# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _publ_contact_author ; Matthew D Jones University of Bath Department of Chemistry Bath, BA2 7AY United Kingdom ; _publ_contact_author_phone '# 44 1225 38 4908' _publ_contact_author_fax '# 44 1225 82 6231' _publ_contact_author_email mj205@bath.ac.uk _publ_requested_coeditor_name ; Ben J. Jeffery, Emma L. Whitelaw, Daniel Garcia-Vio, Joseph A. Stewart, Mary F. Mahon Matthew G. Davidson and Matthew D. Jones ; _publ_contact_letter ; ; #================================================= # 3. TITLE AND AUTHOR LIST _publ_section_title ; Group 4 initiators for the production of syndiotactically enriched polybutyrolacton ; loop_ _publ_author_name _publ_author_address E.L.Whitelaw ; University of Bath Department of Chemistry Bath, BA2 7AY United Kingdom ; 'Mary F. Mahon' ; University of Bath Department of Chemistry Bath, BA2 7AY United Kingdom ; 'Ben J. Jeffery' ; University of Bath Department of Chemistry Bath, BA2 7AY United Kingdom ; 'Daniel Garcia-Vio' ; University of Bath Department of Chemistry Bath, BA2 7AY United Kingdom ; 'Matthew G. Davidson' ; University of Bath Department of Chemistry Bath, BA2 7AY United Kingdom ; 'Joseph A. Stewart' ; University of Bath Department of Chemistry Bath, BA2 7AY United Kingdom ; 'Matthew D. Jones' '' _publ_contact_author_name 'Matthew D. Jones' #========================================================= data_Hf2 _database_code_depnum_ccdc_archive 'CCDC 841995' #TrackingRef '- cif.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C78 H110 Hf2 N2 O8, 3(C7 H8)' _chemical_formula_sum 'C99 H134 Hf2 N2 O8' _chemical_formula_weight 1837.06 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 P21/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 12.7000(3) _cell_length_b 15.7100(3) _cell_length_c 22.5950(6) _cell_angle_alpha 90.00 _cell_angle_beta 91.8780(10) _cell_angle_gamma 90.00 _cell_volume 4505.67(18) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 123023 _cell_measurement_theta_min 3.51 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.354 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1900 _exptl_absorpt_coefficient_mu 2.358 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6499 _exptl_absorpt_correction_T_max 0.7984 _exptl_absorpt_process_details 'multi-scan Sortav (Blessing 1995)' _exptl_special_details ; The crystal contained two molecules of toluene. One molecule C104-C110 was left isotropic. The other was also lesft isotropic, but best convergence was reaced when the solvent was modelled with a centre of symmetry. Thus, Alert A and B errors are due to solvent. