# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name 'P. Scott' 'Guy J. Clarkson' 'R Deeth' 'Andrew L. Gott' 'Max Hammond' 'Colin Morton' _publ_contact_author_name 'Peter Scott' _publ_contact_author_address ; Department of Chemistry University of Warwick Gibbett Hill Rd COVENTRY CV4 7AL UNITED KINGDOM ; _publ_contact_author_email PETER.SCOTT@WARWICK.AC.UK _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Constrained geometry aminooxazolinate ligands giving chiral zirconium guanidinates; catalytic cyclohydroamination ; data_ag15 _database_code_depnum_ccdc_archive 'CCDC 680408' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H42 N4 O Si Zr' _chemical_formula_weight 497.91 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 9.8832(2) _cell_length_b 15.3216(3) _cell_length_c 17.2098(3) _cell_angle_alpha 90.000(5) _cell_angle_beta 90.000(5) _cell_angle_gamma 90.000(5) _cell_volume 2606.02(9) _cell_formula_units_Z 4 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 9789 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.46 _exptl_crystal_size_mid 0.42 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.269 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1056 _exptl_absorpt_coefficient_mu 0.487 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7816 _exptl_absorpt_correction_T_max 0.8292 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cooler (Cosier & