(17) -0.056(17) 0.029(19) C4 0.17(3) 0.073(16) 0.10(2) -0.004(14) 0.03(2) -0.025(18) C5 0.080(17) 0.13(2) 0.077(18) 0.027(15) -0.021(14) -0.023(15) C6 0.034(12) 0.15(2) 0.086(18) -0.033(16) 0.009(12) -0.007(14) C7 0.19(3) 0.048(14) 0.17(3) -0.055(16) 0.00(2) -0.025(18) C8 0.12(2) 0.11(2) 0.17(3) -0.015(19) -0.06(2) 0.045(18) C9 0.13(2) 0.12(2) 0.064(18) -0.012(15) 0.031(15) 0.033(18) C10 0.043(15) 0.15(2) 0.083(18) -0.029(15) 0.012(12) 0.012(14) C11 0.13(2) 0.082(15) 0.038(14) 0.018(12) 0.019(13) 0.007(14) C12 0.041(13) 0.109(18) 0.059(16) 0.000(13) 0.010(10) 0.018(12) C13 0.052(14) 0.084(16) 0.057(16) 0.000(13) 0.005(11) -0.006(11) C14 0.042(15) 0.15(2) 0.13(2) -0.025(18) -0.026(14) -0.003(15) C15 0.067(15) 0.039(12) 0.106(19) 0.020(12) 0.011(14) 0.002(11) _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 Cl2 2.361(5) . ? Hf Cl1 2.367(5) . ? Hf N2 2.378(14) . ? Hf Cl3 2.392(5) . ? Hf N1 2.473(14) . ? Hf Si1 2.802(6) . ? Si1 Si4 2.359(7) . ? Si1 Si3 2.367(8) . ? Si1 Si2 2.380(8) . ? Si2 C2 1.85(2) . ? Si2 C1 1.89(2) . ? Si2 C3 1.90(2) . ? Si3 C4 1.83(2) . ? Si3 C5 1.87(2) . ? Si3 C6 1.918(18) . ? Si4 C9 1.863(19) . ? Si4 C7 1.86(2) . ? Si4 C8 1.90(2) . ? N1 C11 1.46(2) . ? N1 C10 1.49(2) . ? N1 C12 1.50(2) . ? N2 C14 1.52(2) . ? N2 C13 1.53(2) . ? N2 C15 1.53(2) . ? C1 H21A 0.9600 . ? C1 H21B 0.9600 . ? C1 H21C 0.9600 . ? C2 H17A 0.9600 . ? C2 H17B 0.9600 . ? C2 H17C 0.9600 . ? C3 H16A 0.9600 . ? C3 H16B 0.9600 . ? C3 H16C 0.9600 . ? C4 H11A 0.9600 . ? C4 H11B 0.9600 . ? C4 H11C 0.9600 . ? C5 H12A 0.9600 . ? C5 H12B 0.9600 . ? C5 H12C 0.9600 . ? C6 H15A 0.9600 . ? C6 H15B 0.9600 . ? C6 H15C 0.9600 . ? C7 H14A 0.9600 . ? C7 H14B 0.9600 . ? C7 H14C 0.9600 . ? C8 H20A 0.9600 . ? C8 H20B 0.9600 . ? C8 H20C 0.9600 . ? C9 H13A 0.9600 . ? C9 H13B 0.9600 . ? C9 H13C 0.9600 . ? C10 H63A 0.9600 . ? C10 H63B 0.9600 . ? C10 H63C 0.9600 . ? C11 H62A 0.9600 . ? C11 H62B 0.9600 . ? C11 H62C 0.9600 . ? C12 C13 1.54(2) . ? C12 H18A 0.9700 . ? C12 H18B 0.9700 . ? C13 H19A 0.9700 . ? C13 H19B 0.9700 . ? C14 H9A 0.9600 . ? C14 H9B 0.9600 . ? C14 H9C 0.9600 . ? C15 H4A 0.9600 . ? C15 H4B 0.9600 . ? C15 