Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2004 data_global _publ_contact_author_email ERNST@CHEM.UTAH.EDU _publ_contact_author_name 'Dr Richard Ernst' _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_address ; Department of Chemistry University of Utah 315 S. 1400 East, room 2020 Salt Lake City Utah 84112-0850 UNITED STATES OF AMERICA ; _publ_section_title ; Syntheses and Structural Systematics of Trialkylphosphine Complexes of Open Titanocenes, Zirconocenes, and Hafnocenes ; loop_ _publ_author_name 'Richard Ernst' 'Atta Arif' 'Rehan Basta' 'Benjamin G. Harvey' data_shelxl_a _database_code_depnum_ccdc_archive 'CCDC 212749' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C17 H31 P Zr' _chemical_formula_weight 357.61 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' P P 0.1023 0.0942 '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 'P 21/c' 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 7.9971(1) _cell_length_b 15.5057(3) _cell_length_c 15.0008(3) _cell_angle_alpha 90.00 _cell_angle_beta 102.460(1) _cell_angle_gamma 90.00 _cell_volume 1816.30(6) _cell_formula_units_Z 4 _cell_measurement_temperature 200(1) _cell_measurement_reflns_used 17763 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 27.48 _exptl_crystal_description prism _exptl_crystal_colour 'dark green' _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.308 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 752 _exptl_absorpt_coefficient_mu 0.682 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.8321 _exptl_absorpt_correction_T_max 0.8481 _exptl_absorpt_process_details 'DENZO-SMN (Otwinowski & Minor, 1997)' _exptl_special_details ; The program Denzo-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL-97 input file. ; _diffrn_ambient_temperature 200(1) _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 'Nonius KappaCCD Diffractometer' _diffrn_measurement_method 'Phi plus Omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2.0 _diffrn_reflns_number 7050 _diffrn_reflns_av_R_equivalents 0.0172 _diffrn_reflns_av_sigmaI/netI 0.0319 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.38 _diffrn_reflns_theta_max 27.48 _reflns_number_total 4136 _reflns_number_gt 3703 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius COLLECT' _computing_cell_refinement DENZO-SMN _computing_data_reduction DENZO-SMN _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'WinGX, Ortep3' _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^)+(0.0156P)^2^+0.7499P] 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 0.0111(6) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 4136 _refine_ls_number_parameters 297 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0278 _refine_ls_R_factor_gt 0.0226 _refine_ls_wR_factor_ref 0.0531 _refine_ls_wR_factor_gt 0.0507 _refine_ls_goodness_of_fit_ref 1.040 _refine_ls_restrained_S_all 1.040 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.673203(17) 0.190676(9) 0.771920(9) 0.01829(7) Uani 1 1 d . . . P1 P 0.85913(5) 0.33537(3) 0.78367(3) 0.02640(11) Uani 1 1 d . . . C1 C 0.4653(2) 0.29227(12) 0.68504(13) 0.0323(4) Uani 1 1 d . . . C2 C 0.37811(19) 0.21317(11) 0.68716(11) 0.0276(3) Uani 1 1 d . . . C3 C 0.37182(19) 0.16632(11) 0.76773(11) 0.0245(3) Uani 1 1 d . . . C4 C 0.4495(2) 0.18394(10) 0.86097(11) 0.0251(3) Uani 1 1 d . . . C5 C 0.5524(2) 0.25593(12) 0.89314(12) 0.0300(4) Uani 1 1 d . . . C6 C 0.2938(2) 0.17246(16) 0.59705(13) 0.0386(4) Uani 1 1 d . . . C7 C 0.4229(2) 0.11693(14) 0.92954(12) 0.0341(4) Uani 1 1 d . . . C8 C 0.8569(2) 0.15840(12) 0.66458(12) 0.0304(4) Uani 1 1 d . . . C9 C 0.7605(2) 0.08324(10) 0.67164(11) 0.0268(3) Uani 1 1 d . . . C10 C 0.7497(2) 0.04136(10) 0.75442(11) 0.0252(3) Uani 1 1 d . . . C11 C 0.82573(19) 0.06289(10) 0.84678(11) 0.0251(3) Uani 1 1 d . . . C12 C 0.9324(2) 0.13428(11) 0.87501(12) 0.0290(3) Uani 1 1 d . . . C13 C 0.6490(3) 0.04712(13) 0.58525(12) 0.0374(4) Uani 1 1 d . . . C14 C 0.7770(3) 0.00630(12) 0.91896(13) 0.0339(4) Uani 1 1 d . . . C15 C 1.0878(3) 0.33011(15) 0.8308(2) 0.0504(6) Uani 1 1 d . . . C16 C 0.8602(5) 0.3891(2) 0.67543(19) 0.0728(9) Uani 1 1 d . . . C17 C 0.8004(4) 0.42586(16) 0.8476(3) 0.0756(10) Uani 1 1 d . . . H1A H 0.471(3) 0.3141(12) 0.6287(15) 0.040(6) Uiso 1 1 d . . . H1B H 0.466(2) 0.3348(13) 0.7357(14) 0.037(5) Uiso 1 1 d . . . H3 H 0.317(2) 0.1120(12) 0.7579(12) 0.028(4) Uiso 1 1 d . . . H5A H 0.603(2) 0.2561(12) 0.9557(13) 0.034(5) Uiso 1 1 d . . . H5B H 0.525(3) 0.3089(12) 0.8658(14) 0.036(5) Uiso 1 1 d . . . H6A H 0.287(3) 0.1101(16) 0.6015(15) 0.052(6) Uiso 1 1 d . . . H6B H 0.183(3) 0.1927(15) 0.5748(17) 0.061(7) Uiso 1 1 d . . . H6C H 0.352(3) 0.1848(13) 0.5491(16) 0.050(6) Uiso 1 1 d . . . H7A H 0.400(3) 0.0622(14) 0.9026(14) 0.043(6) Uiso 1 1 d . . . H7B H 0.326(3) 0.1342(14) 0.9532(15) 0.051(6) Uiso 1 1 d . . . H7C H 0.521(2) 0.1145(12) 0.9788(13) 0.033(5) Uiso 1 1 d . . . H8A H 0.844(3) 0.1828(12) 0.6059(15) 0.039(5) Uiso 1 1 d . . . H8B H 0.968(3) 0.1709(12) 0.6978(13) 0.030(5) Uiso 1 1 d . . . H10 H 0.672(2) -0.0060(12) 0.7475(11) 0.023(4) Uiso 1 1 d . . . H12A H 0.964(2) 0.1447(13) 0.9394(14) 0.038(5) Uiso 1 1 d . . . H12B H 1.011(2) 0.1527(12) 0.8419(13) 0.030(5) Uiso 1 1 d . . . H13A H 0.554(3) 0.0149(14) 0.5983(14) 0.044(6) Uiso 1 1 d . . . H13B H 0.602(3) 0.0935(15) 0.5444(15) 0.049(6) Uiso 1 1 d . . . H13C H 0.717(3) 0.0081(15) 0.5565(15) 0.055(6) Uiso 1 1 d . . . H14A H 0.857(3) -0.0375(15) 0.9343(15) 0.056(7) Uiso 1 1 d . . . H14B H 0.665(3) -0.0180(14) 0.9002(14) 0.045(6) Uiso 1 1 d . . . H14C H 0.777(3) 0.0351(13) 0.9739(14) 0.042(5) Uiso 1 1 d . . . H15A H 1.136(3) 0.3850(17) 0.8304(16) 0.060(7) Uiso 1 1 d . . . H15B H 1.100(4) 0.3087(17) 0.893(2) 0.083(10) Uiso 1 1 d . . . H15C H 1.145(4) 0.289(2) 0.796(2) 0.085(9) Uiso 1 1 d . . . H16A H 0.753(6) 0.399(3) 0.640(3) 0.138(15) Uiso 1 1 d . . . H16B H 0.926(3) 0.4414(17) 0.6808(16) 0.062(7) Uiso 1 1 d . . . H16C H 0.921(6) 0.350(3) 0.642(3) 0.16(2) Uiso 1 1 d . . . H17A H 0.877(3) 0.4736(17) 0.8470(16) 0.063(7) Uiso 1 1 d . . . H17B H 0.835(4) 0.405(2) 0.911(2) 0.085(11) Uiso 1 1 d . . . H17C H 0.678(5) 0.443(2) 0.805(3) 0.136(15) 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 Zr1 0.01756(9) 0.01766(9) 0.01999(10) 0.00180(5) 0.00483(6) 0.00065(5) P1 0.0243(2) 0.0209(2) 0.0346(2) 0.00288(17) 0.00769(17) -0.00153(16) C1 0.0274(9) 0.0329(9) 0.0355(10) 0.0127(8) 0.0043(7) 0.0066(7) C2 0.0187(7) 0.0353(9) 0.0281(8) 0.0051(7) 0.0038(6) 0.0039(6) C3 0.0182(7) 0.0292(8) 0.0268(8) 0.0018(7) 0.0063(6) -0.0009(6) C4 0.0203(7) 0.0312(9) 0.0258(8) -0.0004(6) 0.0095(6) 0.0013(6) C5 0.0312(9) 0.0314(9) 0.0286(9) -0.0051(7) 0.0093(7) 0.0008(7) C6 0.0286(10) 0.0585(13) 0.0260(9) 0.0037(9) 0.0001(7) -0.0034(9) C7 0.0317(9) 0.0452(11) 0.0274(9) 0.0047(8) 0.0106(7) -0.0038(8) C8 0.0298(9) 0.0361(9) 0.0287(9) 0.0024(7) 0.0137(7) 0.0008(7) C9 0.0284(8) 0.0276(8) 0.0260(8) -0.0029(7) 0.0095(6) 0.0046(6) C10 0.0282(8) 0.0194(7) 0.0285(8) -0.0004(6) 0.0070(6) 0.0029(6) C11 0.0245(7) 0.0225(8) 0.0281(8) 0.0053(6) 0.0054(6) 0.0075(6) C12 0.0251(8) 0.0321(9) 0.0274(9) 0.0038(7) 0.0000(7) 0.0016(7) C13 0.0486(11) 0.0379(10) 0.0256(9) -0.0057(8) 0.0075(8) -0.0009(9) C14 0.0415(10) 0.0292(9) 0.0307(9) 0.0084(8) 0.0073(8) 0.0043(8) C15 0.0309(10) 0.0341(11) 0.0800(17) 0.0030(11) -0.0017(10) -0.0086(9) C16 0.083(2) 0.0688(19) 0.0578(16) 0.0304(14) -0.0042(15) -0.0448(16) C17 0.0724(19) 0.0314(12) 0.139(3) -0.0273(16) 0.057(2) -0.0152(12) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zr1 C10 2.4233(15) . ? Zr1 C3 2.4270(15) . ? Zr1 C9 2.4452(15) . ? Zr1 C1 2.4513(16) . ? Zr1 C2 2.4521(15) . ? Zr1 C8 2.4538(16) . ? Zr1 C5 2.4538(17) . ? Zr1 C4 2.4552(15) . ? Zr1 C12 2.4634(16) . ? Zr1 C11 2.4665(14) . ? Zr1 P1 2.6763(4) . ? P1 C15 1.814(2) . ? P1 C17 1.817(3) . ? P1 C16 1.827(2) . ? C1 C2 1.415(2) . ? C1 H1A 0.92(2) . ? C1 H1B 1.01(2) . ? C2 C3 1.420(2) . ? C2 C6 1.512(2) . ? C3 C4 1.429(2) . ? C3 H3 0.945(19) . ? C4 C5 1.409(2) . ? C4 C7 1.509(2) . ? C5 H5A 0.939(19) . ? C5 H5B 0.92(2) . ? C6 H6A 0.97(2) . ? C6 H6B 0.93(3) . ? C6 H6C 0.95(2) . ? C7 H7A 0.94(2) . ? C7 H7B 0.96(2) . ? C7 H7C 0.954(19) . ? C8 C9 1.414(2) . ? C8 H8A 0.94(2) . ? C8 H8B 0.94(2) . ? C9 C10 1.420(2) . ? C9 C13 1.513(2) . ? C10 C11 1.427(2) . ? C10 H10 0.951(18) . ? C11 C12 1.406(2) . ? C11 C14 1.509(2) . ? C12 H12A 0.96(2) . ? C12 H12B 0.924(19) . ? C13 H13A 0.96(2) . ? C13 H13B 0.97(2) . ? C13 H13C 0.97(2) . ? C14 H14A 0.93(2) . ? C14 H14B 0.96(2) . ? C14 H14C 0.94(2) . ? C15 H15A 0.94(3) . ? C15 H15B 0.97(3) . ? C15 H15C 1.00(3) . ? C16 H16A 0.91(4) . ? C16 H16B 0.96(3) . ? C16 H16C 0.97(5) . ? C17 H17A 0.96(3) . ? C17 H17B 0.99(3) . ? C17 H17C 1.08(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C10 Zr1 C3 96.95(6) . . ? C10 Zr1 C9 33.92(5) . . ? C3 Zr1 C9 106.97(5) . . ? C10 Zr1 C1 135.60(6) . . ? C3 Zr1 C1 61.99(6) . . ? C9 Zr1 C1 111.20(6) . . ? C10 Zr1 C2 108.47(6) . . ? C3 Zr1 C2 33.84(5) . . ? C9 Zr1 C2 98.54(5) . . ? C1 Zr1 C2 33.54(6) . . ? C10 Zr1 C8 62.18(6) . . ? C3 Zr1 C8 133.08(6) . . ? C9 Zr1 C8 33.54(6) . . ? C1 Zr1 C8 102.45(6) . . ? C2 Zr1 C8 109.52(6) . . ? C10 Zr1 C5 128.55(6) . . ? C3 Zr1 C5 62.35(6) . . ? C9 Zr1 C5 161.29(6) . . ? C1 Zr1 C5 78.39(7) . . ? C2 Zr1 C5 80.62(6) . . ? C8 Zr1 C5 163.22(6) . . ? C10 Zr1 C4 104.41(5) . . ? C3 Zr1 C4 34.03(5) . . ? C9 Zr1 C4 130.10(5) . . ? C1 Zr1 C4 80.00(6) . . ? C2 Zr1 C4 63.60(5) . . ? C8 Zr1 C4 163.34(6) . . ? C5 Zr1 C4 33.36(5) . . ? C10 Zr1 C12 62.03(6) . . ? C3 Zr1 C12 131.09(6) . . ? C9 Zr1 C12 80.28(6) . . ? C1 Zr1 C12 160.75(6) . . ? C2 Zr1 C12 163.99(6) . . ? C8 Zr1 C12 78.34(6) . . ? C5 Zr1 C12 95.37(6) . . ? C4 Zr1 C12 104.86(6) . . ? C10 Zr1 C11 33.93(5) . . ? C3 Zr1 C11 106.12(5) . . ? C9 Zr1 C11 63.51(5) . . ? C1 Zr1 C11 166.01(6) . . ? C2 Zr1 C11 132.57(6) . . ? C8 Zr1 C11 80.08(6) . . ? C5 Zr1 C11 103.24(6) . . ? C4 Zr1 C11 93.72(5) . . ? C12 Zr1 C11 33.13(5) . . ? C10 Zr1 P1 131.18(4) . . ? C3 Zr1 P1 131.81(4) . . ? C9 Zr1 P1 112.54(4) . . ? C1 Zr1 P1 78.45(4) . . ? C2 Zr1 P1 111.95(4) . . ? C8 Zr1 P1 79.14(4) . . ? C5 Zr1 P1 84.69(4) . . ? C4 Zr1 P1 117.36(4) . . ? C12 Zr1 P1 82.88(4) . . ? C11 Zr1 P1 115.49(4) . . ? C15 P1 C17 100.51(15) . . ? C15 P1 C16 99.76(15) . . ? C17 P1 C16 99.67(19) . . ? C15 P1 Zr1 119.13(8) . . ? C17 P1 Zr1 118.62(9) . . ? C16 P1 Zr1 115.64(9) . . ? C2 C1 Zr1 73.26(9) . . ? C2 C1 H1A 117.5(12) . . ? Zr1 C1 H1A 124.1(13) . . ? C2 C1 H1B 118.2(11) . . ? Zr1 C1 H1B 97.3(11) . . ? H1A C1 H1B 117.4(17) . . ? C1 C2 C3 124.80(16) . . ? C1 C2 C6 117.96(16) . . ? C3 C2 C6 117.14(16) . . ? C1 C2 Zr1 73.20(9) . . ? C3 C2 Zr1 72.11(8) . . ? C6 C2 Zr1 126.71(12) . . ? C2 C3 C4 130.35(15) . . ? C2 C3 Zr1 74.05(8) . . ? C4 C3 Zr1 74.07(9) . . ? C2 C3 H3 115.0(11) . . ? C4 C3 H3 114.3(11) . . ? Zr1 C3 H3 124.4(11) . . ? C5 C4 C3 125.81(15) . . ? C5 C4 C7 118.03(16) . . ? C3 