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'nonius kappa ccd' _diffrn_measurement_method ccd _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 75384 _diffrn_reflns_av_R_equivalents 0.0823 _diffrn_reflns_av_sigmaI/netI 0.0463 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 3.52 _diffrn_reflns_theta_max 27.50 _reflns_number_total 10293 _reflns_number_gt 8054 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius BV, 1997-2000)' _computing_cell_refinement 'HKL Scalepack (Otwinski & Minor, 1997)' _computing_data_reduction 'HKL Denzo & Scalepack (Otwinski & Minor 1997)' _computing_structure_solution ; SIR97- Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C. , Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R. (1999) J. Appl. Cryst. 32, 115-119. ; _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' _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^)+(0.0474P)^2^+12.1368P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 10293 _refine_ls_number_parameters 450 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0636 _refine_ls_R_factor_gt 0.0416 _refine_ls_wR_factor_ref 0.1072 _refine_ls_wR_factor_gt 0.0962 _refine_ls_goodness_of_fit_ref 1.059 _refine_ls_restrained_S_all 1.059 _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 0.410468(13) 0.013206(11) 0.060514(8) 0.02346(7) Uani 1 1 d . . . O1 O 0.3168(3) 0.0970(2) 0.02704(15) 0.0345(8) Uani 1 1 d . . . N1 N 0.5222(3) -0.0786(2) 0.12116(16) 0.0232(7) Uani 1 1 d . . . C1 C 0.2275(4) 0.1489(4) 0.0143(3) 0.0428(13) Uani 1 1 d . . . H1 H 0.1949 0.1307 -0.0246 0.051 Uiso 1 1 calc R . . O2 O 0.3154(2) -0.08255(19) 0.07708(14) 0.0275(7) Uani 1 1 d . . . C2 C 0.1479(4) 0.1359(4) 0.0620(3) 0.0524(15) Uani 1 1 d . . . H2A H 0.1240 0.0766 0.0615 0.079 Uiso 1 1 calc R . . H2B H 0.0875 0.1738 0.0546 0.079 Uiso 1 1 calc R . . H2C H 0.1808 0.1491 0.1008 0.079 Uiso 1 1 calc R . . O3 O 0.5688(2) 0.0313(2) 0.03314(14) 0.0273(7) Uani 1 1 d . . . C3 C 0.2609(5) 0.2404(4) 0.0095(3) 0.0573(17) Uani 1 1 d . . . H3A H 0.2867 0.2607 0.0483 0.086 Uiso 1 1 calc R . . H3B H 0.2006 0.2750 -0.0041 0.086 Uiso 1 1 calc R . . H3C H 0.3172 0.2451 -0.0190 0.086 Uiso 1 1 calc R . . O4 O 0.4338(2) 0.08115(19) 0.13392(14) 0.0262(6) Uani 1 1 d . . . C4 C 0.3110(3) -0.1628(3) 0.0986(2) 0.0287(10) Uani 1 1 d . . . C5 C 0.4049(4) -0.2082(3) 0.1094(2) 0.0307(10) Uani 1 1 d . . . C6 C 0.4032(4) -0.2894(3) 0.1337(3) 0.0393(12) Uani 1 1 d . . . H6 H 0.4677 -0.3186 0.1414 0.047 Uiso 1 1 calc R . . C7 C 0.3086(4) -0.3291(3) 0.1471(3) 0.0468(14) Uani 1 1 d . . . C8 C 0.2164(4) -0.2822(3) 0.1363(3) 0.0421(13) Uani 1 1 d . . . H8 H 0.1514 -0.3082 0.1453 0.051 Uiso 1 1 calc R . . C9 C 0.2131(4) -0.2003(3) 0.1133(2) 0.0325(10) Uani 1 1 d . . . C10 C 0.1094(3) -0.1501(3) 0.1083(2) 0.0307(10) Uani 1 1 d . . . C11 C 0.1155(4) -0.0784(3) 0.1540(2) 0.0363(11) Uani 1 1 d . . . H11A H 0.1745 -0.0407 0.1453 0.054 Uiso 1 1 calc R . . H11B H 0.1264 -0.1027 0.1937 0.054 Uiso 1 1 calc R . . H11C H 0.0497 -0.0459 0.1523 0.054 Uiso 1 1 calc R . . C12 C 0.0893(4) -0.1133(4) 0.0459(2) 0.0390(12) Uani 1 1 d . . . H12A H 0.0206 -0.0848 0.0439 0.058 Uiso 1 1 calc R . . H12B H 0.0898 -0.1595 0.0167 0.058 Uiso 1 1 calc R . . H12C H 0.1447 -0.0721 0.0372 0.058 Uiso 1 1 calc R . . C13 C 0.0137(4) -0.2065(4) 0.1213(3) 0.0434(13) Uani 1 1 d . . . H13A H -0.0506 -0.1720 0.1191 0.065 Uiso 1 1 calc R . . H13B H 0.0225 -0.2310 0.1610 0.065 Uiso 1 1 calc R . . H13C H 0.0083 -0.2524 0.0920 0.065 Uiso 1 1 calc R . . C14 C 0.3022(5) -0.4181(4) 0.1768(4) 0.072(2) Uani 1 1 d . . . C15 C 0.2310(8) -0.4750(5) 0.1410(6) 0.119(5) Uani 1 1 d . . . H15A H 0.2529 -0.4753 0.0998 0.178 Uiso 1 1 calc R . . H15B H 0.1584 -0.4541 0.1426 0.178 Uiso 1 1 calc R . . H15C H 0.2349 -0.5329 0.1570 0.178 Uiso 1 1 calc R . . C16 C 0.2564(7) -0.4078(6) 0.2398(5) 0.108(4) Uani 1 1 d . . . H16A H 0.1803 -0.3980 0.2361 0.162 Uiso 1 1 calc R . . H16B H 0.2902 -0.3594 0.2600 0.162 Uiso 1 1 calc R . . H16C H 0.2700 -0.4598 0.2628 0.162 Uiso 1 1 calc R . . C17 C 0.4104(6) -0.4588(4) 0.1834(4) 0.082(3) Uani 1 1 d . . . H17A H 0.4047 -0.5131 0.2044 0.123 Uiso 1 1 calc R . . H17B H 0.4579 -0.4208 0.2059 0.123 Uiso 1 1 calc R . . H17C H 0.4384 -0.4688 0.1441 0.123 Uiso 1 1 calc R . . C18 C 0.5102(3) -0.1672(3) 0.0968(2) 0.0287(10) Uani 1 1 d . . . H18A H 0.5673 -0.2033 0.1139 0.034 Uiso 1 1 calc R . . H18B H 0.5186 -0.1653 0.0534 0.034 Uiso 1 1 calc R . . C19 C 0.4870(3) -0.0741(3) 0.18418(19) 0.0249(9) Uani 1 1 d . . . H19A H 0.4093 -0.0789 0.1847 0.030 Uiso 1 1 calc R . . H19B H 0.5176 -0.1224 0.2070 0.030 Uiso 1 1 calc R . . C20 C 0.5210(3) 0.0084(3) 0.2127(2) 0.0252(9) Uani 1 1 d . . . C21 C 0.4954(3) 0.0847(3) 0.18391(19) 0.0246(9) Uani 1 1 d . . . C22 C 0.5359(3) 0.1625(3) 0.2060(2) 0.0281(9) Uani 1 1 d . . . C23 C 0.6008(4) 0.1589(3) 0.2570(2) 0.0305(10) Uani 1 1 d . . . H23 H 0.6296 0.2107 0.2720 0.037 Uiso 1 1 calc R . . C24 C 0.6260(3) 0.0835(3) 0.2875(2) 0.0294(10) Uani 1 1 d . . . C25 C 0.5834(3) 0.0085(3) 0.2640(2) 0.0265(9) Uani 1 1 d . . . H25 H 0.5977 -0.0439 0.2837 0.032 Uiso 1 1 calc R . . C26 C 0.5126(4) 0.2476(3) 0.1743(2) 0.0346(11) Uani 1 1 d . . . C27 C 0.5479(5) 0.2435(4) 0.1098(3) 0.0479(14) Uani 1 1 d . . . H27A H 0.6219 0.2259 0.1092 0.072 Uiso 1 1 calc R . . H27B H 0.5400 0.2998 0.0915 0.072 Uiso 1 1 calc R . . H27C H 0.5043 0.2022 0.0877 0.072 Uiso 1 1 calc R . . C28 C 0.3933(4) 0.2653(3) 0.1754(3) 0.0426(13) Uani 1 1 d . . . H28A H 0.3548 0.2181 0.1563 0.064 Uiso 1 1 calc R . . H28B H 0.3773 0.3183 0.1541 0.064 Uiso 1 1 calc R . . H28C H 0.3719 0.2707 0.2165 0.064 Uiso 1 1 calc R . . C29 C 0.5695(4) 0.3224(3) 0.2040(3) 0.0452(13) Uani 1 1 d . . . H29A H 0.5473 0.3275 0.2450 0.068 Uiso 1 1 calc R . . H29B H 0.5521 0.3749 0.1824 0.068 Uiso 1 1 calc R . . H29C H 0.6457 0.3127 0.2038 0.068 Uiso 1 1 calc R . . C30 C 0.6983(4) 0.0812(3) 0.3432(2) 0.0357(11) Uani 1 1 d . . . C31 C 0.7569(5) 0.1648(4) 0.3533(3) 0.0469(14) Uani 1 1 d . . . H31A H 0.7060 0.2104 0.3602 0.070 Uiso 1 1 calc R . . H31B H 0.7972 0.1784 0.3183 