H4C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag Cl2 Hf Cl1 92.7(2) . . ? Cl2 Hf N2 158.8(4) . . ? Cl1 Hf N2 92.6(4) . . ? Cl2 Hf Cl3 88.12(19) . . ? Cl1 Hf Cl3 177.52(19) . . ? N2 Hf Cl3 85.8(4) . . ? Cl2 Hf N1 85.2(4) . . ? Cl1 Hf N1 85.0(4) . . ? N2 Hf N1 74.8(6) . . ? Cl3 Hf N1 92.7(4) . . ? Cl2 Hf Si1 105.54(17) . . ? Cl1 Hf Si1 87.60(17) . . ? N2 Hf Si1 95.2(4) . . ? Cl3 Hf Si1 94.43(16) . . ? N1 Hf Si1 167.3(4) . . ? Si4 Si1 Si3 104.2(3) . . ? Si4 Si1 Si2 101.8(3) . . ? Si3 Si1 Si2 105.3(3) . . ? Si4 Si1 Hf 107.9(2) . . ? Si3 Si1 Hf 115.7(2) . . ? Si2 Si1 Hf 120.0(3) . . ? C2 Si2 C1 110.7(11) . . ? C2 Si2 C3 104.3(10) . . ? C1 Si2 C3 104.0(11) . . ? C2 Si2 Si1 111.7(7) . . ? C1 Si2 Si1 113.5(7) . . ? C3 Si2 Si1 112.0(8) . . ? C4 Si3 C5 105.5(10) . . ? C4 Si3 C6 108.2(11) . . ? C5 Si3 C6 108.0(9) . . ? C4 Si3 Si1 114.2(8) . . ? C5 Si3 Si1 113.8(7) . . ? C6 Si3 Si1 106.8(7) . . ? C9 Si4 C7 107.1(11) . . ? C9 Si4 C8 103.2(12) . . ? C7 Si4 C8 107.5(11) . . ? C9 Si4 Si1 114.0(7) . . ? C7 Si4 Si1 110.9(8) . . ? C8 Si4 Si1 113.6(8) . . ? C11 N1 C10 105.6(16) . . ? C11 N1 C12 107.1(15) . . ? C10 N1 C12 106.4(15) . . ? C11 N1 Hf 116.7(11) . . ? C10 N1 Hf 111.6(11) . . ? C12 N1 Hf 108.9(11) . . ? C14 N2 C13 108.9(15) . . ? C14 N2 C15 109.6(16) . . ? C13 N2 C15 105.5(14) . . ? C14 N2 Hf 111.5(11) . . ? C13 N2 Hf 109.0(12) . . ? C15 N2 Hf 112.1(11) . . ? Si2 C1 H21A 109.5 . . ? Si2 C1 H21B 109.5 . . ? H21A C1 H21B 109.5 . . ? Si2 C1 H21C 109.5 . . ? H21A C1 H21C 109.5 . . ? H21B C1 H21C 109.5 . . ? Si2 C2 H17A 109.5 . . ? Si2 C2 H17B 109.5 . . ? H17A C2 H17B 109.5 . . ? Si2 C2 H17C 109.5 . . ? H17A C2 H17C 109.5 . . ? H17B C2 H17C 109.5 . . ? Si2 C3 H16A 109.5 . . ? Si2 C3 H16B 109.5 . . ? H16A C3 H16B 109.5 . . ? Si2 C3 H16C 109.5 . . ? H16A C3 H16C 109.5 . . ? H16B C3 H16C 109.5 . . ? Si3 C4 H11A 109.5 . . ? Si3 C4 H11B 109.5 . . ? H11A C4 H11B 109.5 . . ? Si3 C4 H11C 109.5 . . ? H11A C4 H11C 109.5 . . ? H11B C4 H11C 109.5 . . ? Si3 C5 H12A 109.5 . . ? Si3 C5 H12B 109.5 . . ? H12A C5 H12B 109.5 . . ? Si3 C5 H12C 109.5 . . ? H12A C5 H12C 109.5 . . ? H12B C5 H12C 109.5 . . ? Si3 C6 H15A 109.5 . . ? Si3 C6 H15B 109.5 . . ? H15A C6 H15B 109.5 . . ? Si3 C6 H15C 109.5 . . ? H15A C6 H15C 109.5 . . ? H15B C6 H15C 109.5 . . ? Si4 C7 H14A 109.5 . . ? Si4 C7 H14B 109.5 . . ? H14A C7 H14B 109.5 . . ? Si4 C7 H14C 109.5 . . ? H14A C7 H14C 109.5 . . ? H14B C7 H14C 109.5 . . ? Si4 C8 H20A 109.5 . . ? Si4 C8 H20B 109.5 . . ? H20A C8 H20B 109.5 . . ? Si4 C8 H20C 109.5 . . ? H20A C8 H20C 109.5 . . ? H20B C8 H20C 109.5 . . ? Si4 C9 H13A 109.5 . . ? Si4 C9 H13B 109.5 . . ? H13A C9 H13B 109.5 . . ? Si4 C9 H13C 109.5 . . ? H13A C9 H13C 109.5 . . ? H13B C9 H13C 109.5 . . ? N1 C10 H63A 109.5 . . ? N1 C10 H63B 109.5 . . ? H63A C10 H63B 109.5 . . ? N1 C10 H63C 109.5 . . ? H63A C10 H63C 109.5 . . ? H63B C10 H63C 109.5 . . ? N1 C11 H62A 109.5 . . ? N1 C11 H62B 109.5 . . ? H62A C11 H62B 109.5 . . ? N1 C11 H62C 109.5 . . ? H62A C11 H62C 109.5 . . ? H62B C11 H62C 109.5 . . ? N1 C12 C13 110.9(15) . . ? N1 C12 H18A 109.5 . . ? C13 C12 H18A 109.5 . . ? N1 C12 H18B 109.5 . . ? C13 C12 H18B 109.5 . . ? H18A C12 H18B 108.1 . . ? N2 C13 C12 109.8(16) . . ? N2 C13 H19A 109.7 . . ? C12 C13 H19A 109.7 . . ? N2 C13 H19B 109.7 . . ? C12 C13 H19B 109.7 . . ? H19A C13 H19B 108.2 . . ? N2 C14 H9A 109.5 . . ? N2 C14 H9B 109.5 . . ? H9A C14 H9B 109.5 . . ? N2 C14 H9C 109.5 . . ? H9A C14 H9C 109.5 . . ? H9B C14 H9C 109.5 . . ? N2 C15 H4A 109.5 . . ? N2 C15 H4B 109.5 . . ? H4A C15 H4B 109.5 . . ? N2 C15 H4C 109.5 . . ? H4A C15 H4C 109.5 . . ? H4B C15 H4C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag Cl2 Hf Si1 Si4 -26.6(3) . . . . ? Cl1 Hf Si1 Si4 65.6(3) . . . . ? N2 Hf Si1 Si4 158.0(4) . . . . ? Cl3 Hf Si1 Si4 -115.8(3) . . . . ? N1 Hf Si1 Si4 120.3(17) . . . . ? Cl2 Hf Si1 Si3 89.6(3) . . . . ? Cl1 Hf Si1 Si3 -178.2(3) . . . . ? N2 Hf Si1 Si3 -85.8(4) . . . . ? Cl3 Hf Si1 Si3 0.3(3) . . . . ? N1 Hf Si1 Si3 -123.5(17) . . . . ? Cl2 Hf Si1 Si2 -142.4(3) . . . . ? Cl1 Hf Si1 Si2 -50.2(3) . . . . ? N2 Hf Si1 Si2 42.2(4) . . . . ? Cl3 Hf Si1 Si2 128.4(3) . . . . ? N1 Hf Si1 Si2 4.5(18) . . . . ? Si4 Si1 Si2 C2 158.5(9) . . . . ? Si3 Si1 Si2 C2 50.0(9) . . . . ? Hf Si1 Si2 C2 -82.6(9) . . . . ? Si4 Si1 Si2 C1 -75.5(9) . . . . ? Si3 Si1 Si2 C1 176.0(9) . . . . ? Hf