C4 C7 116.11(15) . . ? C5 C4 Zr1 73.26(9) . . ? C3 C4 Zr1 71.90(9) . . ? C7 C4 Zr1 128.79(11) . . ? C4 C5 Zr1 73.37(9) . . ? C4 C5 H5A 116.1(12) . . ? Zr1 C5 H5A 126.0(11) . . ? C4 C5 H5B 119.1(12) . . ? Zr1 C5 H5B 97.6(13) . . ? H5A C5 H5B 116.9(17) . . ? C2 C6 H6A 112.0(13) . . ? C2 C6 H6B 112.7(15) . . ? H6A C6 H6B 107.0(19) . . ? C2 C6 H6C 113.2(13) . . ? H6A C6 H6C 107.3(18) . . ? H6B C6 H6C 104(2) . . ? C4 C7 H7A 111.8(13) . . ? C4 C7 H7B 107.7(13) . . ? H7A C7 H7B 108.4(18) . . ? C4 C7 H7C 110.0(11) . . ? H7A C7 H7C 110.4(17) . . ? H7B C7 H7C 108.5(17) . . ? C9 C8 Zr1 72.89(9) . . ? C9 C8 H8A 116.6(12) . . ? Zr1 C8 H8A 124.6(12) . . ? C9 C8 H8B 126.7(12) . . ? Zr1 C8 H8B 104.1(11) . . ? H8A C8 H8B 108.3(17) . . ? C8 C9 C10 125.41(15) . . ? C8 C9 C13 118.10(16) . . ? C10 C9 C13 116.34(15) . . ? C8 C9 Zr1 73.56(9) . . ? C10 C9 Zr1 72.19(9) . . ? C13 C9 Zr1 125.83(12) . . ? C9 C10 C11 130.40(15) . . ? C9 C10 Zr1 73.88(9) . . ? C11 C10 Zr1 74.70(9) . . ? C9 C10 H10 114.7(10) . . ? C11 C10 H10 114.7(10) . . ? Zr1 C10 H10 125.2(10) . . ? C12 C11 C10 125.47(15) . . ? C12 C11 C14 118.40(15) . . ? C10 C11 C14 116.02(15) . . ? C12 C11 Zr1 73.31(9) . . ? C10 C11 Zr1 71.38(8) . . ? C14 C11 Zr1 127.95(11) . . ? C11 C12 Zr1 73.56(9) . . ? C11 C12 H12A 116.7(12) . . ? Zr1 C12 H12A 125.4(12) . . ? C11 C12 H12B 121.2(12) . . ? Zr1 C12 H12B 97.4(11) . . ? H12A C12 H12B 115.1(16) . . ? C9 C13 H13A 111.3(12) . . ? C9 C13 H13B 110.1(13) . . ? H13A C13 H13B 107.6(18) . . ? C9 C13 H13C 109.1(13) . . ? H13A C13 H13C 107.9(18) . . ? H13B C13 H13C 110.9(18) . . ? C11 C14 H14A 109.3(14) . . ? C11 C14 H14B 112.8(12) . . ? H14A C14 H14B 109.8(19) . . ? C11 C14 H14C 113.7(12) . . ? H14A C14 H14C 105.1(18) . . ? H14B C14 H14C 105.8(17) . . ? P1 C15 H15A 110.0(14) . . ? P1 C15 H15B 105.7(18) . . ? H15A C15 H15B 111(2) . . ? P1 C15 H15C 111.3(16) . . ? H15A C15 H15C 110(2) . . ? H15B C15 H15C 109(2) . . ? P1 C16 H16A 114(2) . . ? P1 C16 H16B 114.7(14) . . ? H16A C16 H16B 110(3) . . ? P1 C16 H16C 105(3) . . ? H16A C16 H16C 108(3) . . ? H16B C16 H16C 104(3) . . ? P1 C17 H17A 110.6(15) . . ? P1 C17 H17B 102.0(18) . . ? H17A C17 H17B 102(2) . . ? P1 C17 H17C 100(2) . . ? H17A C17 H17C 108(3) . . ? H17B C17 H17C 133(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 C10 Zr1 P1 C15 -28.47(13) . . . . ? C3 Zr1 P1 C15 155.02(12) . . . . ? C9 Zr1 P1 C15 -62.31(12) . . . . ? C1 Zr1 P1 C15 -170.66(12) . . . . ? C2 Zr1 P1 C15 -172.23(12) . . . . ? C8 Zr1 P1 C15 -65.40(12) . . . . ? C5 Zr1 P1 C15 110.13(12) . . . . ? C4 Zr1 P1 C15 117.12(12) . . . . ? C12 Zr1 P1 C15 14.03(12) . . . . ? C11 Zr1 P1 C15 7.99(12) . . . . ? C10 Zr1 P1 C17 -151.29(18) . . . . ? C3 Zr1 P1 C17 32.20(18) . . . . ? C9 Zr1 P1 C17 174.87(17) . . . . ? C1 Zr1 P1 C17 66.52(17) . . . . ? C2 Zr1 P1 C17 64.96(17) . . . . ? C8 Zr1 P1 C17 171.78(17) . . . . ? C5 Zr1 P1 C17 -12.69(17) . . . . ? C4 Zr1 P1 C17 -5.70(17) . . . . ? C12 Zr1 P1 C17 -108.79(17) . . . . ? C11 Zr1 P1 C17 -114.83(17) . . . . ? C10 Zr1 P1 C16 90.39(17) . . . . ? C3 Zr1 P1 C16 -86.12(17) . . . . ? C9 Zr1 P1 C16 56.55(16) . . . . ? C1 Zr1 P1 C16 -51.80(17) . . . . ? C2 Zr1 P1 C16 -53.36(16) . . . . ? C8 Zr1 P1 C16 53.46(16) . . . . ? C5 Zr1 P1 C16 -131.00(17) . . . . ? C4 Zr1 P1 C16 -124.02(16) . . . . ? C12 Zr1 P1 C16 132.90(16) . . . . ? C11 Zr1 P1 C16 126.85(16) . . . . ? C10 Zr1 C1 C2 43.88(14) . . . . ? C3 Zr1 C1 C2 -25.80(10) . . . . ? C9 Zr1 C1 C2 72.73(11) . . . . ? C8 Zr1 C1 C2 106.64(11) . . . . ? C5 Zr1 C1 C2 -90.50(11) . . . . ? C4 Zr1 C1 C2 -56.56(10) . . . . ? C12 Zr1 C1 C2 -163.12(16) . . . . ? C11 Zr1 C1 C2 7.7(3) . . . . ? P1 Zr1 C1 C2 -177.37(11) . . . . ? Zr1 C1 C2 C3 53.09(15) . . . . ? Zr1 C1 C2 C6 -123.13(15) . . . . ? C10 Zr1 C2 C1 -149.24(11) . . . . ? C3 Zr1 C2 C1 136.37(16) . . . . ? C9 Zr1 C2 C1 -115.81(11) . . . . ? C8 Zr1 C2 C1 -83.05(12) . . . . ? C5 Zr1 C2 C1 83.11(11) . . . . ? C4 Zr1 C2 C1 113.45(12) . . . . ? C12 Zr1 C2 C1 159.7(2) . . . . ? C11 Zr1 C2 C1 -177.49(10) . . . . ? P1 Zr1 C2 C1 2.77(11) . . . . ? C10 Zr1 C2 C3 74.38(11) . . . . ? C9 Zr1 C2 C3 107.82(10) . . . . ? C1 Zr1 C2 C3 -136.37(16) . . . . ? C8 Zr1 C2 C3 140.57(10) . . . . ? C5 Zr1 C2 C3 -53.26(10) . . . . ? C4 Zr1 C2 C3 -22.92(9) . . . . ? C12 Zr1 C2 C3 23.3(3) . . . . ? C11 Zr1 C2 C3 46.14(13) . . . . ? P1 Zr1 C2 C3 -133.60(9) . . . . ? C10 Zr1 C2 C6 -36.55(16) . . . . ? C3 Zr1 C2 C6 -110.93(19) . . . . ? C9 Zr1 C2 C6 -3.12(16) . . . . ? C1 Zr1 C2 C6 112.7(2) . . . . ? C8 Zr1 C2 C6 29.64(17) . . . . ? C5 Zr1 C2 C6 -164.19(16) . . . . ? C4 Zr1 C2 C6 -133.85(17) . . . . ? C12 Zr1 C2 C6 -87.6(3) . . . . ? C11 Zr1 C2 C6 -64.79(17) . . . . ? P1 Zr1 C2 C6 115.47(15) . . . . ? C1 C2 C3 C4 -1.7(3) . . . . ? C6 C2 C3 C4 174.57(17) . . . . ? Zr1 C2 C3 C4 51.86(16) . . . . ? C1 C2 C3 Zr1 -53.55(15) . . . . ? C6 C2 C3 Zr1 122.70(15) . . . . ? C10 Zr1 C3 C2 -113.04(10) . . . . ? C9 Zr1 C3 C2 -79.85(11) . . . . ? C1 Zr1 C3 C2 25.58(10) . . . . ? C8 Zr1 C3 C2 -55.03(13) . . . . ? C5 Zr1 C3 C2 116.80(12) . . . . ? C4 Zr1 C3 C2 141.44(15) . . . . ? C12 Zr1 C3 C2 -171.67(10) . . . . ? C11 Zr1 C3 C2 -146.44(10) . . . . ? P1 Zr1 C3 C2 64.31(11) . . . . ? C10 Zr1 C3 C4 105.52(10) . . . . ? C9 Zr1 C3 C4 138.71(9) . . . . ? C1 Zr1 C3 C4 -115.86(11) . . . . ? C2 Zr1 C3 C4 -141.44(15) . . . . ? C8 Zr1 C3 C4 163.53(9) . . . . ? C5 Zr1 C3 C4 -24.64(9) . . . . ? C12 Zr1 C3 C4 46.89(12) . . . . ? C11 Zr1 C3 C4 72.12(10) . . . . ? P1 Zr1 C3 C4 -77.13(10) . . . . ? C2 C3 C4 C5 0.6(3) . . . . ? Zr1 C3 C4 C5 52.46(15) . . . . ? C2 C3 C4 C7 -176.88(16) . . . . ? Zr1 C3 C4 C7 -125.02(14) . . . . ? C2 C3 C4 Zr1 -51.86(16) . . . . ? C10 Zr1 C4 C5 141.23(10) . . . . ? C3 Zr1 C4 C5 -137.82(15) . . . . ? C9 Zr1 C4 C5 166.59(10) . . . . ? C1 Zr1 C4 C5 -84.04(11) . . . . ? C2 Zr1 C4 C5 -115.01(11) . . . . ? C8 Zr1 C4 C5 175.93(19) . . . . ? C12 Zr1 C4 C5 76.88(11) . . . . ? C11 Zr1 C4 C5 108.56(11) . . . . ? P1 Zr1 C4 C5 -12.72(11) . . . . ? C10 Zr1 C4 C3 -80.95(10) . . . . ? C9 Zr1 C4 C3 -55.59(12) . . . . ? C1 Zr1 C4 C3 53.78(10) . . . . ? C2 Zr1 C4 C3 22.80(10) . . . . ? C8 Zr1 C4 C3 -46.2(2) . . . . ? C5 Zr1 C4 C3 137.82(15) . . . . ? C12 Zr1 C4 C3 -145.31(10) . . . . ? C11 Zr1 C4 C3 -113.62(10) . . . . ? P1 Zr1 C4 C3 125.10(9) . . . . ? C10 Zr1 C4 C7 28.41(16) . . . . ? C3 Zr1 C4 C7 109.36(18) . . . . ? C9 Zr1 C4 C7 53.76(17) . . . . ? C1 Zr1 C4 C7 163.13(16) . . . . ? C2 Zr1 C4 C7 132.16(16) . . . . ? C8 Zr1 C4 C7 63.1(3) . . . . ? C5 Zr1 C4 C7 -112.83(19) . . . . ? C12 Zr1 C4 C7 -35.95(16) . . . . ? C11 Zr1 C4 C7 -4.26(16) . . . . ? P1 Zr1 C4 C7 -125.54(14) . . . . ? C3 C4 C5 Zr1 -51.91(15) . . . . ? C7 C4 C5 Zr1 125.53(14) . . . . ? C10 Zr1 C5 C4 -50.84(13) . . . . ? C3 Zr1 C5 C4 25.10(9) . . . . ? C9 Zr1 C5 C4 -33.6(2) . . . . ? C1 Zr1 C5 C4 89.41(11) . . . . ? C2 Zr1 C5 C4 55.36(10) . . . . ? C8 Zr1 C5 C4 -175.96(19) . . . . ? C12 Zr1 C5 C4 -109.01(10) . . . . ? C11 Zr1 C5 C4 -76.36(11) . . . . ? P1 Zr1 C5 C4 168.68(10) . . . . ? C10 Zr1 C8 C9 25.58(9) . . . . ? C3 Zr1 C8 C9 -46.59(13) . . . . ? C1 Zr1 C8 C9 -109.72(10) . . . . ? C2 Zr1 C8 C9 -75.55(11) . . . . ? C5 Zr1 C8 C9 159.25(19) . . . . ? C4 Zr1 C8 C9 -13.0(3) . . . . ? C12 Zr1 C8 C9 89.95(10) . . . . ? C11 Zr1 C8 C9 56.25(10) . . . . ? P1 Zr1 C8 C9 174.83(10) . . . . ? Zr1 C8 C9 C10 -53.07(15) . . . . ? Zr1 C8 C9 C13 122.30(15) . . . . ? C10 Zr1 C9 C8 -136.82(15) . . . . ? C3 Zr1 C9 C8 146.30(10) . . . . ? C1 Zr1 C9 C8 80.40(11) . . . . ? C2 Zr1 C9 C8 112.64(10) . . . . ? C5 Zr1 C9 C8 -161.41(17) . . . . ? C4 Zr1 C9 C8 175.17(10) . . . . ? C12 Zr1 C9 C8 -83.54(11) . . . . ? C11 Zr1 C9 C8 -113.78(11) . . . . ? P1 Zr1 C9 C8 -5.50(11) . . . . ? C3 Zr1 C9 C10 -76.87(10) . . . . ? C1 Zr1 C9 C10 -142.78(9) . . . . ? C2 Zr1 C9 C10 -110.54(10) . . . . ? C8 Zr1 C9 C10 136.82(15) . . . . ? C5 Zr1 C9 C10 -24.6(2) . . . . ? C4 Zr1 C9 C10 -48.01(12) . . . . ? C12 Zr1 C9 C10 53.29(10) . . . . ? C11 Zr1 C9 C10 23.04(9) . . . . ? P1 Zr1 C9 C10 131.33(8) . . . . ? C10 Zr1 C9 C13 110.05(18) . . . . ? C3 Zr1 C9 C13 33.18(16) . . . . ? C1 Zr1 C9 C13 -32.73(16) . . . . ? C2 Zr1 C9 C13 -0.49(15) . . . . ? C8 Zr1 C9 C13 -113.13(19) . . . . ? C5 Zr1 C9 C13 85.5(2) . . . . ? C4 Zr1 C9 C13 62.04(17) . . . . ? C12 Zr1 C9 C13 163.34(15) . . . . ? C11 Zr1 C9 C13 133.09(16) . . . . ? P1 Zr1 C9 C13 -118.62(14) . . . . ? C8 C9 C10 C11 1.0(3) . . . . ? C13 C9 C10 C11 -174.45(16) . . . . ? Zr1 C9 C10 C11 -52.65(16) . . . . ? C8 C9 C10 Zr1 53.63(15) . . . . ? C13 C9 C10 Zr1 -121.80(14) . . . . ? C3 Zr1 C10 C9 110.22(9) . . . . ? C1 Zr1 C10 C9 53.70(12) . . . . ? C2 Zr1 C10 C9 77.51(10) . . . . ? C8 Zr1 C10 C9 -25.31(9) . . . . ? C5 Zr1 C10 C9 170.17(9) . . . . ? C4 Zr1 C10 C9 144.05(9) . . . . ? C12 Zr1 C10 C9 -116.54(11) . . . . ? C11 Zr1 C10 C9 -141.13(14) . . . . ? P1 Zr1 C10 C9 -67.16(10) . . . . ? C3 Zr1 C10 C11 -108.65(9) . . . . ? C9 Zr1 C10 C11 141.13(14) . . . . ? C1 Zr1 C10 C11 -165.17(9) . . . . ? C2 Zr1 C10 C11 -141.36(9) . . . . ? C8 Zr1 C10 C11 115.81(11) . . . . ? C5 Zr1 C10 C11 -48.70(12) . . . . ? C4 Zr1 C10 C11 -74.82(10) . . . . ? C12 Zr1 C10 C11 24.58(9) . . . . ? P1 Zr1 C10 C11 73.97(10) . . . . ? C9 C10 C11 C12 0.1(3) . . . . ? Zr1 C10 C11 C12 -52.24(15) . . . . ? C9 C10 C11 C14 176.25(16) . . . . ? Zr1 C10 C11 C14 123.90(13) . . . . ? C9 C10 C11 Zr1 52.35(16) . . . . ? C10 Zr1 C11 C12 137.76(15) . . . . ? C3 Zr1 C11 C12 -144.00(10) . . . . ? C9 Zr1 C11 C12 114.73(11) . . . . ? C1 Zr1 C11 C12 -174.5(2) . . . . ? C2 Zr1 C11 C12 -168.71(10) . . . . ? C8 Zr1 C11 C12 83.84(11) . . . . ? C5 Zr1 C11 C12 -79.37(11) . . . . ? C4 Zr1 C11 C12 -111.75(10) . . . . ? P1 Zr1 C11 C12 11.02(11) . . . . ? C3 Zr1 C11 C10 78.23(10) . . . . ? C9 Zr1 C11 C10 -23.04(9) . . . . ? C1 Zr1 C11 C10 47.8(3) . . . . ? C2 Zr1 C11 C10 53.53(12) . . . . ? C8 Zr1 C11 C10 -53.92(10) . . . . ? C5 Zr1 C11 C10 142.87(9) . . . . ? C4 Zr1 C11 C10 110.49(9) . . . . ? C12 Zr1 C11 C10 -137.76(15) . . . . ? P1 Zr1 C11 C10 -126.74(8) . . . . ? C10 Zr1 C11 C14 -108.92(18) . . . . ? C3 Zr1 C11 C14 -30.69(16) . . . . ? C9 Zr1 C11 C14 -131.96(16) . . . . ? C1 Zr1 C11 C14 -61.1(3) . . . . ? C2 Zr1 C11 C14 -55.40(17) . . . . ? C8 Zr1 C11 C14 -162.84(16) . . . . ? C5 Zr1 C11 C14 33.95(16) . . . . ? C4 Zr1 C11 C14 1.57(15) . . . . ? C12 Zr1 C11 C14 113.32(19) . . . . ? P1 Zr1 C11 C14 124.34(14) . . . . ? C10 C11 C12 Zr1 51.46(14) . . . . ? C14 C11 C12 Zr1 -124.60(14) . . . . ? C10 Zr1 C12 C11 -25.14(9) . . . . ? C3 Zr1 C12 C11 48.52(13) . . . . ? C9 Zr1 C12 C11 -55.57(10) . . . . ? C1 Zr1 C12 C11 175.94(16) . . . . ? C2 Zr1 C12 C11 31.5(3) . . . . ? C8 Zr1 C12 C11 -89.67(10) . . . . ? C5 Zr1 C12 C11 106.07(10) . . . . ? C4 Zr1 C12 C11 73.53(10) . . . . ? P1 Zr1 C12 C11 -169.99(10) . . . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.409 _refine_diff_density_min -0.306 _refine_diff_density_rms 0.054 data_shelxl_b _database_code_depnum_ccdc_archive 'CCDC 212750' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C17 H31 Hf P' _chemical_formula_weight 444.88 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' P P 0.1023 0.0942 '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 monoclinic _symmetry_space_group_name_H-M 'P 21/c' 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 7.9542(1) _cell_length_b 15.4479(3) _cell_length_c 15.0000(3) _cell_angle_alpha 90.00 _cell_angle_beta 102.3556(12) _cell_angle_gamma 90.00 _cell_volume 1800.44(6) _cell_formula_units_Z 4 _cell_measurement_temperature 200(1) _cell_measurement_reflns_used 16693 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 27.48 _exptl_crystal_description prism _exptl_crystal_colour black-red _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.641 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 880 _exptl_absorpt_coefficient_mu 5.871 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.3215 _exptl_absorpt_correction_T_max 0.3719 _exptl_absorpt_process_details 'DENZO-SMN (Otwinowski & Minor 1997)' _exptl_special_details ; The program Denzo-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL-97 input file. ; _diffrn_ambient_temperature 200(1) _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 'Nonius KappaCCD Diffractometer' _diffrn_measurement_method 'Phi plus Omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2.0 _diffrn_reflns_number 7039 _diffrn_reflns_av_R_equivalents 0.0216 _diffrn_reflns_av_sigmaI/netI 0.0330 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.64 _diffrn_reflns_theta_max 27.46 _reflns_number_total 4054 _reflns_number_gt 3648 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius COLLECT' _computing_cell_refinement DENZO-SMN _computing_data_reduction DENZO-SMN _computing_structure_solution SIR97 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'WinGx, Ortep3' _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^)+(0.0129P)^2^+1.8326P] 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 0.0057(2) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 4054 _refine_ls_number_parameters 288 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0254 _refine_ls_R_factor_gt 0.0207 _refine_ls_wR_factor_ref 0.0470 _refine_ls_wR_factor_gt 0.0451 _refine_ls_goodness_of_fit_ref 1.052 _refine_ls_restrained_S_all 1.052 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Hf1 Hf 0.676789(14) 0.191599(7) 0.772547(7) 0.01705(6) Uani 1 1 d . . . P1 P 0.86192(10) 0.33470(5) 0.78453(5) 0.02337(17) Uani 1 1 d . . . C1 C 0.4724(4) 0.2910(2) 0.6855(3) 0.0289(7) Uani 1 1 d . . . H1A H 0.469(5) 0.309(2) 0.627(3) 0.036(10) Uiso 1 1 d . . . H1B H 0.464(4) 0.331(2) 0.722(3) 0.033(10) Uiso 1 1 d . . . C2 C 0.3834(4) 0.2121(2) 0.6873(2) 0.0238(6) Uani 1 1 d . . . C3 C 0.3765(3) 0.1651(2) 0.76787(19) 0.0206(6) Uani 1 1 d . . . H3 H 0.326(4) 0.110(2) 0.759(2) 0.016(7) Uiso 1 1 d . . . C4 C 0.4544(4) 0.18289(19) 0.8606(2) 0.0226(6) Uani 1 1 d . . . C5 C 0.5577(4) 0.2556(2) 0.8923(2) 0.0256(6) Uani 1 1 d . . . H5B H 0.531(4) 0.310(2) 0.869(2) 0.025(9) Uiso 1 1 d . . . H5A H 0.617(4) 0.252(2) 0.957(2) 0.032(9) Uiso 1 1 d . . . C6 C 0.2985(5) 0.1715(3) 0.5969(2) 0.0362(8) Uani 1 1 d . . . H6A H 0.279(5) 0.109(3) 0.601(2) 0.041(10) Uiso 1 1 d . . . H6B H 0.192(7) 0.202(3) 0.576(3) 0.066(15) Uiso 1 1 d . . . H6C H 0.365(5) 0.184(2) 0.553(3) 0.033(10) Uiso 1 1 d . . . C7 C 0.4250(4) 0.1166(2) 0.9300(2) 0.0295(7) Uani 1 1 d . . . H7A H 0.409(4) 0.062(2) 0.907(2) 0.032(10) Uiso 1 1 d . . . H7B H 0.328(5) 0.137(2) 0.953(2) 0.034(9) Uiso 1 1 d . . . H7C H 0.520(4) 0.113(2) 0.980(2) 0.032(9) Uiso 1 1 d . . . C8 C 0.8564(4) 0.1597(2) 0.6654(2) 0.0255(6) Uani 1 1 d . . . H8A H 0.850(4) 0.184(2) 0.613(2) 0.024(9) Uiso 1 1 d . . . H8B H 0.970(5) 0.171(2) 0.697(2) 0.029 Uiso 1 1 d . . . C9 C 0.7583(4) 0.08429(19) 0.67256(19) 0.0240(6) Uani 1 1 d . . . C10 C 0.7472(4) 0.04186(19) 0.7544(2) 0.0223(6) Uani 1 1 d . . . H10 H 0.674(4) -0.006(2) 0.747(2) 0.020(8) Uiso 1 1 d . . . C11 C 0.8233(3) 0.06359(18) 0.84683(19) 0.0215(6) Uani 1 1 d . . . C12 C 0.9313(4) 0.1351(2) 0.8746(2) 0.0252(6) Uani 1 1 d . . . H12A H 0.960(4) 0.144(2) 0.935(2) 0.023(8) Uiso 1 1 d . . . H12B H 1.009(4) 0.151(2) 0.844(2) 0.026(9) Uiso 1 1 d . . . C13 C 0.6478(5) 0.0479(2) 0.5856(2) 0.0334(7) Uani 1 1 d . . . H13A H 0.553(5) 0.014(3) 0.595(2) 0.042(11) Uiso 1 1 d . . . H13B H 0.604(4) 0.091(2) 0.544(2) 0.036(10) Uiso 1 1 d . . . H13C H 0.706(5) 0.012(3) 0.556(3) 0.045(11) Uiso 1 1 d . . . C14 C 0.7764(5) 0.0061(2) 0.9193(2) 0.0293(7) Uani 1 1 d . . . H14A H 0.855(5) -0.038(3) 0.935(3) 0.051(11) Uiso 1 1 d . . . H14B H 0.671(5) -0.020(2) 0.900(2) 0.029(9) Uiso 1 1 d . . . H14C H 0.774(4) 0.035(2) 0.973(2) 0.034(9) Uiso 1 1 d . . . C15 C 1.0920(5) 0.3291(3) 0.8307(4) 0.0458(10) Uani 1 1 d . . . H15A H 1.147(5) 0.386(3) 0.830(3) 0.046(11) Uiso 1 1 d . . . H15B H 1.107(6) 0.304(3) 0.894(3) 0.063(15) Uiso 1 1 d . . . H15C H 1.133(7) 0.294(4) 0.797(4) 0.08(2) Uiso 1 1 d . . . C16 C 0.8612(8) 0.3894(4) 0.6763(4) 0.0670(16) Uani 1 1 d . . . H16A H 0.735(8) 0.404(4) 0.651(4) 0.10(2) Uiso 1 1 d . . . H16B H 0.936(6) 0.438(4) 0.686(3) 0.077(15) Uiso 1 1 d . . . H16C H 0.933(8) 0.351(4) 0.649(4) 0.11(2) Uiso 1 1 d . . . C17 C 0.8061(7) 0.4243(3) 0.8500(4) 0.0723(16) Uani 1 1 d . . . H17A H 0.8810 0.4737 0.8452 0.079(15) Uiso 1 1 calc R . . H17B H 0.8212 0.4071 0.9141 0.10(2) Uiso 1 1 calc R . . H17C H 0.6859 0.4407 0.8261 0.15(3) 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 0.01708(9) 0.01602(8) 0.01828(8) 0.00163(4) 0.00430(5) 0.00059(4) P1 0.0214(4) 0.0177(4) 0.0313(4) 0.0027(3) 0.0064(3) -0.0011(3) C1 0.0270(16) 0.0293(18) 0.0289(17) 0.0094(16) 0.0023(13) 0.0075(14) C2 0.0160(14) 0.0291(16) 0.0259(15) 0.0045(13) 0.0039(11) 0.0005(12) C3 0.0159(13) 0.0242(15) 0.0218(14) 0.0003(12) 0.0042(11) -0.0007(11) C4 0.0169(14) 0.0274(16) 0.0257(15) 0.0007(12) 0.0090(12) 0.0020(11) C5 0.0252(15) 0.0274(17) 0.0256(16) -0.0052(13) 0.0085(12) 0.0010(12) C6 0.0274(19) 0.056(3) 0.0229(17) 0.0053(16) -0.0006(14) -0.0042(17) C7 0.0301(18) 0.038(2) 0.0219(16) 0.0057(14) 0.0102(14) -0.0025(14) C8 0.0268(17) 0.0285(17) 0.0243(16) 0.0022(13) 0.0127(13) 0.0015(13) C9 0.0266(15) 0.0227(15) 0.0238(14) -0.0020(12) 0.0084(12) 0.0046(12) C10 0.0248(15) 0.0152(14) 0.0281(15) -0.0032(12) 0.0083(12) 0.0019(11) C11 0.0223(14) 0.0179(14) 0.0244(14) 0.0056(11) 0.0050(11) 0.0074(11) C12 0.0211(15) 0.0281(17) 0.0240(16) 0.0042(13) -0.0006(12) 0.0048(12) C13 0.043(2) 0.0318(19) 0.0244(17) -0.0065(15) 0.0051(15) 0.0001(16) C14 0.0358(19) 0.0238(17) 0.0278(17) 0.0073(14) 0.0060(14) 0.0040(14) C15 0.0234(18) 0.034(2) 0.075(3) 0.000(2) -0.0011(18) -0.0077(15) C16 0.074(4) 0.056(3) 0.063(3) 0.030(3) -0.003(3) -0.039(3) C17 0.073(3) 0.028(2) 0.132(5) -0.031(3) 0.060(3) -0.016(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Hf1 C1 2.408(3) . ? Hf1 C10 2.409(3) . ? Hf1 C3 2.410(3) . ? Hf1 C5 2.415(3) . ? Hf1 C9 2.415(3) . ? Hf1 C8 2.418(3) . ? Hf1 C12 2.424(3) . ? Hf1 C4 2.427(3) . ? Hf1 C2 2.430(3) . ? Hf1 C11 2.440(3) . ? Hf1 P1 2.6409(8) . ? P1 C17 1.806(4) . ? P1 C15 1.815(4) . ? P1 C16 1.829(5) . ? C1 C2 1.412(5) . ? C1 H1A 0.92(4) . ? C1 H1B 0.85(4) . ? C2 C3 1.422(4) . ? C2 C6 1.516(5) . ? C3 C4 1.424(4) . ? C3 H3 0.93(3) . ? C4 C5 1.413(4) . ? C4 C7 1.513(4) . ? C5 H5B 0.92(3) . ? C5 H5A 0.98(3) . ? C6 H6A 0.98(4) . ? C6 H6B 0.96(5) . ? C6 H6C 0.95(4) . ? C7 H7A 0.91(4) . ? C7 H7B 0.96(4) . ? C7 H7C 0.95(4) . ? C8 C9 1.418(4) . ? C8 H8A 0.86(4) . ? C8 H8B 0.94(4) . ? C9 C10 1.411(4) . ? C9 C13 1.516(4) . ? C10 C11 1.429(4) . ? C10 H10 0.93(3) . ? C11 C12 1.406(4) . ? C11 C14 1.510(4) . ? C12 H12A 0.90(3) . ? C12 H12B 0.88(3) . ? C13 H13A 0.95(4) . ? C13 H13B 0.92(4) . ? C13 H13C 0.90(4) . ? C14 H14A 0.92(4) . ? C14 H14B 0.92(4) . ? C14 H14C 0.93(4) . ? C15 H15A 0.98(4) . ? C15 H15B 1.02(5) . ? C15 H15C 0.86(6) . ? C16 H16A 1.02(6) . ? C16 H16B 0.95(5) . ? C16 H16C 0.97(6) . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 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 C1 Hf1 C10 134.23(12) . . ? C1 Hf1 C3 62.78(11) . . ? C10 Hf1 C3 94.94(10) . . ? C1 Hf1 C5 79.34(12) . . ? C10 Hf1 C5 127.95(11) . . ? C3 Hf1 C5 63.07(10) . . ? C1 Hf1 C9 109.94(12) . . ? C10 Hf1 C9 34.02(10) . . ? C3 Hf1 C9 105.15(10) . . ? C5 Hf1 C9 160.61(11) . . ? C1 Hf1 C8 101.33(12) . . ? C10 Hf1 C8 62.90(11) . . ? C3 Hf1 C8 131.97(11) . . ? C5 Hf1 C8 163.61(11) . . ? C9 Hf1 C8 34.12(10) . . ? C1 Hf1 C12 161.41(12) . . ? C10 Hf1 C12 62.77(10) . . ? C3 Hf1 C12 130.21(11) . . ? C5 Hf1 C12 94.90(11) . . ? C9 Hf1 C12 81.13(10) . . ? C8 Hf1 C12 79.27(12) . . ? C1 Hf1 C4 81.04(11) . . ? C10 Hf1 C4 102.84(10) . . ? C3 Hf1 C4 34.24(10) . . ? C5 Hf1 C4 33.93(10) . . ? C9 Hf1 C4 128.59(10) . . ? C8 Hf1 C4 162.40(11) . . ? C12 Hf1 C4 104.09(11) . . ? C1 Hf1 C2 33.94(11) . . ? C10 Hf1 C2 106.63(10) . . ? C3 Hf1 C2 34.17(10) . . ? C5 Hf1 C2 81.53(10) . . ? C9 Hf1 C2 96.77(10) . . ? C8 Hf1 C2 108.32(11) . . ? C12 Hf1 C2 163.22(11) . . ? C4 Hf1 C2 64.17(10) . . ? C1 Hf1 C11 164.91(11) . . ? C10 Hf1 C11 34.27(9) . . ? C3 Hf1 C11 104.41(10) . . ? C5 Hf1 C11 102.55(11) . . ? C9 Hf1 C11 64.02(10) . . ? C8 Hf1 C11 81.13(10) . . ? C12 Hf1 C11 33.60(10) . . ? C4 Hf1 C11 92.23(10) . . ? C2 Hf1 C11 131.08(10) . . ? C1 Hf1 P1 78.76(9) . . ? C10 Hf1 P1 132.20(7) . . ? C3 Hf1 P1 132.78(8) . . ? C5 Hf1 P1 84.74(8) . . ? C9 Hf1 P1 113.38(7) . . ? C8 Hf1 P1 79.39(8) . . ? C12 Hf1 P1 83.14(8) . . ? C4 Hf1 P1 118.03(7) . . ? C2 Hf1 P1 112.66(8) . . ? C11 Hf1 P1 116.26(7) . . ? C17 P1 C15 100.0(2) . . ? C17 P1 C16 100.0(3) . . ? C15 P1 C16 99.9(3) . . ? C17 P1 Hf1 118.69(14) . . ? C15 P1 Hf1 119.23(14) . . ? C16 P1 Hf1 115.50(16) . . ? C2 C1 Hf1 73.90(17) . . ? C2 C1 H1A 111(2) . . ? Hf1 C1 H1A 126(2) . . ? C2 C1 H1B 121(3) . . ? Hf1 C1 H1B 105(2) . . ? H1A C1 H1B 115(3) . . ? C1 C2 C3 124.6(3) . . ? C1 C2 C6 118.1(3) . . ? C3 C2 C6 117.2(3) . . ? C1 C2 Hf1 72.16(17) . . ? C3 C2 Hf1 72.13(15) . . ? C6 C2 Hf1 127.7(2) . . ? C2 C3 C4 130.1(3) . . ? C2 C3 Hf1 73.71(16) . . ? C4 C3 Hf1 73.57(16) . . ? C2 C3 H3 115.9(19) . . ? C4 C3 H3 113.5(19) . . ? Hf1 C3 H3 123.3(18) . . ? C5 C4 C3 125.6(3) . . ? C5 C4 C7 118.1(3) . . ? C3 C4 C7 116.2(3) . . ? C5 C4 Hf1 72.53(16) . . ? C3 C4 Hf1 72.19(16) . . ? C7 C4 Hf1 130.5(2) . . ? C4 C5 Hf1 73.54(17) . . ? C4 C5 H5B 122(2) . . ? Hf1 C5 H5B 101(2) . . ? C4 C5 H5A 114(2) . . ? Hf1 C5 H5A 122(2) . . ? H5B C5 H5A 116(3) . . ? C2 C6 H6A 113(2) . . ? C2 C6 H6B 106(3) . . ? H6A C6 H6B 112(3) . . ? C2 C6 H6C 109(2) . . ? H6A C6 H6C 111(3) . . ? H6B C6 H6C 105(3) . . ? C4 C7 H7A 113(2) . . ? C4 C7 H7B 106(2) . . ? H7A C7 H7B 112(3) . . ? C4 C7 H7C 112(2) . . ? H7A C7 H7C 105(3) . . ? H7B C7 H7C 108(3) . . ? C9 C8 Hf1 72.83(16) . . ? C9 C8 H8A 120(2) . . ? Hf1 C8 H8A 126(2) . . ? C9 C8 H8B 126(2) . . ? Hf1 C8 H8B 105(2) . . ? H8A C8 H8B 104(3) . . ? C10 C9 C8 125.8(3) . . ? C10 C9 C13 116.3(3) . . ? C8 C9 C13 117.8(3) . . ? C10 C9 Hf1 72.75(16) . . ? C8 C9 Hf1 73.05(17) . . ? C13 C9 Hf1 127.2(2) . . ? C9 C10 C11 130.0(3) . . ? C9 C10 Hf1 73.24(17) . . ? C11 C10 Hf1 74.06(16) . . ? C9 C10 H10 114.7(19) . . ? C11 C10 H10 115.2(19) . . ? Hf1 C10 H10 128.2(19) . . ? C12 C11 C10 125.2(3) . . ? C12 C11 C14 118.5(3) . . ? C10 C11 C14 116.2(3) . . ? C12 C11 Hf1 72.57(16) . . ? C10 C11 Hf1 71.68(15) . . ? C14 C11 Hf1 129.6(2) . . ? C11 C12 Hf1 73.83(16) . . ? C11 C12 H12A 115(2) . . ? Hf1 C12 H12A 126(2) . . ? C11 C12 H12B 121(2) . . ? Hf1 C12 H12B 99(2) . . ? H12A C12 H12B 115(3) . . ? C9 C13 H13A 114(2) . . ? C9 C13 H13B 112(2) . . ? H13A C13 H13B 107(3) . . ? C9 C13 H13C 113(2) . . ? H13A C13 H13C 104(3) . . ? H13B C13 H13C 106(3) . . ? C11 C14 H14A 111(2) . . ? C11 C14 H14B 112(2) . . ? H14A C14 H14B 107(3) . . ? C11 C14 H14C 113(2) . . ? H14A C14 H14C 106(3) . . ? H14B C14 H14C 107(3) . . ? P1 C15 H15A 112(2) . . ? P1 C15 H15B 107(3) . . ? H15A C15 H15B 113(3) . . ? P1 C15 H15C 107(4) . . ? H15A C15 H15C 109(5) . . ? H15B C15 H15C 110(4) . . ? P1 C16 H16A 104(3) . . ? P1 C16 H16B 110(3) . . ? H16A C16 H16B 115(4) . . ? P1 C16 H16C 102(4) . . ? H16A C16 H16C 127(5) . . ? H16B C16 H16C 98(4) . . ? P1 C17 H17A 109.5 . . ? P1 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? P1 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 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 C1 Hf1 P1 C17 68.4(3) . . . . ? C10 Hf1 P1 C17 -150.3(3) . . . . ? C3 Hf1 P1 C17 33.4(3) . . . . ? C5 Hf1 P1 C17 -11.7(3) . . . . ? C9 Hf1 P1 C17 175.4(3) . . . . ? C8 Hf1 P1 C17 172.4(3) . . . . ? C12 Hf1 P1 C17 -107.3(3) . . . . ? C4 Hf1 P1 C17 -5.0(3) . . . . ? C2 Hf1 P1 C17 66.8(3) . . . . ? C11 Hf1 P1 C17 -113.2(3) . . . . ? C1 Hf1 P1 C15 -169.4(2) . . . . ? C10 Hf1 P1 C15 -28.1(2) . . . . ? C3 Hf1 P1 C15 155.7(2) . . . . ? C5 Hf1 P1 C15 110.5(2) . . . . ? C9 Hf1 P1 C15 -62.3(2) . . . . ? C8 Hf1 P1 C15 -65.4(2) . . . . ? C12 Hf1 P1 C15 14.9(2) . . . . ? C4 Hf1 P1 C15 117.2(2) . . . . ? C2 Hf1 P1 C15 -171.0(2) . . . . ? C11 Hf1 P1 C15 9.1(2) . . . . ? C1 Hf1 P1 C16 -50.3(3) . . . . ? C10 Hf1 P1 C16 90.9(3) . . . . ? C3 Hf1 P1 C16 -85.3(3) . . . . ? C5 Hf1 P1 C16 -130.5(3) . . . . ? C9 Hf1 P1 C16 56.7(3) . . . . ? C8 Hf1 P1 C16 53.6(3) . . . . ? C12 Hf1 P1 C16 133.9(3) . . . . ? C4 Hf1 P1 C16 -123.7(3) . . . . ? C2 Hf1 P1 C16 -51.9(3) . . . . ? C11 Hf1 P1 C16 128.1(3) . . . . ? C10 Hf1 C1 C2 43.0(3) . . . . ? C3 Hf1 C1 C2 -25.56(18) . . . . ? C5 Hf1 C1 C2 -90.6(2) . . . . ? C9 Hf1 C1 C2 71.7(2) . . . . ? C8 Hf1 C1 C2 106.0(2) . . . . ? C12 Hf1 C1 C2 -164.0(3) . . . . ? C4 Hf1 C1 C2 -56.2(2) . . . . ? C11 Hf1 C1 C2 8.1(6) . . . . ? P1 Hf1 C1 C2 -177.3(2) . . . . ? Hf1 C1 C2 C3 52.2(3) . . . . ? Hf1 C1 C2 C6 -123.8(3) . . . . ? C10 Hf1 C2 C1 -149.3(2) . . . . ? C3 Hf1 C2 C1 136.9(3) . . . . ? C5 Hf1 C2 C1 83.5(2) . . . . ? C9 Hf1 C2 C1 -116.0(2) . . . . ? C8 Hf1 C2 C1 -83.0(2) . . . . ? C12 Hf1 C2 C1 162.2(4) . . . . ? C4 Hf1 C2 C1 114.2(2) . . . . ? C11 Hf1 C2 C1 -177.2(2) . . . . ? P1 Hf1 C2 C1 2.8(2) . . . . ? C1 Hf1 C2 C3 -136.9(3) . . . . ? C10 Hf1 C2 C3 73.76(19) . . . . ? C5 Hf1 C2 C3 -53.43(19) . . . . ? C9 Hf1 C2 C3 107.07(18) . . . . ? C8 Hf1 C2 C3 140.06(18) . . . . ? C12 Hf1 C2 C3 25.3(5) . . . . ? C4 Hf1 C2 C3 -22.74(17) . . . . ? C11 Hf1 C2 C3 45.9(2) . . . . ? P1 Hf1 C2 C3 -134.07(16) . . . . ? C1 Hf1 C2 C6 112.1(4) . . . . ? C10 Hf1 C2 C6 -37.2(3) . . . . ? C3 Hf1 C2 C6 -111.0(4) . . . . ? C5 Hf1 C2 C6 -164.4(3) . . . . ? C9 Hf1 C2 C6 -3.9(3) . . . . ? C8 Hf1 C2 C6 29.1(3) . . . . ? C12 Hf1 C2 C6 -85.7(5) . . . . ? C4 Hf1 C2 C6 -133.7(3) . . . . ? C11 Hf1 C2 C6 -65.1(3) . . . . ? P1 Hf1 C2 C6 114.9(3) . . . . ? C1 C2 C3 C4 -1.3(5) . . . . ? C6 C2 C3 C4 174.6(3) . . . . ? Hf1 C2 C3 C4 50.8(3) . . . . ? C1 C2 C3 Hf1 -52.2(3) . . . . ? C6 C2 C3 Hf1 123.8(3) . . . . ? C1 Hf1 C3 C2 25.40(19) . . . . ? C10 Hf1 C3 C2 -112.58(18) . . . . ? C5 Hf1 C3 C2 117.0(2) . . . . ? C9 Hf1 C3 C2 -79.56(19) . . . . ? C8 Hf1 C3 C2 -55.1(2) . . . . ? C12 Hf1 C3 C2 -170.69(17) . . . . ? C4 Hf1 C3 C2 141.8(3) . . . . ? C11 Hf1 C3 C2 -146.04(18) . . . . ? P1 Hf1 C3 C2 64.6(2) . . . . ? C1 Hf1 C3 C4 -116.4(2) . . . . ? C10 Hf1 C3 C4 105.63(18) . . . . ? C5 Hf1 C3 C4 -24.80(17) . . . . ? C9 Hf1 C3 C4 138.65(17) . . . . ? C8 Hf1 C3 C4 163.14(17) . . . . ? C12 Hf1 C3 C4 47.5(2) . . . . ? C2 Hf1 C3 C4 -141.8(3) . . . . ? C11 Hf1 C3 C4 72.16(19) . . . . ? P1 Hf1 C3 C4 -77.19(19) . . . . ? C2 C3 C4 C5 0.9(5) . . . . ? Hf1 C3 C4 C5 51.8(3) . . . . ? C2 C3 C4 C7 -177.9(3) . . . . ? Hf1 C3 C4 C7 -127.0(3) . . . . ? C2 C3 C4 Hf1 -50.9(3) . . . . ? C1 Hf1 C4 C5 -84.2(2) . . . . ? C10 Hf1 C4 C5 142.31(19) . . . . ? C3 Hf1 C4 C5 -137.9(3) . . . . ? C9 Hf1 C4 C5 167.39(18) . . . . ? C8 Hf1 C4 C5 176.6(3) . . . . ? C12 Hf1 C4 C5 77.6(2) . . . . ? C2 Hf1 C4 C5 -115.2(2) . . . . ? C11 Hf1 C4 C5 109.38(19) . . . . ? P1 Hf1 C4 C5 -12.1(2) . . . . ? C1 Hf1 C4 C3 53.74(19) . . . . ? C10 Hf1 C4 C3 -79.76(19) . . . . ? C5 Hf1 C4 C3 137.9(3) . . . . ? C9 Hf1 C4 C3 -54.7(2) . . . . ? C8 Hf1 C4 C3 -45.5(4) . . . . ? C12 Hf1 C4 C3 -144.50(18) . . . . ? C2 Hf1 C4 C3 22.70(17) . . . . ? C11 Hf1 C4 C3 -112.68(18) . . . . ? P1 Hf1 C4 C3 125.83(16) . . . . ? C1 Hf1 C4 C7 163.4(3) . . . . ? C10 Hf1 C4 C7 29.9(3) . . . . ? C3 Hf1 C4 C7 109.6(4) . . . . ? C5 Hf1 C4 C7 -112.4(4) . . . . ? C9 Hf1 C4 C7 55.0(3) . . . . ? C8 Hf1 C4 C7 64.1(5) . . . . ? C12 Hf1 C4 C7 -34.9(3) . . . . ? C2 Hf1 C4 C7 132.3(3) . . . . ? C11 Hf1 C4 C7 -3.1(3) . . . . ? P1 Hf1 C4 C7 -124.5(3) . . . . ? C3 C4 C5 Hf1 -51.7(3) . . . . ? C7 C4 C5 Hf1 127.1(3) . . . . ? C1 Hf1 C5 C4 89.8(2) . . . . ? C10 Hf1 C5 C4 -49.1(2) . . . . ? C3 Hf1 C5 C4 25.01(17) . . . . ? C9 Hf1 C5 C4 -30.9(4) . . . . ? C8 Hf1 C5 C4 -176.3(3) . . . . ? C12 Hf1 C5 C4 -108.08(19) . . . . ? C2 Hf1 C5 C4 55.40(19) . . . . ? C11 Hf1 C5 C4 -74.95(19) . . . . ? P1 Hf1 C5 C4 169.29(18) . . . . ? C1 Hf1 C8 C9 -108.93(19) . . . . ? C10 Hf1 C8 C9 25.23(17) . . . . ? C3 Hf1 C8 C9 -45.5(2) . . . . ? C5 Hf1 C8 C9 160.4(4) . . . . ? C12 Hf1 C8 C9 90.00(19) . . . . ? C4 Hf1 C8 C9 -12.8(5) . . . . ? C2 Hf1 C8 C9 -74.5(2) . . . . ? C11 Hf1 C8 C9 55.94(18) . . . . ? P1 Hf1 C8 C9 174.94(19) . . . . ? Hf1 C8 C9 C10 -53.0(3) . . . . ? Hf1 C8 C9 C13 123.7(3) . . . . ? C1 Hf1 C9 C10 -142.08(17) . . . . ? C3 Hf1 C9 C10 -76.03(18) . . . . ? C5 Hf1 C9 C10 -26.1(4) . . . . ? C8 Hf1 C9 C10 137.3(3) . . . . ? C12 Hf1 C9 C10 53.37(17) . . . . ? C4 Hf1 C9 C10 -47.6(2) . . . . ? C2 Hf1 C9 C10 -109.82(17) . . . . ? C11 Hf1 C9 C10 22.89(16) . . . . ? P1 Hf1 C9 C10 131.88(15) . . . . ? C1 Hf1 C9 C8 80.6(2) . . . . ? C10 Hf1 C9 C8 -137.3(3) . . . . ? C3 Hf1 C9 C8 146.67(19) . . . . ? C5 Hf1 C9 C8 -163.4(3) . . . . ? C12 Hf1 C9 C8 -83.9(2) . . . . ? C4 Hf1 C9 C8 175.07(18) . . . . ? C2 Hf1 C9 C8 112.88(19) . . . . ? C11 Hf1 C9 C8 -114.4(2) . . . . ? P1 Hf1 C9 C8 -5.4(2) . . . . ? C1 Hf1 C9 C13 -31.8(3) . . . . ? C10 Hf1 C9 C13 110.3(3) . . . . ? C3 Hf1 C9 C13 34.3(3) . . . . ? C5 Hf1 C9 C13 84.2(4) . . . . ? C8 Hf1 C9 C13 -112.4(3) . . . . ? C12 Hf1 C9 C13 163.7(3) . . . . ? C4 Hf1 C9 C13 62.7(3) . . . . ? C2 Hf1 C9 C13 0.5(3) . . . . ? C11 Hf1 C9 C13 133.2(3) . . . . ? P1 Hf1 C9 C13 -117.8(3) . . . . ? C8 C9 C10 C11 1.9(5) . . . . ? C13 C9 C10 C11 -174.8(3) . . . . ? Hf1 C9 C10 C11 -51.2(3) . . . . ? C8 C9 C10 Hf1 53.1(3) . . . . ? C13 C9 C10 Hf1 -123.6(3) . . . . ? C1 Hf1 C10 C9 53.7(2) . . . . ? C3 Hf1 C10 C9 109.92(17) . . . . ? C5 Hf1 C10 C9 169.32(16) . . . . ? C8 Hf1 C10 C9 -25.30(17) . . . . ? C12 Hf1 C10 C9 -116.9(2) . . . . ? C4 Hf1 C10 C9 143.68(17) . . . . ? C2 Hf1 C10 C9 77.15(18) . . . . ? C11 Hf1 C10 C9 -141.6(3) . . . . ? P1 Hf1 C10 C9 -67.29(19) . . . . ? C1 Hf1 C10 C11 -164.65(17) . . . . ? C3 Hf1 C10 C11 -108.47(17) . . . . ? C5 Hf1 C10 C11 -49.1(2) . . . . ? C9 Hf1 C10 C11 141.6(3) . . . . ? C8 Hf1 C10 C11 116.32(19) . . . . ? C12 Hf1 C10 C11 24.71(16) . . . . ? C4 Hf1 C10 C11 -74.70(18) . . . . ? C2 Hf1 C10 C11 -141.23(16) . . . . ? P1 Hf1 C10 C11 74.32(18) . . . . ? C9 C10 C11 C12 -0.8(5) . . . . ? Hf1 C10 C11 C12 -51.7(3) . . . . ? C9 C10 C11 C14 176.7(3) . . . . ? Hf1 C10 C11 C14 125.8(2) . . . . ? C9 C10 C11 Hf1 50.9(3) . . . . ? C1 Hf1 C11 C12 -175.4(4) . . . . ? C10 Hf1 C11 C12 137.8(3) . . . . ? C3 Hf1 C11 C12 -144.86(18) . . . . ? C5 Hf1 C11 C12 -79.81(19) . . . . ? C9 Hf1 C11 C12 115.1(2) . . . . ? C8 Hf1 C11 C12 83.94(19) . . . . ? C4 Hf1 C11 C12 -112.45(19) . . . . ? C2 Hf1 C11 C12 -169.45(18) . . . . ? P1 Hf1 C11 C12 10.48(19) . . . . ? C1 Hf1 C11 C10 46.8(5) . . . . ? C3 Hf1 C11 C10 77.34(18) . . . . ? C5 Hf1 C11 C10 142.39(17) . . . . ? C9 Hf1 C11 C10 -22.73(16) . . . . ? C8 Hf1 C11 C10 -53.86(17) . . . . ? C12 Hf1 C11 C10 -137.8(3) . . . . ? C4 Hf1 C11 C10 109.75(17) . . . . ? C2 Hf1 C11 C10 52.7(2) . . . . ? P1 Hf1 C11 C10 -127.32(15) . . . . ? C1 Hf1 C11 C14 -62.5(6) . . . . ? C10 Hf1 C11 C14 -109.2(3) . . . . ? C3 Hf1 C11 C14 -31.9(3) . . . . ? C5 Hf1 C11 C14 33.2(3) . . . . ? C9 Hf1 C11 C14 -132.0(3) . . . . ? C8 Hf1 C11 C14 -163.1(3) . . . . ? C12 Hf1 C11 C14 113.0(3) . . . . ? C4 Hf1 C11 C14 0.5(3) . . . . ? C2 Hf1 C11 C14 -56.5(3) . . . . ? P1 Hf1 C11 C14 123.4(3) . . . . ? C10 C11 C12 Hf1 51.3(3) . . . . ? C14 C11 C12 Hf1 -126.2(3) . . . . ? C1 Hf1 C12 C11 176.3(3) . . . . ? C10 Hf1 C12 C11 -25.17(16) . . . . ? C3 Hf1 C12 C11 46.9(2) . . . . ? C5 Hf1 C12 C11 105.37(18) . . . . ? C9 Hf1 C12 C11 -55.50(18) . . . . ? C8 Hf1 C12 C11 -90.09(19) . . . . ? C4 Hf1 C12 C11 72.21(19) . . . . ? C2 Hf1 C12 C11 28.5(5) . . . . ? P1 Hf1 C12 C11 -170.54(18) . . . . ? _diffrn_measured_fraction_theta_max 0.985 _diffrn_reflns_theta_full 27.46 _diffrn_measured_fraction_theta_full 0.985 _refine_diff_density_max 0.885 _refine_diff_density_min -0.806 _refine_diff_density_rms 0.100 data_shelxl_c _database_code_depnum_ccdc_archive 'CCDC 212751' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H37 P Ti' _chemical_formula_weight 356.37 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.7597(3) _cell_length_b 8.7193(5) _cell_length_c 15.3947(9) _cell_angle_alpha 87.728(2) _cell_angle_beta 75.724(3) _cell_angle_gamma 87.803(3) _cell_volume 1008.19(9) _cell_formula_units_Z 2 _cell_measurement_temperature 200(1) _cell_measurement_reflns_used 13924 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 27.48 _exptl_crystal_description plate _exptl_crystal_colour orange-red _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.174 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 388 _exptl_absorpt_coefficient_mu 0.501 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.9153 _exptl_absorpt_correction_T_max 0.9517 _exptl_absorpt_process_details 'DENZO-SMN (Otwinowski & Minor, 1997)' _exptl_special_details ; The program Denzo-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL-97 input file. ; _diffrn_ambient_temperature 