0.070 Uiso 1 1 calc R . . H31C H 0.8050 0.1594 0.3879 0.070 Uiso 1 1 calc R . . C32 C 0.7811(5) 0.0099(4) 0.3373(3) 0.0580(17) Uani 1 1 d . . . H32A H 0.8291 0.0104 0.3722 0.087 Uiso 1 1 calc R . . H32B H 0.8213 0.0195 0.3016 0.087 Uiso 1 1 calc R . . H32C H 0.7455 -0.0453 0.3345 0.087 Uiso 1 1 calc R . . C33 C 0.6316(5) 0.0635(4) 0.3970(3) 0.0494(14) Uani 1 1 d . . . H33A H 0.5793 0.1088 0.4009 0.074 Uiso 1 1 calc R . . H33B H 0.6773 0.0616 0.4328 0.074 Uiso 1 1 calc R . . H33C H 0.5955 0.0087 0.3919 0.074 Uiso 1 1 calc R . . C34 C 0.6484(3) 0.0127(3) 0.0743(2) 0.0247(9) Uani 1 1 d . . . C35 C 0.7453(3) 0.0534(3) 0.0723(2) 0.0291(10) Uani 1 1 d . . . H35 H 0.7563 0.0970 0.0440 0.035 Uiso 1 1 calc R . . C36 C 0.8264(4) 0.0294(3) 0.1123(2) 0.0329(10) Uani 1 1 d . . . H36 H 0.8929 0.0569 0.1114 0.039 Uiso 1 1 calc R . . C37 C 0.8096(4) -0.0346(3) 0.1533(2) 0.0337(11) Uani 1 1 d . . . H37 H 0.8651 -0.0518 0.1799 0.040 Uiso 1 1 calc R . . C38 C 0.7121(4) -0.0735(3) 0.1554(2) 0.0302(10) Uani 1 1 d . . . H38 H 0.7008 -0.1174 0.1834 0.036 Uiso 1 1 calc R . . C39 C 0.6302(3) -0.0482(3) 0.1166(2) 0.0256(9) Uani 1 1 d . . . C100 C 0.5092(8) 0.5876(7) 0.0037(4) 0.103(3) Uiso 1 1 d . . . H100 H 0.5163 0.6477 0.0064 0.123 Uiso 1 1 calc R . . C101 C 0.5976(9) 0.5361(7) 0.0025(5) 0.105(3) Uiso 1 1 d . . . H101 H 0.6658 0.5612 0.0040 0.125 Uiso 1 1 calc R A 1 C103 C 0.6889(17) 0.3891(14) -0.0007(10) 0.109(6) Uiso 0.50 1 d P B 1 H12D H 0.7520 0.4234 0.0081 0.163 Uiso 0.50 1 calc PR B 1 H11D H 0.6946 0.3623 -0.0396 0.163 Uiso 0.50 1 calc PR B 1 H10D H 0.6825 0.3450 0.0296 0.163 Uiso 0.50 1 calc PR B 1 C104 C 0.9560(15) 0.3599(12) 0.0310(8) 0.207(8) Uiso 1 1 d . . . H10A H 0.8855 0.3471 0.0144 0.311 Uiso 1 1 calc R . . H10B H 1.0091 0.3335 0.0064 0.311 Uiso 1 1 calc R . . H10C H 0.9666 0.4217 0.0318 0.311 Uiso 1 1 calc R . . C105 C 0.9668(4) 0.3241(4) 0.0949(3) 0.129(4) Uiso 1 1 d G . . C106 C 1.0550(4) 0.3290(4) 0.1328(3) 0.126(4) Uiso 1 1 d G . . H106 H 1.1152 0.3602 0.1214 0.151 Uiso 1 1 calc R . . C107 C 1.0553(5) 0.2883(4) 0.1874(3) 0.131(4) Uiso 1 1 d G . . H107 H 1.1156 0.2917 0.2133 0.158 Uiso 1 1 calc R . . C108 C 0.9673(5) 0.2427(4) 0.2041(3) 0.114(3) Uiso 1 1 d G . . H108 H 0.9675 0.2149 0.2415 0.137 Uiso 1 1 calc R . . C109 C 0.8791(4) 0.2378(4) 0.1663(3) 0.107(3) Uiso 1 1 d G . . H109 H 0.8190 0.2067 0.1777 0.128 Uiso 1 1 calc R . . C110 C 0.8788(4) 0.2785(3) 0.1116(2) 0.102(3) Uiso 1 1 d G . . H110 H 0.8185 0.2752 0.0857 0.122 Uiso 1 1 calc R . . C202 C 0.5876(6) 0.4487(6) -0.0009(4) 0.23(2) Uiso 0.50 1 d PG . 1 C102 C 0.5876(6) 0.4487(6) -0.0009(4) 0.050(3) Uiso 0.50 1 d PG . 2 H102 H 0.6487 0.4140 -0.0014 0.059 Uiso 0.50 1 calc PR . 