Si1 Si2 C1 43.5(9) . . . . ? Si4 Si1 Si2 C3 42.0(9) . . . . ? Si3 Si1 Si2 C3 -66.5(9) . . . . ? Hf Si1 Si2 C3 160.9(8) . . . . ? Si4 Si1 Si3 C4 170.1(9) . . . . ? Si2 Si1 Si3 C4 -83.1(9) . . . . ? Hf Si1 Si3 C4 51.8(9) . . . . ? Si4 Si1 Si3 C5 -68.6(8) . . . . ? Si2 Si1 Si3 C5 38.2(8) . . . . ? Hf Si1 Si3 C5 173.1(8) . . . . ? Si4 Si1 Si3 C6 50.5(7) . . . . ? Si2 Si1 Si3 C6 157.3(7) . . . . ? Hf Si1 Si3 C6 -67.8(7) . . . . ? Si3 Si1 Si4 C9 37.8(9) . . . . ? Si2 Si1 Si4 C9 -71.5(9) . . . . ? Hf Si1 Si4 C9 161.3(9) . . . . ? Si3 Si1 Si4 C7 158.7(9) . . . . ? Si2 Si1 Si4 C7 49.4(9) . . . . ? Hf Si1 Si4 C7 -77.9(9) . . . . ? Si3 Si1 Si4 C8 -80.1(10) . . . . ? Si2 Si1 Si4 C8 170.6(10) . . . . ? Hf Si1 Si4 C8 43.4(10) . . . . ? Cl2 Hf N1 C11 56.6(13) . . . . ? Cl1 Hf N1 C11 -36.6(13) . . . . ? N2 Hf N1 C11 -130.6(14) . . . . ? Cl3 Hf N1 C11 144.5(13) . . . . ? Si1 Hf N1 C11 -91(2) . . . . ? Cl2 Hf N1 C10 -65.0(12) . . . . ? Cl1 Hf N1 C10 -158.1(13) . . . . ? N2 Hf N1 C10 107.8(13) . . . . ? Cl3 Hf N1 C10 22.9(13) . . . . ? Si1 Hf N1 C10 147.0(15) . . . . ? Cl2 Hf N1 C12 177.9(12) . . . . ? Cl1 Hf N1 C12 84.7(11) . . . . ? N2 Hf N1 C12 -9.3(11) . . . . ? Cl3 Hf N1 C12 -94.3(11) . . . . ? Si1 Hf N1 C12 30(3) . . . . ? Cl2 Hf N2 C14 120.2(14) . . . . ? Cl1 Hf N2 C14 15.8(14) . . . . ? Cl3 Hf N2 C14 -166.1(14) . . . . ? N1 Hf N2 C14 100.0(14) . . . . ? Si1 Hf N2 C14 -72.0(14) . . . . ? Cl2 Hf N2 C13 -0.1(18) . . . . ? Cl1 Hf N2 C13 -104.4(11) . . . . ? Cl3 Hf N2 C13 73.7(10) . . . . ? N1 Hf N2 C13 -20.2(11) . . . . ? Si1 Hf N2 C13 167.8(10) . . . . ? Cl2 Hf N2 C15 -116.5(14) . . . . ? Cl1 Hf N2 C15 139.2(12) . . . . ? Cl3 Hf N2 C15 -42.7(12) . . . . ? N1 Hf N2 C15 -136.7(13) . . . . ? Si1 Hf N2 C15 51.3(12) . . . . ? C11 N1 C12 C13 165.0(16) . . . . ? C10 N1 C12 C13 -82.4(19) . . . . ? Hf N1 C12 C13 38.0(18) . . . . ? C14 N2 C13 C12 -74(2) . . . . ? C15 N2 C13 C12 168.6(15) . . . . ? Hf N2 C13 C12 48.0(16) . . . . ? N1 C12 C13 N2 -59(2) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 23.41 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 1.317 _refine_diff_density_min -1.006 _refine_diff_density_rms 0.181