200(1) _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 'Nonius KappaCCD Diffractometer' _diffrn_measurement_method 'Phi Plus Omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2.0 _diffrn_reflns_number 6648 _diffrn_reflns_av_R_equivalents 0.0313 _diffrn_reflns_av_sigmaI/netI 0.0753 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.54 _diffrn_reflns_theta_max 27.50 _reflns_number_total 4453 _reflns_number_gt 3236 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius COLLECT' _computing_cell_refinement DENZO-SMN _computing_data_reduction DENZO-SMN _computing_structure_solution SIR97 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'WinGX, Ortep3' _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^)+(0.0264P)^2^+0.3046P] 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 4453 _refine_ls_number_parameters 347 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0779 _refine_ls_R_factor_gt 0.0444 _refine_ls_wR_factor_ref 0.0955 _refine_ls_wR_factor_gt 0.0836 _refine_ls_goodness_of_fit_ref 1.038 _refine_ls_restrained_S_all 1.038 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.66166(5) 0.33581(4) 0.21033(3) 0.02117(12) Uani 1 1 d . . . P1 P 0.79842(7) 0.25973(7) 0.34507(4) 0.02603(15) Uani 1 1 d . . . C1 C 0.9173(3) 0.1991(3) 0.13173(17) 0.0332(6) Uani 1 1 d . . . H1A H 1.008(3) 0.252(3) 0.1509(15) 0.033(6) Uiso 1 1 d . . . H1B H 0.933(3) 0.087(3) 0.1348(16) 0.039(7) Uiso 1 1 d . . . C2 C 0.8328(3) 0.2627(3) 0.06770(15) 0.0296(5) Uani 1 1 d . . . C3 C 0.7792(3) 0.4186(3) 0.06183(15) 0.0288(5) Uani 1 1 d . . . H3 H 0.716(3) 0.445(3) 0.0140(17) 0.038(7) Uiso 1 1 d . . . C4 C 0.7988(3) 0.5413(3) 0.11554(15) 0.0288(5) Uani 1 1 d . . . C5 C 0.8767(3) 0.5292(3) 0.18836(17) 0.0315(5) Uani 1 1 d . . . H5A H 0.981(3) 0.465(3) 0.1877(17) 0.040(7) Uiso 1 1 d . . . H5B H 0.871(3) 0.617(3) 0.2233(16) 0.034(7) Uiso 1 1 d . . . C6 C 0.7914(4) 0.1580(4) -0.00011(19) 0.0412(6) Uani 1 1 d . . . H6A H 0.684(4) 0.193(3) -0.0158(18) 0.048(8) Uiso 1 1 d . . . H6B H 0.778(4) 0.053(3) 0.0227(19) 0.054(8) Uiso 1 1 d . . . H6C H 0.889(4) 0.165(3) -0.054(2) 0.060(9) Uiso 1 1 d . . . C7 C 0.7234(4) 0.6955(3) 0.0925(2) 0.0413(6) Uani 1 1 d . . . H7A H 0.690(3) 0.757(3) 0.1432(19) 0.040(7) Uiso 1 1 d . . . H7B H 0.811(4) 0.745(3) 0.0483(19) 0.053(8) Uiso 1 1 d . . . H7C H 0.610(4) 0.691(3) 0.0683(18) 0.051(8) Uiso 1 1 d . . . C8 C 0.4927(3) 0.1253(3) 0.26784(18) 0.0301(5) Uani 1 1 d . . . H8A H 0.442(3) 0.157(3) 0.3299(17) 0.031(6) Uiso 1 1 d . . . H8B H 0.535(3) 0.020(3) 0.2609(16) 0.036(7) Uiso 1 1 d . . . C9 C 0.4234(3) 0.1906(3) 0.19773(15) 0.0273(5) Uani 1 1 d . . . C10 C 0.3759(3) 0.3484(3) 0.18979(16) 0.0260(5) Uani 1 1 d . . . H10 H 0.345(3) 0.376(2) 0.1329(15) 0.022(6) Uiso 1 1 d . . . C11 C 0.3889(3) 0.4705(3) 0.24544(16) 0.0276(5) Uani 1 1 d . . . C12 C 0.4533(3) 0.4538(3) 0.32384(17) 0.0310(5) Uani 1 1 d . . . H12A H 0.473(3) 0.548(3) 0.3482(15) 0.030(6) Uiso 1 1 d . . . H12B H 0.417(3) 0.371(3) 0.3650(16) 0.030(6) Uiso 1 1 d . . . C13 C 0.4006(4) 0.0871(3) 0.1254(2) 0.0368(6) Uani 1 1 d . . . H13A H 0.497(4) 0.010(3) 0.1119(17) 0.043(7) Uiso 1 1 d . . . H13B H 0.290(4) 0.032(3) 0.1465(18) 0.055(8) Uiso 1 1 d . . . H13C H 0.401(4) 0.145(3) 0.067(2) 0.055(8) Uiso 1 1 d . . . C14 C 0.3337(4) 0.6291(3) 0.2180(2) 0.0387(6) Uani 1 1 d . . . H14A H 0.339(3) 0.640(3) 0.1512(19) 0.045(8) Uiso 1 1 d . . . H14B H 0.208(4) 0.652(3) 0.2506(17) 0.040(7) Uiso 1 1 d . . . H14C H 0.408(4) 0.707(3) 0.2318(18) 0.051(8) Uiso 1 1 d . . . C15 C 0.6453(3) 0.2020(3) 0.45253(17) 0.0368(6) Uani 1 1 d . . . H15A H 0.579(3) 0.127(3) 0.4400(15) 0.031(7) Uiso 1 1 d . . . H15B H 0.568(3) 0.284(3) 0.4660(17) 0.040(8) Uiso 1 1 d . . . C16 C 0.7233(5) 0.1566(4) 0.5319(2) 0.0498(7) Uani 1 1 d . . . H16A H 0.628(4) 0.130(3) 0.586(2) 0.061(9) Uiso 1 1 d . . . H16B H 0.802(4) 0.066(4) 0.516(2) 0.068(10) Uiso 1 1 d . . . H16C H 0.790(4) 0.240(4) 0.545(2) 0.073(10) Uiso 1 1 d . . . C17 C 0.9639(4) 0.0986(4) 0.3322(2) 0.0480(7) Uani 1 1 d . . . H17A H 1.014(4) 0.103(3) 0.384(2) 0.062(9) Uiso 1 1 d . . . H17B H 1.059(4) 0.126(3) 0.282(2) 0.057(9) Uiso 1 1 d . . . C18 C 0.8943(6) -0.0570(4) 0.3207(3) 0.0680(10) Uani 1 1 d . . . H18A H 0.798(5) -0.082(4) 0.373(3) 0.090(13) Uiso 1 1 d . . . H18B H 0.843(5) -0.059(4) 0.265(3) 0.100(13) Uiso 1 1 d . . . H18C H 0.990(6) -0.123(5) 0.309(3) 0.102(13) Uiso 1 1 d . . . C19 C 0.9295(4) 0.4032(3) 0.38337(19) 0.0434(7) Uani 1 1 d . . . H19A H 0.991(3) 0.354(3) 0.4233(19) 0.046(7) Uiso 1 1 d . . . H19B H 1.025(3) 0.428(3) 0.3322(18) 0.038(7) Uiso 1 1 d . . . C20 C 0.8250(6) 0.5426(4) 0.4239(2) 0.0580(9) Uani 1 1 d . . . H20A H 0.738(5) 0.518(4) 0.480(3) 0.084(11) Uiso 1 1 d . . . H20B H 0.755(4) 0.601(3) 0.386(2) 0.053(8) Uiso 1 1 d . . . H20C H 0.902(5) 0.613(4) 0.437(2) 0.090(11) 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 Ti1 0.0191(2) 0.0236(2) 0.0212(2) -0.00089(16) -0.00564(15) 0.00045(15) P1 0.0251(3) 0.0302(3) 0.0236(3) 0.0021(3) -0.0081(2) -0.0004(2) C1 0.0302(13) 0.0350(15) 0.0333(15) -0.0055(11) -0.0061(11) 0.0071(11) C2 0.0254(11) 0.0374(14) 0.0235(13) -0.0071(10) -0.0007(9) 0.0011(10) C3 0.0261(12) 0.0386(14) 0.0209(13) 0.0008(10) -0.0045(9) -0.0019(10) C4 0.0276(12) 0.0314(13) 0.0245(13) 0.0056(10) -0.0011(9) -0.0040(10) C5 0.0331(13) 0.0314(14) 0.0307(14) -0.0010(11) -0.0083(11) -0.0079(11) C6 0.0423(16) 0.0495(18) 0.0315(16) -0.0138(13) -0.0069(13) -0.0005(13) C7 0.0438(16) 0.0349(15) 0.0415(18) 0.0103(14) -0.0051(13) -0.0030(12) C8 0.0288(12) 0.0270(13) 0.0352(15) 0.0029(11) -0.0095(11) -0.0042(10) C9 0.0205(11) 0.0309(13) 0.0315(13) -0.0029(10) -0.0077(9) -0.0037(9) C10 0.0193(10) 0.0327(13) 0.0269(13) 0.0012(10) -0.0081(9) 0.0007(9) C11 0.0202(11) 0.0285(12) 0.0336(13) -0.0015(10) -0.0063(9) 0.0019(9) C12 0.0302(12) 0.0320(14) 0.0295(14) -0.0056(12) -0.0045(10) 0.0013(10) C13 0.0332(14) 0.0377(15) 0.0427(17) -0.0101(13) -0.0141(12) -0.0022(12) C14 0.0298(14) 0.0322(14) 0.0530(19) -0.0006(13) -0.0091(13) 0.0060(11) C15 0.0371(14) 0.0426(16) 0.0313(15) 0.0080(12) -0.0102(11) -0.0069(13) C16 0.063(2) 0.059(2) 0.0294(16) 0.0146(15) -0.0162(15) -0.0055(17) C17 0.0446(16) 0.061(2) 0.0406(18) 0.0024(15) -0.0178(14) 0.0190(14) C18 0.089(3) 0.0404(19) 0.073(3) -0.0014(18) -0.021(2) 0.0307(19) C19 0.0458(16) 0.0589(19) 0.0322(16) 0.0105(14) -0.0216(14) -0.0201(14) C20 0.094(3) 0.049(2) 0.0396(19) -0.0005(15) -0.0293(19) -0.0245(19) _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 Ti1 C12 2.313(2) . ? Ti1 C10 2.314(2) . ? Ti1 C8 2.314(2) . ? Ti1 C9 2.331(2) . ? Ti1 C11 2.333(2) . ? Ti1 C3 2.339(2) . ? Ti1 C1 2.360(2) . ? Ti1 C2 2.366(2) . ? Ti1 C5 2.373(2) . ? Ti1 C4 2.376(2) . ? Ti1 P1 2.6060(7) . ? P1 C19 1.844(3) . ? P1 C15 1.847(3) . ? P1 C17 1.850(3) . ? C1 C2 1.399(3) . ? C1 H1A 0.96(2) . ? C1 H1B 0.98(3) . ? C2 C3 1.412(3) . ? C2 C6 1.513(3) . ? C3 C4 1.413(3) . ? C3 H3 1.00(2) . ? C4 C5 1.398(3) . ? C4 C7 1.510(3) . ? C5 H5A 0.96(3) . ? C5 H5B 0.95(2) . ? C6 H6A 0.96(3) . ? C6 H6B 0.97(3) . ? C6 H6C 0.98(3) . ? C7 H7A 0.94(3) . ? C7 H7B 0.94(3) . ? C7 H7C 1.04(3) . ? C8 C9 1.411(3) . ? C8 H8A 0.98(2) . ? C8 H8B 0.96(2) . ? C9 C10 1.419(3) . ? C9 C13 1.509(3) . ? C10 C11 1.414(3) . ? C10 H10 0.98(2) . ? C11 C12 1.416(3) . ? C11 C14 1.508(3) . ? C12 H12A 0.95(2) . ? C12 H12B 0.95(2) . ? C13 H13A 0.97(3) . ? C13 H13B 0.98(3) . ? C13 H13C 1.01(3) . ? C14 H14A 1.02(3) . ? C14 H14B 1.00(3) . ? C14 H14C 0.97(3) . ? C15 C16 1.524(4) . ? C15 H15A 0.91(2) . ? C15 H15B 0.91(3) . ? C16 H16A 0.99(3) . ? C16 H16B 0.98(3) . ? C16 H16C 0.96(3) . ? C17 C18 1.512(5) . ? C17 H17A 0.97(3) . ? C17 H17B 0.96(3) . ? C18 H18A 0.98(4) . ? C18 H18B 1.03(4) . ? C18 H18C 0.91(4) . ? C19 C20 1.503(5) . ? C19 H19A 0.94(3) . ? C19 H19B 0.96(3) . ? C20 H20A 0.98(4) . ? C20 H20B 1.00(3) . ? C20 H20C 0.94(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C12 Ti1 C10 65.52(8) . . ? C12 Ti1 C8 81.06(10) . . ? C10 Ti1 C8 65.49(8) . . ? C12 Ti1 C9 84.27(8) . . ? C10 Ti1 C9 35.58(7) . . ? C8 Ti1 C9 35.37(8) . . ? C12 Ti1 C11 35.48(8) . . ? C10 Ti1 C11 35.43(8) . . ? C8 Ti1 C11 84.12(8) . . ? C9 Ti1 C11 66.61(8) . . ? C12 Ti1 C3 129.97(9) . . ? C10 Ti1 C3 91.25(8) . . ? C8 Ti1 C3 130.50(9) . . ? C9 Ti1 C3 102.12(8) . . ? C11 Ti1 C3 101.76(8) . . ? C12 Ti1 C1 162.02(9) . . ? C10 Ti1 C1 130.15(9) . . ? C8 Ti1 C1 97.29(10) . . ? C9 Ti1 C1 104.83(9) . . ? C11 Ti1 C1 162.49(8) . . ? C3 Ti1 C1 64.09(9) . . ? C12 Ti1 C2 163.04(8) . . ? C10 Ti1 C2 102.29(8) . . ? C8 Ti1 C2 105.24(9) . . ? C9 Ti1 C2 91.96(8) . . ? C11 Ti1 C2 128.37(8) . . ? C3 Ti1 C2 34.92(8) . . ? C1 Ti1 C2 34.43(8) . . ? C12 Ti1 C5 96.66(9) . . ? C10 Ti1 C5 129.75(9) . . ? C8 Ti1 C5 162.10(9) . . ? C9 Ti1 C5 162.47(8) . . ? C11 Ti1 C5 104.39(9) . . ? C3 Ti1 C5 63.94(8) . . ? C1 Ti1 C5 79.38(10) . . ? C2 Ti1 C5 82.06(9) . . ? C12 Ti1 C4 104.67(9) . . ? C10 Ti1 C4 102.20(8) . . ? C8 Ti1 C4 163.34(8) . . ? C9 Ti1 C4 128.62(8) . . ? C11 Ti1 C4 91.65(8) . . ? C3 Ti1 C4 34.86(8) . . ? C1 Ti1 C4 82.01(9) . . ? C2 Ti1 C4 65.10(8) . . ? C5 Ti1 C4 34.23(8) . . ? C12 Ti1 P1 80.66(6) . . ? C10 Ti1 P1 134.43(6) . . ? C8 Ti1 P1 80.38(6) . . ? C9 Ti1 P1 115.59(6) . . ? C11 Ti1 P1 115.95(6) . . ? C3 Ti1 P1 134.32(6) . . ? C1 Ti1 P1 81.41(6) . . ? C2 Ti1 P1 115.68(6) . . ? C5 Ti1 P1 81.73(6) . . ? C4 Ti1 P1 115.78(6) . . ? C19 P1 C15 100.62(13) . . ? C19 P1 C17 97.88(14) . . ? C15 P1 C17 100.36(14) . . ? C19 P1 Ti1 118.06(9) . . ? C15 P1 Ti1 117.92(8) . . ? C17 P1 Ti1 118.32(10) . . ? C2 C1 Ti1 73.03(13) . . ? C2 C1 H1A 122.4(14) . . ? Ti1 C1 H1A 99.8(14) . . ? C2 C1 H1B 117.9(14) . . ? Ti1 C1 H1B 124.4(14) . . ? H1A C1 H1B 113(2) . . ? C1 C2 C3 125.0(2) . . ? C1 C2 C6 118.5(2) . . ? C3 C2 C6 116.5(2) . . ? C1 C2 Ti1 72.54(13) . . ? C3 C2 Ti1 71.48(13) . . ? C6 C2 Ti1 130.94(17) . . ? C2 C3 C4 129.2(2) . . ? C2 C3 Ti1 73.60(13) . . ? C4 C3 Ti1 74.00(13) . . ? C2 C3 H3 115.2(14) . . ? C4 C3 H3 115.6(14) . . ? Ti1 C3 H3 128.9(14) . . ? C5 C4 C3 125.2(2) . . ? C5 C4 C7 118.7(2) . . ? C3 C4 C7 116.1(2) . . ? C5 C4 Ti1 72.79(13) . . ? C3 C4 Ti1 71.15(12) . . ? C7 C4 Ti1 130.57(16) . . ? C4 C5 Ti1 72.97(13) . . ? C4 C5 H5A 122.3(15) . . ? Ti1 C5 H5A 99.4(14) . . ? C4 C5 H5B 117.7(14) . . ? Ti1 C5 H5B 126.5(14) . . ? H5A C5 H5B 112(2) . . ? C2 C6 H6A 110.2(16) . . ? C2 C6 H6B 111.8(17) . . ? H6A C6 H6B 109(2) . . ? C2 C6 H6C 107.1(17) . . ? H6A C6 H6C 108(2) . . ? H6B C6 H6C 111(2) . . ? C4 C7 H7A 111.2(16) . . ? C4 C7 H7B 108.3(17) . . ? H7A C7 H7B 109(2) . . ? C4 C7 H7C 114.7(14) . . ? H7A C7 H7C 105(2) . . ? H7B C7 H7C 108(2) . . ? C9 C8 Ti1 72.99(12) . . ? C9 C8 H8A 119.7(13) . . ? Ti1 C8 H8A 100.6(13) . . ? C9 C8 H8B 115.8(14) . . ? Ti1 C8 H8B 124.7(14) . . ? H8A C8 H8B 116(2) . . ? C8 C9 C10 124.3(2) . . ? C8 C9 C13 118.2(2) . . ? C10 C9 C13 117.5(2) . . ? C8 C9 Ti1 71.63(12) . . ? C10 C9 Ti1 71.53(11) . . ? C13 C9 Ti1 131.65(17) . . ? C11 C10 C9 129.4(2) . . ? C11 C10 Ti1 73.05(12) . . ? C9 C10 Ti1 72.89(11) . . ? C11 C10 H10 116.7(12) . . ? C9 C10 H10 113.4(12) . . ? Ti1 C10 H10 124.9(12) . . ? C10 C11 C12 124.4(2) . . ? C10 C11 C14 117.4(2) . . ? C12 C11 C14 118.2(2) . . ? C10 C11 Ti1 71.52(12) . . ? C12 C11 Ti1 71.46(13) . . ? C14 C11 Ti1 131.80(16) . . ? C11 C12 Ti1 73.06(13) . . ? C11 C12 H12A 114.4(14) . . ? Ti1 C12 H12A 123.0(14) . . ? C11 C12 H12B 120.3(14) . . ? Ti1 C12 H12B 101.8(14) . . ? H12A C12 H12B 117(2) . . ? C9 C13 H13A 110.7(15) . . ? C9 C13 H13B 109.3(16) . . ? H13A C13 H13B 107(2) . . ? C9 C13 H13C 112.5(16) . . ? H13A C13 H13C 107(2) . . ? H13B C13 H13C 110(2) . . ? C11 C14 H14A 112.8(14) . . ? C11 C14 H14B 109.4(14) . . ? H14A C14 H14B 107(2) . . ? C11 C14 H14C 111.6(15) . . ? H14A C14 H14C 108(2) . . ? H14B C14 H14C 108(2) . . ? C16 C15 P1 118.6(2) . . ? C16 C15 H15A 111.5(15) . . ? P1 C15 H15A 106.3(15) . . ? C16 C15 H15B 110.4(16) . . ? P1 C15 H15B 104.1(16) . . ? H15A C15 H15B 105(2) . . ? C15 C16 H16A 111.1(17) . . ? C15 C16 H16B 108.4(19) . . ? H16A C16 H16B 108(2) . . ? C15 C16 H16C 110.2(19) . . ? H16A C16 H16C 109(3) . . ? H16B C16 H16C 110(3) . . ? C18 C17 P1 115.4(2) . . ? C18 C17 H17A 113.6(17) . . ? P1 C17 H17A 104.8(17) . . ? C18 C17 H17B 111.0(18) . . ? P1 C17 H17B 106.3(17) . . ? H17A C17 H17B 105(2) . . ? C17 C18 H18A 109(2) . . ? C17 C18 H18B 112(2) . . ? H18A C18 H18B 107(3) . . ? C17 C18 H18C 106(2) . . ? H18A C18 H18C 117(3) . . ? H18B C18 H18C 106(3) . . ? C20 C19 P1 115.0(2) . . ? C20 C19 H19A 111.2(16) . . ? P1 C19 H19A 108.8(16) . . ? C20 C19 H19B 113.1(15) . . ? P1 C19 H19B 105.5(15) . . ? H19A C19 H19B 102(2) . . ? C19 C20 H20A 113(2) . . ? C19 C20 H20B 116.7(16) . . ? H20A C20 H20B 104(3) . . ? C19 C20 H20C 110(2) . . ? H20A C20 H20C 107(3) . . ? H20B C20 H20C 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 C12 Ti1 P1 C19 -80.34(13) . . . . ? C10 Ti1 P1 C19 -121.82(14) . . . . ? C8 Ti1 P1 C19 -162.76(14) . . . . ? C9 Ti1 P1 C19 -159.33(13) . . . . ? C11 Ti1 P1 C19 -84.18(13) . . . . ? C3 Ti1 P1 C19 58.20(15) . . . . ? C1 Ti1 P1 C19 98.28(13) . . . . ? C2 Ti1 P1 C19 94.87(13) . . . . ? C5 Ti1 P1 C19 17.86(13) . . . . ? C4 Ti1 P1 C19 21.52(13) . . . . ? C12 Ti1 P1 C15 40.91(13) . . . . ? C10 Ti1 P1 C15 -0.57(14) . . . . ? C8 Ti1 P1 C15 -41.51(13) . . . . ? C9 Ti1 P1 C15 -38.08(13) . . . . ? C11 Ti1 P1 C15 37.07(13) . . . . ? C3 Ti1 P1 C15 179.44(14) . . . . ? C1 Ti1 P1 C15 -140.47(13) . . . . ? C2 Ti1 P1 C15 -143.88(13) . . . . ? C5 Ti1 P1 C15 139.11(13) . . . . ? C4 Ti1 P1 C15 142.77(13) . . . . ? C12 Ti1 P1 C17 162.03(14) . . . . ? C10 Ti1 P1 C17 120.55(14) . . . . ? C8 Ti1 P1 C17 79.61(14) . . . . ? C9 Ti1 P1 C17 83.04(14) . . . . ? C11 Ti1 P1 C17 158.18(13) . . . . ? C3 Ti1 P1 C17 -59.44(15) . . . . ? C1 Ti1 P1 C17 -19.35(14) . . . . ? C2 Ti1 P1 C17 -22.77(14) . . . . ? C5 Ti1 P1 C17 -99.77(14) . . . . ? C4 Ti1 P1 C17 -96.11(13) . . . . ? C12 Ti1 C1 C2 -170.1(3) . . . . ? C10 Ti1 C1 C2 42.44(19) . . . . ? C8 Ti1 C1 C2 106.38(15) . . . . ? C9 Ti1 C1 C2 71.12(15) . . . . ? C11 Ti1 C1 C2 12.8(4) . . . . ? C3 Ti1 C1 C2 -25.36(13) . . . . ? C5 Ti1 C1 C2 -91.43(15) . . . . ? C4 Ti1 C1 C2 -56.82(15) . . . . ? P1 Ti1 C1 C2 -174.56(15) . . . . ? Ti1 C1 C2 C3 51.2(2) . . . . ? Ti1 C1 C2 C6 -127.7(2) . . . . ? C12 Ti1 C2 C1 169.6(3) . . . . ? C10 Ti1 C2 C1 -148.14(15) . . . . ? C8 Ti1 C2 C1 -80.51(16) . . . . ? C9 Ti1 C2 C1 -113.77(15) . . . . ? C11 Ti1 C2 C1 -175.12(14) . . . . ? C3 Ti1 C2 C1 137.7(2) . . . . ? C5 Ti1 C2 C1 82.78(16) . . . . ? C4 Ti1 C2 C1 113.97(16) . . . . ? P1 Ti1 C2 C1 5.97(16) . . . . ? C12 Ti1 C2 C3 31.9(3) . . . . ? C10 Ti1 C2 C3 74.16(13) . . . . ? C8 Ti1 C2 C3 141.79(13) . . . . ? C9 Ti1 C2 C3 108.54(13) . . . . ? C11 Ti1 C2 C3 47.18(15) . . . . ? C1 Ti1 C2 C3 -137.7(2) . . . . ? C5 Ti1 C2 C3 -54.91(13) . . . . ? C4 Ti1 C2 C3 -23.73(12) . . . . ? P1 Ti1 C2 C3 -131.72(11) . . . . ? C12 Ti1 C2 C6 -77.6(4) . . . . ? C10 Ti1 C2 C6 -35.3(3) . . . . ? C8 Ti1 C2 C6 32.4(3) . . . . ? C9 Ti1 C2 C6 -0.9(2) . . . . ? C11 Ti1 C2 C6 -62.2(3) . . . . ? C3 Ti1 C2 C6 -109.4(3) . . . . ? C1 Ti1 C2 C6 112.9(3) . . . . ? C5 Ti1 C2 C6 -164.3(3) . . . . ? C4 Ti1 C2 C6 -133.2(3) . . . . ? P1 Ti1 C2 C6 118.8(2) . . . . ? C1 C2 C3 C4 0.8(4) . . . . ? C6 C2 C3 C4 179.6(2) . . . . ? Ti1 C2 C3 C4 52.4(2) . . . . ? C1 C2 C3 Ti1 -51.6(2) . . . . ? C6 C2 C3 Ti1 127.2(2) . . . . ? C12 Ti1 C3 C2 -168.41(12) . . . . ? C10 Ti1 C3 C2 -109.91(13) . . . . ? C8 Ti1 C3 C2 -51.72(16) . . . . ? C9 Ti1 C3 C2 -75.73(13) . . . . ? C11 Ti1 C3 C2 -144.02(12) . . . . ? C1 Ti1 C3 C2 25.03(13) . . . . ? C5 Ti1 C3 C2 115.56(15) . . . . ? C4 Ti1 C3 C2 140.30(19) . . . . ? P1 Ti1 C3 C2 70.08(14) . . . . ? C12 Ti1 C3 C4 51.29(17) . . . . ? C10 Ti1 C3 C4 109.79(13) . . . . ? C8 Ti1 C3 C4 167.98(13) . . . . ? C9 Ti1 C3 C4 143.96(13) . . . . ? C11 Ti1 C3 C4 75.68(14) . . . . ? C1 Ti1 C3 C4 -115.27(15) . . . . ? C2 Ti1 C3 C4 -140.30(19) . . . . ? C5 Ti1 C3 C4 -24.74(13) . . . . ? P1 Ti1 C3 C4 -70.22(15) . . . . ? C2 C3 C4 C5 -0.8(4) . . . . ? Ti1 C3 C4 C5 51.4(2) . . . . ? C2 C3 C4 C7 -179.0(2) . . . . ? Ti1 C3 C4 C7 -126.73(19) . . . . ? C2 C3 C4 Ti1 -52.2(2) . . . . ? C12 Ti1 C4 C5 80.12(16) . . . . ? C10 Ti1 C4 C5 147.68(15) . . . . ? C8 Ti1 C4 C5 -171.6(3) . . . . ? C9 Ti1 C4 C5 174.53(14) . . . . ? C11 Ti1 C4 C5 113.55(15) . . . . ? C3 Ti1 C4 C5 -138.1(2) . . . . ? C1 Ti1 C4 C5 -82.84(16) . . . . ? C2 Ti1 C4 C5 -114.29(16) . . . . ? P1 Ti1 C4 C5 -6.45(16) . . . . ? C12 Ti1 C4 C3 -141.82(13) . . . . ? C10 Ti1 C4 C3 -74.25(14) . . . . ? C8 Ti1 C4 C3 -33.5(4) . . . . ? C9 Ti1 C4 C3 -47.40(17) . . . . ? C11 Ti1 C4 C3 -108.38(14) . . . . ? C1 Ti1 C4 C3 55.22(14) . . . . ? C2 Ti1 C4 C3 23.78(12) . . . . ? C5 Ti1 C4 C3 138.1(2) . . . . ? P1 Ti1 C4 C3 131.61(12) . . . . ? C12 Ti1 C4 C7 -33.2(2) . . . . ? C10 Ti1 C4 C7 34.4(2) . . . . ? C8 Ti1 C4 C7 75.1(4) . . . . ? C9 Ti1 C4 C7 61.2(3) . . . . ? C11 Ti1 C4 C7 0.2(2) . . . . ? C3 Ti1 C4 C7 108.6(3) . . . . ? C1 Ti1 C4 C7 163.9(2) . . . . ? C2 Ti1 C4 C7 132.4(3) . . . . ? C5 Ti1 C4 C7 -113.3(3) . . . . ? P1 Ti1 C4 C7 -119.8(2) . . . . ? C3 C4 C5 Ti1 -50.7(2) . . . . ? C7 C4 C5 Ti1 127.4(2) . . . . ? C12 Ti1 C5 C4 -106.36(15) . . . . ? C10 Ti1 C5 C4 -42.82(19) . . . . ? C8 Ti1 C5 C4 172.1(3) . . . . ? C9 Ti1 C5 C4 -14.3(4) . . . . ? C11 Ti1 C5 C4 -71.09(16) . . . . ? C3 Ti1 C5 C4 25.16(14) . . . . ? C1 Ti1 C5 C4 91.39(15) . . . . ? C2 Ti1 C5 C4 56.59(15) . . . . ? P1 Ti1 C5 C4 174.13(15) . . . . ? C12 Ti1 C8 C9 92.69(15) . . . . ? C10 Ti1 C8 C9 25.60(13) . . . . ? C11 Ti1 C8 C9 57.03(15) . . . . ? C3 Ti1 C8 C9 -43.43(19) . . . . ? C1 Ti1 C8 C9 -105.39(15) . . . . ? C2 Ti1 C8 C9 -71.19(15) . . . . ? C5 Ti1 C8 C9 176.6(3) . . . . ? C4 Ti1 C8 C9 -18.9(4) . . . . ? P1 Ti1 C8 C9 174.65(15) . . . . ? Ti1 C8 C9 C10 -50.9(2) . . . . ? Ti1 C8 C9 C13 128.1(2) . . . . ? C12 Ti1 C9 C8 -82.62(16) . . . . ? C10 Ti1 C9 C8 -137.5(2) . . . . ? C11 Ti1 C9 C8 -114.60(16) . . . . ? C3 Ti1 C9 C8 147.68(15) . . . . ? C1 Ti1 C9 C8 81.60(16) . . . . ? C2 Ti1 C9 C8 113.96(15) . . . . ? C5 Ti1 C9 C8 -176.6(3) . . . . ? C4 Ti1 C9 C8 173.17(15) . . . . ? P1 Ti1 C9 C8 -5.85(16) . . . . ? C12 Ti1 C9 C10 54.87(14) . . . . ? C8 Ti1 C9 C10 137.5(2) . . . . ? C11 Ti1 C9 C10 22.89(13) . . . . ? C3 Ti1 C9 C10 -74.83(14) . . . . ? C1 Ti1 C9 C10 -140.92(14) . . . . ? C2 Ti1 C9 C10 -108.55(14) . . . . ? C5 Ti1 C9 C10 -39.1(3) . . . . ? C4 Ti1 C9 C10 -49.35(17) . . . . ? P1 Ti1 C9 C10 131.64(12) . . . . ? C12 Ti1 C9 C13 165.6(2) . . . . ? C10 Ti1 C9 C13 110.7(3) . . . . ? C8 Ti1 C9 C13 -111.8(3) . . . . ? C11 Ti1 C9 C13 133.6(2) . . . . ? C3 Ti1 C9 C13 35.9(2) . . . . ? C1 Ti1 C9 C13 -30.2(2) . . . . ? C2 Ti1 C9 C13 2.2(2) . . . . ? C5 Ti1 C9 C13 71.6(4) . . . . ? C4 Ti1 C9 C13 61.4(3) . . . . ? P1 Ti1 C9 C13 -117.7(2) . . . . ? C8 C9 C10 C11 1.3(4) . . . . ? C13 C9 C10 C11 -177.7(2) . . . . ? Ti1 C9 C10 C11 -49.6(2) . . . . ? C8 C9 C10 Ti1 50.9(2) . . . . ? C13 C9 C10 Ti1 -128.0(2) . . . . ? C12 Ti1 C10 C11 25.39(13) . . . . ? C8 Ti1 C10 C11 116.53(16) . . . . ? C9 Ti1 C10 C11 142.0(2) . . . . ? C3 Ti1 C10 C11 -108.72(14) . . . . ? C1 Ti1 C10 C11 -165.13(13) . . . . ? C2 Ti1 C10 C11 -142.15(13) . . . . ? C5 Ti1 C10 C11 -52.31(17) . . . . ? C4 Ti1 C10 C11 -75.34(14) . . . . ? P1 Ti1 C10 C11 71.29(15) . . . . ? C12 Ti1 C10 C9 -116.60(15) . . . . ? C8 Ti1 C10 C9 -25.47(14) . . . . ? C11 Ti1 C10 C9 -142.0(2) . . . . ? C3 Ti1 C10 C9 109.29(14) . . . . ? C1 Ti1 C10 C9 52.87(17) . . . . ? C2 Ti1 C10 C9 75.86(14) . . . . ? C5 Ti1 C10 C9 165.70(13) . . . . ? C4 Ti1 C10 C9 142.67(13) . . . . ? P1 Ti1 C10 C9 -70.71(15) . . . . ? C9 C10 C11 C12 -1.0(4) . . . . ? Ti1 C10 C11 C12 -50.6(2) . . . . ? C9 C10 C11 C14 177.8(2) . . . . ? Ti1 C10 C11 C14 128.19(19) . . . . ? C9 C10 C11 Ti1 49.6(2) . . . . ? C12 Ti1 C11 C10 -137.8(2) . . . . ? C8 Ti1 C11 C10 -54.92(14) . . . . ? C9 Ti1 C11 C10 -22.98(13) . . . . ? C3 Ti1 C11 C10 75.28(14) . . . . ? C1 Ti1 C11 C10 40.7(3) . . . . ? C2 Ti1 C11 C10 49.88(16) . . . . ? C5 Ti1 C11 C10 141.09(13) . . . . ? C4 Ti1 C11 C10 108.92(14) . . . . ? P1 Ti1 C11 C10 -131.22(12) . . . . ? C10 Ti1 C11 C12 137.8(2) . . . . ? C8 Ti1 C11 C12 82.83(15) . . . . ? C9 Ti1 C11 C12 114.78(15) . . . . ? C3 Ti1 C11 C12 -146.96(14) . . . . ? C1 Ti1 C11 C12 178.4(3) . . . . ? C2 Ti1 C11 C12 -172.37(14) . . . . ? C5 Ti1 C11 C12 -81.15(15) . . . . ? C4 Ti1 C11 C12 -113.32(15) . . . . ? P1 Ti1 C11 C12 6.54(15) . . . . ? C12 Ti1 C11 C14 111.6(3) . . . . ? C10 Ti1 C11 C14 -110.6(3) . . . . ? C8 Ti1 C11 C14 -165.6(2) . . . . ? C9 Ti1 C11 C14 -133.6(3) . . . . ? C3 Ti1 C11 C14 -35.4(2) . . . . ? C1 Ti1 C11 C14 -70.0(4) . . . . ? C2 Ti1 C11 C14 -60.8(3) . . . . ? C5 Ti1 C11 C14 30.4(2) . . . . ? C4 Ti1 C11 C14 -1.7(2) . . . . ? P1 Ti1 C11 C14 118.1(2) . . . . ? C10 C11 C12 Ti1 50.6(2) . . . . ? C14 C11 C12 Ti1 -128.16(19) . . . . ? C10 Ti1 C12 C11 -25.35(13) . . . . ? C8 Ti1 C12 C11 -92.41(14) . . . . ? C9 Ti1 C12 C11 -56.88(14) . . . . ? C3 Ti1 C12 C11 44.14(18) . . . . ? C1 Ti1 C12 C11 -178.5(3) . . . . ? C2 Ti1 C12 C11 20.9(4) . . . . ? C5 Ti1 C12 C11 105.51(14) . . . . ? C4 Ti1 C12 C11 71.59(14) . . . . ? P1 Ti1 C12 C11 -174.04(14) . . . . ? C19 P1 C15 C16 -50.4(3) . . . . ? C17 P1 C15 C16 49.8(3) . . . . ? Ti1 P1 C15 C16 179.8(2) . . . . ? C19 P1 C17 C18 166.9(3) . . . . ? C15 P1 C17 C18 64.5(3) . . . . ? Ti1 P1 C17 C18 -65.2(3) . . . . ? C15 P1 C19 C20 -63.2(2) . . . . ? C17 P1 C19 C20 -165.4(2) . . . . ? Ti1 P1 C19 C20 66.5(2) . . . . ? _diffrn_measured_fraction_theta_max 0.961 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.961 _refine_diff_density_max 0.291 _refine_diff_density_min -0.352 _refine_diff_density_rms 0.059 data_shelxl_d _database_code_depnum_ccdc_archive 'CCDC 212752' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H37 Hf P' _chemical_formula_weight 486.96 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' P P 0.1023 0.0942 '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 triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.8898(3) _cell_length_b 8.6491(3) _cell_length_c 15.5788(3) _cell_angle_alpha 88.1613(20) _cell_angle_beta 76.1834(19) _cell_angle_gamma 88.4466(15) _cell_volume 1031.59(6) _cell_formula_units_Z 2 _cell_measurement_temperature 200(1) _cell_measurement_reflns_used 13830 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 27.48 _exptl_crystal_description prism _exptl_crystal_colour 'dark brown' _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.568 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 488 _exptl_absorpt_coefficient_mu 5.131 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.3276 _exptl_absorpt_correction_T_max 0.5133 _exptl_absorpt_process_details 'DENZO-SMN (Otwinowski & Minor, 1997)' _exptl_special_details ; The program Denzo-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL-97 input file. ; _diffrn_ambient_temperature 200(1) _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 'Nonius KappaCCD Diffractometer' _diffrn_measurement_method 'Phi plus Omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2.0 _diffrn_reflns_number 6762 _diffrn_reflns_av_R_equivalents 0.0219 _diffrn_reflns_av_sigmaI/netI 0.0439 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.51 _diffrn_reflns_theta_max 27.48 _reflns_number_total 4472 _reflns_number_gt 4218 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius COLLECT' _computing_cell_refinement DENZO-SMN _computing_data_reduction DENZO-SMN _computing_structure_solution DIRDIF99 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'WinGx, Ortep3' _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^)+(0.0073P)^2^+1.3348P] 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 0.0012(5) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 4472 _refine_ls_number_parameters 274 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0262 _refine_ls_R_factor_gt 0.0235 _refine_ls_wR_factor_ref 0.0589 _refine_ls_wR_factor_gt 0.0573 _refine_ls_goodness_of_fit_ref 1.099 _refine_ls_restrained_S_all 1.099 _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 Hf1 Hf 0.163363(16) -0.158815(14) 0.211355(8) 0.01923(8) Uani 1 1 d . . . P1 P 0.30596(11) -0.23383(10) 0.34768(5) 0.01909(18) Uani 1 1 d . . . C1 C 0.4236(5) -0.2937(5) 0.1263(2) 0.0257(7) Uani 1 1 d . . . H1A H 0.511(6) -0.236(5) 0.144(3) 0.034(11) Uiso 1 1 d . . . H1B H 0.433(6) -0.405(5) 0.130(3) 0.034(11) Uiso 1 1 d . . . C2 C 0.3379(4) -0.2267(4) 0.0639(2) 0.0222(7) Uani 1 1 d . . . C3 C 0.2850(5) -0.0696(4) 0.0608(2) 0.0219(7) Uani 1 1 d . . . H3 H 0.235(5) -0.046(5) 0.024(3) 0.028(11) Uiso 1 1 d . . . C4 C 0.3043(4) 0.0552(4) 0.1141(2) 0.0211(7) Uani 1 1 d . . . C5 C 0.3843(5) 0.0434(5) 0.1859(2) 0.0238(7) Uani 1 1 d . . . H5A H 0.474(5) -0.013(4) 0.182(2) 0.019(10) Uiso 1 1 d . . . H5B H 0.377(5) 0.114(5) 0.215(3) 0.018(10) Uiso 1 1 d . . . C6 C 0.2901(5) -0.3300(5) -0.0023(2) 0.0328(9) Uani 1 1 d . . . H6A H 0.1781 -0.2950 -0.0136 0.031(11) Uiso 1 1 calc R . . H6B H 0.2803 -0.4367 0.0213 0.043(12) Uiso 1 1 calc R . . H6C H 0.3808 -0.3256 -0.0576 0.046(13) Uiso 1 1 calc R . . C7 C 0.2263(5) 0.2090(4) 0.0941(3) 0.0319(8) Uani 1 1 d . . . H7A H 0.3140 0.2683 0.0514 0.049(13) Uiso 1 1 calc R . . H7B H 0.1883 0.2667 0.1487 0.031(11) Uiso 1 1 calc R . . H7C H 0.1258 0.1922 0.0690 0.038(12) Uiso 1 1 calc R . . C8 C -0.0113(5) -0.3787(4) 0.2671(3) 0.0247(7) Uani 1 1 d . . . H8A H -0.068(6) -0.355(5) 0.331(3) 0.039(12) Uiso 1 1 d . . . H8B H 0.027(5) -0.468(5) 0.257(2) 0.022(10) Uiso 1 1 d . . . C9 C -0.0818(4) -0.3100(4) 0.1981(2) 0.0213(7) Uani 1 1 d . . . C10 C -0.1307(4) -0.1513(4) 0.1928(2) 0.0193(6) Uani 1 1 d . . . H10 H -0.153(5) -0.122(4) 0.140(3) 0.023(10) Uiso 1 1 d . . . C11 C -0.1173(4) -0.0264(4) 0.2479(2) 0.0206(7) Uani 1 1 d . . . C12 C -0.0525(5) -0.0415(5) 0.3262(2) 0.0230(7) Uani 1 1 d . . . H12A H -0.097(6) -0.112(5) 0.361(3) 0.032(12) Uiso 1 1 d . . . H12B H -0.041(5) 0.043(5) 0.352(2) 0.019(9) Uiso 1 1 d . . . C13 C -0.1040(5) -0.4124(4) 0.1251(2) 0.0287(8) Uani 1 1 d . . . H13A H -0.2136 -0.4683 0.1444 0.044(13) Uiso 1 1 calc R . . H13B H -0.0060 -0.4868 0.1113 0.021(9) Uiso 1 1 calc R . . H13C H -0.1068 -0.3487 0.0723 0.032(11) Uiso 1 1 calc R . . C14 C -0.1691(5) 0.1329(4) 0.2201(3) 0.0307(8) Uani 1 1 d . . . H14A H -0.1637 0.1355 0.1566 0.023(10) Uiso 1 1 calc R . . H14B H -0.0890 0.2088 0.2328 0.036(11) Uiso 1 1 calc R . . H14C H -0.2885 0.1579 0.2529 0.039(12) Uiso 1 1 calc R . . C15 C 0.1539(5) -0.2981(5) 0.4509(2) 0.0297(8) Uani 1 1 d . . . H15A H 0.0666 -0.2140 0.4696 0.034(11) Uiso 1 1 calc R . . H15B H 0.0905 -0.3880 0.4375 0.033(11) Uiso 1 1 calc R . . C16 C 0.2312(6) -0.3437(6) 0.5294(3) 0.0440(11) Uani 1 1 d . . . H16A H 0.3080 -0.4349 0.5148 0.072(18) Uiso 1 1 calc R . . H16B H 0.1367 -0.3678 0.5811 0.065(16) Uiso 1 1 calc R . . H16C H 0.2986 -0.2577 0.5425 0.043(13) Uiso 1 1 calc R . . C17 C 0.4756(5) -0.3884(5) 0.3316(3) 0.0405(10) Uani 1 1 d . . . H17A H 0.5705 -0.3594 0.2800 0.057(15) Uiso 1 1 calc R . . H17B H 0.5257 -0.3944 0.3842 0.036(11) Uiso 1 1 calc R . . C18 C 0.4131(8) -0.5466(6) 0.3171(4) 0.0630(15) Uani 1 1 d . . . H18A H 0.3270 -0.5812 0.3702 0.09(2) Uiso 1 1 calc R . . H18B H 0.5124 -0.6198 0.3053 0.09(2) Uiso 1 1 calc R . . H18C H 0.3592 -0.5415 0.2665 0.056(15) Uiso 1 1 calc R . . C19 C 0.4262(6) -0.0824(5) 0.3871(3) 0.0377(10) Uani 1 1 d . . . H19A H 0.4811 -0.1283 0.4331 0.052(14) Uiso 1 1 calc R . . H19B H 0.5210 -0.0463 0.3372 0.042(12) Uiso 1 1 calc R . . C20 C 0.3144(8) 0.0563(5) 0.4249(3) 0.0500(13) Uani 1 1 d . . . H20A H 0.2477 0.0947 0.3828 0.056(15) Uiso 1 1 calc R . . H20B H 0.3896 0.1382 0.4358 0.067(16) Uiso 1 1 calc R . . H20C H 0.2337 0.0255 0.4807 0.054(14) 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 0.01863(10) 0.02049(10) 0.01906(10) -0.00014(5) -0.00562(6) 0.00060(6) P1 0.0183(4) 0.0231(4) 0.0169(4) 0.0044(3) -0.0067(3) -0.0006(3) C1 0.0219(18) 0.030(2) 0.0240(18) -0.0048(14) -0.0047(14) 0.0087(15) C2 0.0208(16) 0.0280(18) 0.0165(16) -0.0032(13) -0.0018(13) 0.0017(14) C3 0.0223(17) 0.0307(19) 0.0129(16) 0.0039(13) -0.0053(13) -0.0005(14) C4 0.0211(17) 0.0232(17) 0.0163(16) 0.0062(12) 0.0005(13) -0.0036(13) C5 0.0240(19) 0.0241(19) 0.0235(19) -0.0015(15) -0.0055(14) -0.0064(16) C6 0.038(2) 0.036(2) 0.0242(19) -0.0119(16) -0.0072(16) 0.0003(17) C7 0.033(2) 0.0230(18) 0.037(2) 0.0103(15) -0.0040(16) 0.0014(16) C8 0.0260(18) 0.0158(17) 0.034(2) 0.0026(14) -0.0104(15) -0.0029(14) C9 0.0163(15) 0.0240(17) 0.0248(18) -0.0001(13) -0.0067(13) -0.0043(13) C10 0.0130(15) 0.0246(17) 0.0210(17) 0.0012(13) -0.0060(12) 0.0003(13) C11 0.0108(14) 0.0229(17) 0.0270(17) -0.0002(13) -0.0024(12) 0.0023(12) C12 0.0227(18) 0.0247(19) 0.0195(18) -0.0071(15) -0.0008(14) 0.0039(15) C13 0.0281(19) 0.0280(19) 0.035(2) -0.0086(15) -0.0154(16) -0.0036(15) C14 0.0246(19) 0.0215(18) 0.046(2) 0.0021(15) -0.0087(16) 0.0023(15) C15 0.030(2) 0.037(2) 0.0216(18) 0.0110(15) -0.0062(15) -0.0071(17) C16 0.057(3) 0.054(3) 0.023(2) 0.0172(18) -0.0146(19) -0.006(2) C17 0.035(2) 0.055(3) 0.031(2) 0.0076(18) -0.0103(17) 0.019(2) C18 0.091(4) 0.038(3) 0.057(3) 0.003(2) -0.017(3) 0.033(3) C19 0.042(2) 0.049(3) 0.029(2) 0.0130(18) -0.0232(18) -0.022(2) C20 0.091(4) 0.035(2) 0.033(2) -0.0005(18) -0.029(2) -0.021(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Hf1 C12 2.387(3) . ? Hf1 C8 2.395(3) . ? Hf1 C10 2.405(3) . ? Hf1 C11 2.416(3) . ? Hf1 C9 2.417(3) . ? Hf1 C3 2.423(3) . ? Hf1 C1 2.450(3) . ? Hf1 C5 2.458(4) . ? Hf1 C2 2.459(3) . ? Hf1 C4 2.466(3) . ? Hf1 P1 2.6852(8) . ? P1 C19 1.841(4) . ? P1 C15 1.842(3) . ? P1 C17 1.845(4) . ? C1 C2 1.412(5) . ? C1 H1A 0.96(4) . ? C1 H1B 0.96(4) . ? C2 C3 1.414(5) . ? C2 C6 1.506(5) . ? C3 C4 1.417(5) . ? C3 H3 0.79(4) . ? C4 C5 1.408(5) . ? C4 C7 1.506(5) . ? C5 H5A 0.84(4) . ? C5 H5B 0.77(4) . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C6 H6C 0.9800 . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 C9 1.430(5) . ? C8 H8A 1.02(5) . ? C8 H8B 0.82(4) . ? C9 C10 1.421(5) . ? C9 C13 1.508(4) . ? C10 C11 1.423(5) . ? C10 H10 0.91(4) . ? C11 C12 1.432(5) . ? C11 C14 1.506(5) . ? C12 H12A 0.83(5) . ? C12 H12B 0.86(4) . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C15 C16 1.527(5) . ? C15 H15A 0.9900 . ? C15 H15B 0.9900 . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C17 C18 1.509(7) . ? C17 H17A 0.9900 . ? C17 H17B 0.9900 . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? C18 H18C 0.9800 . ? C19 C20 1.518(7) . ? C19 H19A 0.9900 . ? C19 H19B 0.9900 . ? C20 H20A 0.9800 . ? C20 H20B 0.9800 . ? C20 H20C 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 C12 Hf1 C8 79.95(14) . . ? C12 Hf1 C10 63.59(12) . . ? C8 Hf1 C10 63.46(12) . . ? C12 Hf1 C11 34.69(12) . . ? C8 Hf1 C11 82.16(12) . . ? C10 Hf1 C11 34.32(11) . . ? C12 Hf1 C9 82.23(12) . . ? C8 Hf1 C9 34.58(12) . . ? C10 Hf1 C9 34.28(11) . . ? C11 Hf1 C9 64.64(12) . . ? C12 Hf1 C3 130.12(13) . . ? C8 Hf1 C3 130.53(13) . . ? C10 Hf1 C3 93.17(12) . . ? C11 Hf1 C3 102.77(12) . . ? C9 Hf1 C3 103.08(11) . . ? C12 Hf1 C1 164.45(13) . . ? C8 Hf1 C1 98.95(14) . . ? C10 Hf1 C1 129.90(12) . . ? C11 Hf1 C1 160.85(12) . . ? C9 Hf1 C1 105.78(13) . . ? C3 Hf1 C1 61.94(12) . . ? C12 Hf1 C5 99.26(14) . . ? C8 Hf1 C5 164.13(13) . . ? C10 Hf1 C5 130.50(13) . . ? C11 Hf1 C5 106.32(13) . . ? C9 Hf1 C5 161.28(12) . . ? C3 Hf1 C5 61.66(12) . . ? C1 Hf1 C5 77.52(14) . . ? C12 Hf1 C2 161.63(13) . . ? C8 Hf1 C2 106.36(13) . . ? C10 Hf1 C2 103.21(11) . . ? C11 Hf1 C2 127.82(12) . . ? C9 Hf1 C2 93.33(11) . . ? C3 Hf1 C2 33.65(12) . . ? C1 Hf1 C2 33.44(12) . . ? C5 Hf1 C2 79.37(12) . . ? C12 Hf1 C4 106.10(13) . . ? C8 Hf1 C4 162.12(12) . . ? C10 Hf1 C4 103.59(11) . . ? C11 Hf1 C4 93.37(11) . . ? C9 Hf1 C4 128.35(11) . . ? C3 Hf1 C4 33.67(11) . . ? C1 Hf1 C4 79.69(12) . . ? C5 Hf1 C4 33.22(12) . . ? C2 Hf1 C4 62.96(11) . . ? C12 Hf1 P1 81.61(9) . . ? C8 Hf1 P1 82.13(9) . . ? C10 Hf1 P1 133.80(8) . . ? C11 Hf1 P1 116.11(8) . . ? C9 Hf1 P1 116.50(8) . . ? C3 Hf1 P1 133.02(9) . . ? C1 Hf1 P1 82.87(9) . . ? C5 Hf1 P1 82.08(9) . . ? C2 Hf1 P1 116.04(8) . . ? C4 Hf1 P1 115.14(8) . . ? C19 P1 C15 101.76(18) . . ? C19 P1 C17 98.8(2) . . ? C15 P1 C17 102.23(19) . . ? C19 P1 Hf1 117.28(13) . . ? C15 P1 Hf1 116.21(12) . . ? C17 P1 Hf1 117.68(13) . . ? C2 C1 Hf1 73.7(2) . . ? C2 C1 H1A 119(3) . . ? Hf1 C1 H1A 99(3) . . ? C2 C1 H1B 118(3) . . ? Hf1 C1 H1B 120(3) . . ? H1A C1 H1B 118(4) . . ? C1 C2 C3 125.1(3) . . ? C1 C2 C6 118.5(3) . . ? C3 C2 C6 116.4(3) . . ? C1 C2 Hf1 72.91(19) . . ? C3 C2 Hf1 71.75(19) . . ? C6 C2 Hf1 128.4(2) . . ? C2 C3 C4 130.7(3) . . ? C2 C3 Hf1 74.59(19) . . ? C4 C3 Hf1 74.86(18) . . ? C2 C3 H3 116(3) . . ? C4 C3 H3 113(3) . . ? Hf1 C3 H3 128(3) . . ? C5 C4 C3 124.7(3) . . ? C5 C4 C7 118.5(3) . . ? C3 C4 C7 116.8(3) . . ? C5 C4 Hf1 73.07(19) . . ? C3 C4 