2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Hf1 0.01879(9) 0.02532(11) 0.02647(11) 0.00081(7) 0.00391(6) 0.00336(7) O1 0.0343(18) 0.0380(19) 0.0311(18) -0.0003(14) 0.0003(14) 0.0162(14) N1 0.0190(17) 0.0221(18) 0.029(2) -0.0007(14) 0.0044(14) -0.0001(13) C1 0.039(3) 0.047(3) 0.042(3) -0.002(2) -0.006(2) 0.019(2) O2 0.0191(14) 0.0294(17) 0.0341(18) 0.0034(13) 0.0031(13) 0.0020(12) C2 0.032(3) 0.050(3) 0.076(4) -0.011(3) 0.007(3) 0.011(2) O3 0.0198(14) 0.0337(18) 0.0286(16) 0.0003(13) 0.0035(12) 0.0037(12) C3 0.062(4) 0.049(4) 0.063(4) 0.020(3) 0.023(3) 0.030(3) O4 0.0227(15) 0.0244(16) 0.0314(17) -0.0001(12) 0.0019(13) 0.0028(11) C4 0.023(2) 0.030(2) 0.034(3) -0.0036(19) 0.0034(19) -0.0023(17) C5 0.025(2) 0.028(2) 0.040(3) -0.0090(19) 0.0036(19) -0.0015(17) C6 0.028(2) 0.026(3) 0.064(4) -0.002(2) 0.004(2) 0.0022(18) C7 0.033(3) 0.027(3) 0.081(4) 0.001(3) 0.009(3) -0.001(2) C8 0.027(2) 0.035(3) 0.065(4) 0.000(2) 0.009(2) -0.007(2) C9 0.027(2) 0.029(3) 0.041(3) -0.006(2) 0.006(2) -0.0027(18) C10 0.019(2) 0.035(3) 0.038(3) -0.002(2) 0.0096(19) -0.0028(17) C11 0.031(2) 0.040(3) 0.038(3) -0.002(2) 0.009(2) 0.000(2) C12 0.023(2) 0.052(3) 0.041(3) -0.003(2) 0.002(2) -0.001(2) C13 0.021(2) 0.045(3) 0.064(4) -0.001(3) 0.010(2) -0.004(2) C14 0.042(3) 0.033(3) 0.144(7) 0.018(4) 0.022(4) 0.004(2) C15 0.079(6) 0.039(5) 0.238(15) 0.013(6) -0.006(7) -0.013(4) C16 0.096(6) 0.077(6) 0.157(9) 0.063(6) 0.077(6) 0.039(5) C17 0.064(4) 0.033(3) 0.149(8) 0.032(4) 0.029(5) 0.010(3) C18 0.022(2) 0.026(2) 0.038(3) -0.0043(19) 0.0028(19) 0.0030(16) C19 0.025(2) 0.023(2) 0.028(2) 0.0005(17) 0.0029(18) -0.0005(16) C20 0.021(2) 0.026(2) 0.028(2) -0.0005(17) 0.0069(17) -0.0010(16) C21 0.021(2) 0.029(2) 0.024(2) -0.0015(17) 0.0052(17) 0.0013(16) C22 0.023(2) 0.025(2) 0.036(3) -0.0006(18) 0.0070(19) 0.0017(16) C23 0.026(2) 0.029(2) 0.037(3) -0.0044(19) 0.0030(19) -0.0009(17) C24 0.023(2) 0.030(2) 0.036(3) -0.0030(19) 0.0051(19) -0.0002(17) C25 0.024(2) 0.030(2) 0.026(2) 0.0016(17) 0.0051(17) 0.0029(16) C26 0.036(3) 0.022(2) 0.046(3) 0.002(2) 0.006(2) 0.0011(18) C27 0.062(4) 0.036(3) 0.047(3) 0.012(2) 0.006(3) -0.001(3) C28 0.038(3) 0.030(3) 0.060(4) -0.004(2) -0.001(3) 0.005(2) C29 0.046(3) 0.025(3) 0.065(4) 0.004(2) 0.000(3) -0.004(2) C30 0.034(3) 0.033(3) 0.039(3) -0.005(2) -0.006(2) 0.004(2) C31 0.043(3) 0.050(3) 0.047(3) -0.004(3) -0.007(3) -0.010(2) C32 0.046(3) 0.063(4) 0.063(4) -0.022(3) -0.021(3) 0.020(3) C33 0.048(3) 0.057(4) 0.042(3) 0.007(3) -0.006(3) 0.000(3) C34 0.022(2) 0.026(2) 0.027(2) -0.0024(17) 0.0052(17) 0.0040(16) C35 0.022(2) 0.033(3) 0.033(2) 0.0018(19) 0.0056(18) -0.0019(17) C36 0.021(2) 0.041(3) 0.037(3) -0.003(2) 0.0030(19) -0.0018(18) C37 0.022(2) 0.042(3) 0.037(3) -0.002(2) 0.0004(19) 0.0071(19) C38 0.028(2) 0.029(2) 0.034(3) 0.0007(19) 0.0047(19) 0.0036(18) C39 0.019(2) 0.027(2) 0.031(2) -0.0032(18) 0.0047(17) 0.0005(16) _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 O1 1.913(3) . ? Hf1 O2 1.972(3) . ? Hf1 O4 1.987(3) . ? Hf1 O3 2.142(3) . ? Hf1 O3 2.252(3) 3_655 ? Hf1 N1 2.417(4) . ? O1 C1 1.419(6) . ? N1 C39 1.460(5) . ? N1 C18 1.503(6) . ? N1 C19 1.508(6) . ? C1 C3 1.504(9) . ? C1 C2 1.516(8) . ? C1 H1 1.0000 . ? O2 C4 1.353(6) . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 0.9800 . ? O3 C34 1.382(5) . ? O3 Hf1 2.252(3) 3_655 ? C3 H3A 0.9800 . ? C3 H3B 0.9800 . ? C3 H3C 0.9800 . ? O4 C21 1.354(5) . ? C4 C5 1.404(6) . ? C4 C9 1.425(6) . ? C5 C6 1.390(7) . ? C5 C18 1.519(6) . ? C6 C7 1.394(7) . ? C6 H6 0.9500 . ? C7 C8 1.399(7) . ? C7 C14 1.554(8) . ? C8 C9 1.387(7) . ? C8 H8 0.9500 . ? C9 C10 1.536(6) . ? C10 C11 1.529(7) . ? C10 C12 1.539(7) . ? C10 C13 1.539(6) . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C14 C15 1.491(12) . ? C14 C17 1.519(9) . ? C14 C16 1.564(12) . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C18 H18A 0.9900 . ? C18 H18B 0.9900 . ? C19 C20 1.504(6) . ? C19 H19A 0.9900 . ? C19 H19B 0.9900 . ? C20 C25 1.383(6) . ? C20 C21 1.397(6) . ? C21 C22 1.410(6) . ? C22 C23 1.397(7) . ? C22 C26 1.541(6) . ? C23 C24 1.402(7) . ? C23 H23 0.9500 . ? C24 C25 1.395(6) . ? C24 C30 1.532(7) . ? C25 H25 0.9500 . ? C26 C29 1.523(7) . ? C26 C27 1.540(8) . ? C26 C28 1.541(7) . ? C27 H27A 0.9800 . ? C27 H27B 0.9800 . ? C27 H27C 0.9800 . ? C28 H28A 0.9800 . ? C28 H28B 0.9800 . ? C28 H28C 0.9800 . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? C30 C31 1.524(7) . ? C30 C33 1.531(8) . ? C30 C32 1.545(7) . ? C31 H31A 0.9800 . ? C31 H31B 0.9800 . ? C31 H31C 0.9800 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? C33 H33A 0.9800 . ? C33 H33B 0.9800 . ? C33 H33C 0.9800 . ? C34 C39 1.377(6) . ? C34 C35 1.389(6) . ? C35 C36 1.400(7) . ? C35 H35 0.9500 . ? C36 C37 1.389(7) . ? C36 H36 0.9500 . ? C37 C38 1.383(6) . ? C37 H37 0.9500 . ? C38 C39 1.395(6) . ? C38 H38 0.9500 . ? C100 C102 1.355(15) 3_665 ? C100 C202 1.355(15) 3_665 ? C100 C101 1.385(14) . ? C100 H100 0.9500 . ? C101 C102 1.381(14) . ? C101 C202 1.381(14) . ? C101 H101 0.9500 . ? C103 C202 1.59(2) . ? C103 H12D 0.9800 . ? C103 H11D 0.9800 . ? C103 H10D 0.9800 . ? C104 C105 1.551(19) . ? C104 H10A 0.9800 . ? C104 H10B 0.9800 . ? C104 H10C 0.9800 . ? C105 C106 1.3900 . ? C105 C110 1.3900 . ? C106 C107 1.3900 . ? C106 H106 0.9500 . ? C107 C108 1.3900 . ? C107 H107 0.9500 . ? C108 C109 1.3900 . ? C108 H108 0.9500 . ? C109 C110 1.3900 . ? C109 H109 0.9500 . ? C110 H110 0.9500 . ? C202 C100 1.355(12) 3_665 ? C102 C100 1.355(12) 3_665 ? C102 H102 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Hf1 O2 102.89(14) . . ? O1 Hf1 O4 91.98(13) . . ? O2 Hf1 O4 109.09(13) . . ? O1 Hf1 O3 111.85(13) . . ? O2 Hf1 O3 137.91(12) . . ? O4 Hf1 O3 93.09(12) . . ? O1 Hf1 O3 86.12(12) . 3_655 ? O2 Hf1 O3 91.87(12) . 3_655 ? O4 Hf1 O3 158.81(12) . 3_655 ? O3 Hf1 O3 68.29(13) . 3_655 ? O1 Hf1 N1 168.61(13) . . ? O2 Hf1 N1 77.81(12) . . ? O4 Hf1 N1 77.19(12) . . ? O3 Hf1 N1 72.76(12) . . ? O3 Hf1 N1 105.25(11) 3_655 . ? C1 O1 Hf1 163.4(4) . . ? C39 N1 C18 111.2(3) . . ? C39 N1 C19 111.1(3) . . ? C18 N1 C19 111.1(3) . . ? C39 N1 Hf1 107.5(3) . . ? C18 N1 Hf1 107.1(3) . . ? C19 N1 Hf1 108.7(2) . . ? O1 C1 C3 109.8(5) . . ? O1 C1 C2 109.0(4) . . ? C3 C1 C2 112.1(5) . . ? O1 C1 H1 108.6 . . ? C3 C1 H1 108.6 . . ? C2 C1 H1 108.6 . . ? C4 O2 Hf1 144.3(3) . . ? C1 C2 H2A 109.5 . . ? C1 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? C1 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? C34 O3 Hf1 116.7(3) . . ? C34 O3 Hf1 117.5(2) . 3_655 ? Hf1 O3 Hf1 111.71(13) . 3_655 ? C1 C3 H3A 109.5 . . ? C1 C3 H3B 109.5 . . ? H3A C3 H3B 109.5 . . ? C1 C3 H3C 109.5 . . ? H3A C3 H3C 109.5 . . ? H3B C3 H3C 109.5 . . ? C21 O4 Hf1 141.7(3) . . ? O2 C4 C5 119.4(4) . . ? O2 C4 C9 121.0(4) . . ? C5 C4 C9 119.5(4) . . ? C6 C5 C4 120.7(4) . . ? C6 C5 C18 119.3(4) . . ? C4 C5 C18 120.0(4) . . ? C5 C6 C7 121.4(5) . . ? C5 C6 H6 119.3 . . ? C7 C6 H6 119.3 . . ? C6 C7 C8 116.6(5) . . ? C6 C7 C14 123.6(5) . . ? C8 C7 C14 119.6(5) . . ? C9 C8 C7 124.7(5) . . ? C9 C8 H8 117.6 . . ? C7 C8 H8 117.6 . . ? C8 C9 C4 117.0(4) . . ? C8 C9 C10 121.2(4) . . ? C4 C9 C10 121.6(4) . . ? C11 C10 C9 107.7(4) . . ? C11 C10 C12 110.2(4) . . ? C9 C10 C12 112.1(4) . . ? C11 C10 C13 108.6(4) . . ? C9 C10 C13 111.8(4) . . ? C12 C10 C13 106.4(4) . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C15 C14 C17 109.3(7) . . ? C15 C14 C7 110.2(7) . . ? C17 C14 C7 111.2(5) . . ? C15 C14 C16 108.6(8) . . ? C17 C14 C16 108.4(7) . . ? C7 C14 C16 109.1(6) . . ? C14 C15 H15A 109.5 . . ? C14 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C14 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C14 C16 H16A 109.5 . . ? C14 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C14 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C14 C17 H17A 109.5 . . ? C14 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C14 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? N1 C18 C5 113.8(4) . . ? N1 C18 H18A 108.8 . . ? C5 C18 H18A 108.8 . . ? N1 C18 H18B 108.8 . . ? C5 C18 H18B 108.8 . . ? H18A C18 H18B 107.7 . . ? C20 C19 N1 110.8(3) . . ? C20 C19 H19A 109.5 . . ? N1 C19 H19A 109.5 . . ? C20 C19 H19B 109.5 . . ? N1 C19 H19B 109.5 . . ? H19A C19 H19B 108.1 . . ? C25 C20 C21 120.5(4) . . ? C25 C20 C19 120.6(4) . . ? C21 C20 C19 118.7(4) . . ? O4 C21 C20 118.2(4) . . ? O4 C21 C22 121.6(4) . . ? C20 C21 C22 120.2(4) . . ? C23 C22 C21 117.1(4) . . ? C23 C22 C26 121.1(4) . . ? C21 C22 C26 121.8(4) . . ? C22 C23 C24 124.0(4) . . ? C22 C23 H23 118.0 . . ? C24 C23 H23 118.0 . . ? C25 C24 C23 116.5(4) . . ? C25 C24 C30 120.4(4) . . ? C23 C24 C30 123.0(4) . . ? C20 C25 C24 121.7(4) . . ? C20 C25 H25 119.2 . . ? C24 C25 H25 119.2 . . ? C29 C26 C27 107.5(4) . . ? C29 C26 C28 107.9(4) . . ? C27 C26 C28 109.8(5) . . ? C29 C26 C22 112.5(4) . . ? C27 C26 C22 110.2(4) . . ? C28 C26 C22 108.8(4) . . ? C26 C27 H27A 109.5 . . ? C26 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? C26 