Hf1 71.47(18) . . ? C7 C4 Hf1 128.6(2) . . ? C4 C5 Hf1 73.71(19) . . ? C4 C5 H5A 119(3) . . ? Hf1 C5 H5A 99(3) . . ? C4 C5 H5B 117(3) . . ? Hf1 C5 H5B 123(3) . . ? H5A C5 H5B 116(4) . . ? C2 C6 H6A 109.5 . . ? C2 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C2 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? C4 C7 H7A 109.5 . . ? C4 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C4 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C9 C8 Hf1 73.55(19) . . ? C9 C8 H8A 120(3) . . ? Hf1 C8 H8A 105(2) . . ? C9 C8 H8B 114(3) . . ? Hf1 C8 H8B 121(3) . . ? H8A C8 H8B 117(4) . . ? C10 C9 C8 124.6(3) . . ? C10 C9 C13 117.6(3) . . ? C8 C9 C13 117.9(3) . . ? C10 C9 Hf1 72.39(18) . . ? C8 C9 Hf1 71.87(19) . . ? C13 C9 Hf1 130.6(2) . . ? C9 C10 C11 130.7(3) . . ? C9 C10 Hf1 73.33(18) . . ? C11 C10 Hf1 73.29(18) . . ? C9 C10 H10 114(2) . . ? C11 C10 H10 114(2) . . ? Hf1 C10 H10 121(2) . . ? C10 C11 C12 124.3(3) . . ? C10 C11 C14 117.6(3) . . ? C12 C11 C14 118.0(3) . . ? C10 C11 Hf1 72.38(18) . . ? C12 C11 Hf1 71.52(19) . . ? C14 C11 Hf1 129.7(2) . . ? C11 C12 Hf1 73.80(19) . . ? C11 C12 H12A 115(3) . . ? Hf1 C12 H12A 107(3) . . ? C11 C12 H12B 116(2) . . ? Hf1 C12 H12B 126(3) . . ? H12A C12 H12B 113(4) . . ? C9 C13 H13A 109.5 . . ? C9 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C9 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C11 C14 H14A 109.5 . . ? C11 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C11 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C16 C15 P1 117.5(3) . . ? C16 C15 H15A 107.9 . . ? P1 C15 H15A 107.9 . . ? C16 C15 H15B 107.9 . . ? P1 C15 H15B 107.9 . . ? H15A C15 H15B 107.2 . . ? C15 C16 H16A 109.5 . . ? C15 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C15 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C18 C17 P1 114.9(3) . . ? C18 C17 H17A 108.5 . . ? P1 C17 H17A 108.5 . . ? C18 C17 H17B 108.5 . . ? P1 C17 H17B 108.5 . . ? H17A C17 H17B 107.5 . . ? C17 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C17 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C20 C19 P1 114.3(3) . . ? C20 C19 H19A 108.7 . . ? P1 C19 H19A 108.7 . . ? C20 C19 H19B 108.7 . . ? P1 C19 H19B 108.7 . . ? H19A C19 H19B 107.6 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 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 C12 Hf1 P1 C19 -79.1(2) . . . . ? C8 Hf1 P1 C19 -160.0(2) . . . . ? C10 Hf1 P1 C19 -119.2(2) . . . . ? C11 Hf1 P1 C19 -82.75(19) . . . . ? C9 Hf1 P1 C19 -155.98(19) . . . . ? C3 Hf1 P1 C19 59.8(2) . . . . ? C1 Hf1 P1 C19 99.9(2) . . . . ? C5 Hf1 P1 C19 21.6(2) . . . . ? C2 Hf1 P1 C19 95.61(19) . . . . ? C4 Hf1 P1 C19 24.86(19) . . . . ? C12 Hf1 P1 C15 41.58(18) . . . . ? C8 Hf1 P1 C15 -39.34(18) . . . . ? C10 Hf1 P1 C15 1.42(19) . . . . ? C11 Hf1 P1 C15 37.88(18) . . . . ? C9 Hf1 P1 C15 -35.34(18) . . . . ? C3 Hf1 P1 C15 -179.54(19) . . . . ? C1 Hf1 P1 C15 -139.45(18) . . . . ? C5 Hf1 P1 C15 142.22(18) . . . . ? C2 Hf1 P1 C15 -143.76(18) . . . . ? C4 Hf1 P1 C15 145.49(17) . . . . ? C12 Hf1 P1 C17 163.2(2) . . . . ? C8 Hf1 P1 C17 82.3(2) . . . . ? C10 Hf1 P1 C17 123.1(2) . . . . ? C11 Hf1 P1 C17 159.55(19) . . . . ? C9 Hf1 P1 C17 86.32(19) . . . . ? C3 Hf1 P1 C17 -57.9(2) . . . . ? C1 Hf1 P1 C17 -17.8(2) . . . . ? C5 Hf1 P1 C17 -96.1(2) . . . . ? C2 Hf1 P1 C17 -22.10(19) . . . . ? C4 Hf1 P1 C17 -92.85(19) . . . . ? C12 Hf1 C1 C2 -169.1(4) . . . . ? C8 Hf1 C1 C2 106.2(2) . . . . ? C10 Hf1 C1 C2 43.5(3) . . . . ? C11 Hf1 C1 C2 14.3(5) . . . . ? C9 Hf1 C1 C2 71.4(2) . . . . ? C3 Hf1 C1 C2 -25.2(2) . . . . ? C5 Hf1 C1 C2 -89.6(2) . . . . ? C4 Hf1 C1 C2 -55.7(2) . . . . ? P1 Hf1 C1 C2 -173.0(2) . . . . ? Hf1 C1 C2 C3 51.9(3) . . . . ? Hf1 C1 C2 C6 -124.9(3) . . . . ? C12 Hf1 C2 C1 170.8(4) . . . . ? C8 Hf1 C2 C1 -81.4(2) . . . . ? C10 Hf1 C2 C1 -147.2(2) . . . . ? C11 Hf1 C2 C1 -174.1(2) . . . . ? C9 Hf1 C2 C1 -114.0(2) . . . . ? C3 Hf1 C2 C1 137.3(3) . . . . ? C5 Hf1 C2 C1 83.4(2) . . . . ? C4 Hf1 C2 C1 114.1(2) . . . . ? P1 Hf1 C2 C1 7.8(2) . . . . ? C12 Hf1 C2 C3 33.5(5) . . . . ? C8 Hf1 C2 C3 141.4(2) . . . . ? C10 Hf1 C2 C3 75.5(2) . . . . ? C11 Hf1 C2 C3 48.6(3) . . . . ? C9 Hf1 C2 C3 108.8(2) . . . . ? C1 Hf1 C2 C3 -137.3(3) . . . . ? C5 Hf1 C2 C3 -53.9(2) . . . . ? C4 Hf1 C2 C3 -23.2(2) . . . . ? P1 Hf1 C2 C3 -129.52(18) . . . . ? C12 Hf1 C2 C6 -76.1(5) . . . . ? C8 Hf1 C2 C6 31.8(3) . . . . ? C10 Hf1 C2 C6 -34.1(3) . . . . ? C11 Hf1 C2 C6 -61.0(4) . . . . ? C9 Hf1 C2 C6 -0.8(3) . . . . ? C3 Hf1 C2 C6 -109.6(4) . . . . ? C1 Hf1 C2 C6 113.1(4) . . . . ? C5 Hf1 C2 C6 -163.5(3) . . . . ? C4 Hf1 C2 C6 -132.8(4) . . . . ? P1 Hf1 C2 C6 120.9(3) . . . . ? C1 C2 C3 C4 1.1(6) . . . . ? C6 C2 C3 C4 178.0(3) . . . . ? Hf1 C2 C3 C4 53.5(3) . . . . ? C1 C2 C3 Hf1 -52.4(3) . . . . ? C6 C2 C3 Hf1 124.5(3) . . . . ? C12 Hf1 C3 C2 -166.9(2) . . . . ? C8 Hf1 C3 C2 -52.0(3) . . . . ? C10 Hf1 C3 C2 -109.2(2) . . . . ? C11 Hf1 C3 C2 -142.6(2) . . . . ? C9 Hf1 C3 C2 -76.0(2) . . . . ? C1 Hf1 C3 C2 25.1(2) . . . . ? C5 Hf1 C3 C2 115.6(2) . . . . ? C4 Hf1 C3 C2 140.8(3) . . . . ? P1 Hf1 C3 C2 71.5(2) . . . . ? C12 Hf1 C3 C4 52.3(3) . . . . ? C8 Hf1 C3 C4 167.2(2) . . . . ? C10 Hf1 C3 C4 109.9(2) . . . . ? C11 Hf1 C3 C4 76.6(2) . . . . ? C9 Hf1 C3 C4 143.2(2) . . . . ? C1 Hf1 C3 C4 -115.7(2) . . . . ? C5 Hf1 C3 C4 -25.2(2) . . . . ? C2 Hf1 C3 C4 -140.8(3) . . . . ? P1 Hf1 C3 C4 -69.4(2) . . . . ? C2 C3 C4 C5 -0.7(6) . . . . ? Hf1 C3 C4 C5 52.8(3) . . . . ? C2 C3 C4 C7 -178.1(3) . . . . ? Hf1 C3 C4 C7 -124.6(3) . . . . ? C2 C3 C4 Hf1 -53.5(3) . . . . ? C12 Hf1 C4 C5 82.2(2) . . . . ? C8 Hf1 C4 C5 -170.1(4) . . . . ? C10 Hf1 C4 C5 148.3(2) . . . . ? C11 Hf1 C4 C5 115.1(2) . . . . ? C9 Hf1 C4 C5 175.0(2) . . . . ? C3 Hf1 C4 C5 -136.8(3) . . . . ? C1 Hf1 C4 C5 -82.9(2) . . . . ? C2 Hf1 C4 C5 -113.7(3) . . . . ? P1 Hf1 C4 C5 -5.9(3) . . . . ? C12 Hf1 C4 C3 -140.9(2) . . . . ? C8 Hf1 C4 C3 -33.3(5) . . . . ? C10 Hf1 C4 C3 -74.9(2) . . . . ? C11 Hf1 C4 C3 -108.1(2) . . . . ? C9 Hf1 C4 C3 -48.1(3) . . . . ? C1 Hf1 C4 C3 53.9(2) . . . . ? C5 Hf1 C4 C3 136.8(3) . . . . ? C2 Hf1 C4 C3 23.2(2) . . . . ? P1 Hf1 C4 C3 130.91(18) . . . . ? C12 Hf1 C4 C7 -31.1(3) . . . . ? C8 Hf1 C4 C7 76.6(5) . . . . ? C10 Hf1 C4 C7 35.0(3) . . . . ? C11 Hf1 C4 C7 1.8(3) . . . . ? C9 Hf1 C4 C7 61.7(4) . . . . ? C3 Hf1 C4 C7 109.9(4) . . . . ? C1 Hf1 C4 C7 163.8(3) . . . . ? C5 Hf1 C4 C7 -113.3(4) . . . . ? C2 Hf1 C4 C7 133.0(3) . . . . ? P1 Hf1 C4 C7 -119.2(3) . . . . ? C3 C4 C5 Hf1 -52.1(3) . . . . ? C7 C4 C5 Hf1 125.2(3) . . . . ? C12 Hf1 C5 C4 -105.3(2) . . . . ? C8 Hf1 C5 C4 168.9(4) . . . . ? C10 Hf1 C5 C4 -42.3(3) . . . . ? C11 Hf1 C5 C4 -70.4(2) . . . . ? C9 Hf1 C5 C4 -12.2(5) . . . . ? C3 Hf1 C5 C4 25.5(2) . . . . ? C1 Hf1 C5 C4 90.2(2) . . . . ? C2 Hf1 C5 C4 56.1(2) . . . . ? P1 Hf1 C5 C4 174.6(2) . . . . ? C12 Hf1 C8 C9 90.9(2) . . . . ? C10 Hf1 C8 C9 25.5(2) . . . . ? C11 Hf1 C8 C9 55.8(2) . . . . ? C3 Hf1 C8 C9 -44.3(3) . . . . ? C1 Hf1 C8 C9 -104.9(2) . . . . ? C5 Hf1 C8 C9 179.4(4) . . . . ? C2 Hf1 C8 C9 -71.4(2) . . . . ? C4 Hf1 C8 C9 -20.7(5) . . . . ? P1 Hf1 C8 C9 173.7(2) . . . . ? Hf1 C8 C9 C10 -52.3(3) . . . . ? Hf1 C8 C9 C13 127.0(3) . . . . ? C12 Hf1 C9 C10 53.4(2) . . . . ? C8 Hf1 C9 C10 136.9(3) . . . . ? C11 Hf1 C9 C10 21.98(19) . . . . ? C3 Hf1 C9 C10 -76.1(2) . . . . ? C1 Hf1 C9 C10 -140.3(2) . . . . ? C5 Hf1 C9 C10 -42.6(5) . . . . ? C2 Hf1 C9 C10 -108.7(2) . . . . ? C4 Hf1 C9 C10 -51.0(2) . . . . ? P1 Hf1 C9 C10 129.92(17) . . . . ? C12 Hf1 C9 C8 -83.5(2) . . . . ? C10 Hf1 C9 C8 -136.9(3) . . . . ? C11 Hf1 C9 C8 -114.9(2) . . . . ? C3 Hf1 C9 C8 147.0(2) . . . . ? C1 Hf1 C9 C8 82.8(2) . . . . ? C5 Hf1 C9 C8 -179.5(4) . . . . ? C2 Hf1 C9 C8 114.4(2) . . . . ? C4 Hf1 C9 C8 172.0(2) . . . . ? P1 Hf1 C9 C8 -7.0(2) . . . . ? C12 Hf1 C9 C13 164.9(3) . . . . ? C8 Hf1 C9 C13 -111.5(4) . . . . ? C10 Hf1 C9 C13 111.6(4) . . . . ? C11 Hf1 C9 C13 133.5(3) . . . . ? C3 Hf1 C9 C13 35.4(3) . . . . ? C1 Hf1 C9 C13 -28.7(3) . . . . ? C5 Hf1 C9 C13 69.0(5) . . . . ? C2 Hf1 C9 C13 2.8(3) . . . . ? C4 Hf1 C9 C13 60.5(4) . . . . ? P1 Hf1 C9 C13 -118.5(3) . . . . ? C8 C9 C10 C11 2.8(6) . . . . ? C13 C9 C10 C11 -176.4(3) . . . . ? Hf1 C9 C10 C11 -49.2(3) . . . . ? C8 C9 C10 Hf1 52.0(3) . . . . ? C13 C9 C10 Hf1 -127.2(3) . . . . ? C12 Hf1 C10 C9 -117.4(2) . . . . ? C8 Hf1 C10 C9 -25.7(2) . . . . ? C11 Hf1 C10 C9 -143.1(3) . . . . ? C3 Hf1 C10 C9 108.7(2) . . . . ? C1 Hf1 C10 C9 53.3(2) . . . . ? C5 Hf1 C10 C9 163.42(19) . . . . ? C2 Hf1 C10 C9 76.2(2) . . . . ? C4 Hf1 C10 C9 141.14(19) . . . . ? P1 Hf1 C10 C9 -72.0(2) . . . . ? C12 Hf1 C10 C11 25.7(2) . . . . ? C8 Hf1 C10 C11 117.5(2) . . . . ? C9 Hf1 C10 C11 143.1(3) . . . . ? C3 Hf1 C10 C11 -108.1(2) . . . . ? C1 Hf1 C10 C11 -163.6(2) . . . . ? C5 Hf1 C10 C11 -53.4(2) . . . . ? C2 Hf1 C10 C11 -140.6(2) . . . . ? C4 Hf1 C10 C11 -75.7(2) . . . . ? P1 Hf1 C10 C11 71.2(2) . . . . ? C9 C10 C11 C12 -2.4(6) . . . . ? Hf1 C10 C11 C12 -51.7(3) . . . . ? C9 C10 C11 C14 175.4(3) . . . . ? Hf1 C10 C11 C14 126.2(3) . . . . ? C9 C10 C11 Hf1 49.3(3) . . . . ? C12 Hf1 C11 C10 -136.9(3) . . . . ? C8 Hf1 C11 C10 -53.3(2) . . . . ? C9 Hf1 C11 C10 -21.96(19) . . . . ? C3 Hf1 C11 C10 76.6(2) . . . . ? C1 Hf1 C11 C10 41.5(5) . . . . ? C5 Hf1 C11 C10 140.47(19) . . . . ? C2 Hf1 C11 C10 51.4(2) . . . . ? C4 Hf1 C11 C10 109.3(2) . . . . ? P1 Hf1 C11 C10 -130.47(17) . . . . ? C8 Hf1 C11 C12 83.6(2) . . . . ? C10 Hf1 C11 C12 136.9(3) . . . . ? C9 Hf1 C11 C12 115.0(2) . . . . ? C3 Hf1 C11 C12 -146.5(2) . . . . ? C1 Hf1 C11 C12 178.4(4) . . . . ? C5 Hf1 C11 C12 -82.6(2) . . . . ? C2 Hf1 C11 C12 -171.7(2) . . . . ? C4 Hf1 C11 C12 -113.8(2) . . . . ? P1 Hf1 C11 C12 6.4(2) . . . . ? C12 Hf1 C11 C14 111.5(4) . . . . ? C8 Hf1 C11 C14 -164.9(3) . . . . ? C10 Hf1 C11 C14 -111.6(4) . . . . ? C9 Hf1 C11 C14 -133.6(3) . . . . ? C3 Hf1 C11 C14 -35.0(3) . . . . ? C1 Hf1 C11 C14 -70.2(5) . . . . ? C5 Hf1 C11 C14 28.8(3) . . . . ? C2 Hf1 C11 C14 -60.2(4) . . . . ? C4 Hf1 C11 C14 -2.3(3) . . . . ? P1 Hf1 C11 C14 117.9(3) . . . . ? C10 C11 C12 Hf1 52.1(3) . . . . ? C14 C11 C12 Hf1 -125.8(3) . . . . ? C8 Hf1 C12 C11 -90.7(2) . . . . ? C10 Hf1 C12 C11 -25.47(19) . . . . ? C9 Hf1 C12 C11 -55.8(2) . . . . ? C3 Hf1 C12 C11 44.8(3) . . . . ? C1 Hf1 C12 C11 -178.0(4) . . . . ? C5 Hf1 C12 C11 105.4(2) . . . . ? C2 Hf1 C12 C11 21.2(5) . . . . ? C4 Hf1 C12 C11 72.0(2) . . . . ? P1 Hf1 C12 C11 -174.2(2) . . . . ? C19 P1 C15 C16 -52.2(4) . . . . ? C17 P1 C15 C16 49.7(4) . . . . ? Hf1 P1 C15 C16 179.2(3) . . . . ? C19 P1 C17 C18 167.7(3) . . . . ? C15 P1 C17 C18 63.5(4) . . . . ? Hf1 P1 C17 C18 -65.1(4) . . . . ? C15 P1 C19 C20 -64.1(3) . . . . ? C17 P1 C19 C20 -168.6(3) . . . . ? Hf1 P1 C19 C20 63.9(3) . . . . ? _diffrn_measured_fraction_theta_max 0.944 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.944 _refine_diff_density_max 0.857 _refine_diff_density_min -1.337 _refine_diff_density_rms 0.114