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? C26 C28 H28A 109.5 . . ? C26 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C26 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? C26 C29 H29A 109.5 . . ? C26 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C26 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C31 C30 C33 108.5(5) . . ? C31 C30 C24 112.3(4) . . ? C33 C30 C24 108.9(4) . . ? C31 C30 C32 107.9(5) . . ? C33 C30 C32 109.4(5) . . ? C24 C30 C32 109.8(4) . . ? C30 C31 H31A 109.5 . . ? C30 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? C30 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? C30 C32 H32A 109.5 . . ? C30 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? C30 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C30 C33 H33A 109.5 . . ? C30 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? C30 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? C39 C34 O3 118.6(4) . . ? C39 C34 C35 120.8(4) . . ? O3 C34 C35 120.6(4) . . ? C34 C35 C36 119.2(4) . . ? C34 C35 H35 120.4 . . ? C36 C35 H35 120.4 . . ? C37 C36 C35 120.0(4) . . ? C37 C36 H36 120.0 . . ? C35 C36 H36 120.0 . . ? C38 C37 C36 120.0(4) . . ? C38 C37 H37 120.0 . . ? C36 C37 H37 120.0 . . ? C37 C38 C39 120.2(4) . . ? C37 C38 H38 119.9 . . ? C39 C38 H38 119.9 . . ? C34 C39 C38 119.7(4) . . ? C34 C39 N1 117.1(4) . . ? C38 C39 N1 123.0(4) . . ? C102 C100 C202 0.0(17) 3_665 3_665 ? C102 C100 C101 119.2(11) 3_665 . ? C202 C100 C101 119.2(11) 3_665 . ? C102 C100 H100 120.4 3_665 . ? C202 C100 H100 120.4 3_665 . ? C101 C100 H100 120.4 . . ? C102 C101 C202 0.0(7) . . ? C102 C101 C100 120.5(10) . . ? C202 C101 C100 120.5(10) . . ? C102 C101 H101 119.7 . . ? C202 C101 H101 119.7 . . ? C100 C101 H101 119.7 . . ? C202 C103 H12D 109.5 . . ? C202 C103 H11D 109.5 . . ? H12D C103 H11D 109.5 . . ? C202 C103 H10D 109.5 . . ? H12D C103 H10D 109.5 . . ? H11D C103 H10D 109.5 . . ? C105 C104 H10A 109.5 . . ? C105 C104 H10B 109.5 . . ? H10A C104 H10B 109.5 . . ? C105 C104 H10C 109.5 . . ? H10A C104 H10C 109.5 . . ? H10B C104 H10C 109.5 . . ? C106 C105 C110 120.0 . . ? C106 C105 C104 126.7(8) . . ? C110 C105 C104 113.1(8) . . ? C105 C106 C107 120.0 . . ? C105 C106 H106 120.0 . . ? C107 C106 H106 120.0 . . ? C108 C107 C106 120.0 . . ? C108 C107 H107 120.0 . . ? C106 C107 H107 120.0 . . ? C107 C108 C109 120.0 . . ? C107 C108 H108 120.0 . . ? C109 C108 H108 120.0 . . ? C110 C109 C108 120.0 . . ? C110 C109 H109 120.0 . . ? C108 C109 H109 120.0 . . ? C109 C110 C105 120.0 . . ? C109 C110 H110 120.0 . . ? C105 C110 H110 120.0 . . ? C100 C202 C101 120.2(8) 3_665 . ? C100 C202 C103 119.0(12) 3_665 . ? C101 C202 C103 120.8(11) . . ? C100 C102 C101 120.2(8) 3_665 . ? C100 C102 H102 119.9 3_665 . ? C101 C102 H102 119.9 . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 1.999 _refine_diff_density_min -1.408 _refine_diff_density_rms 0.130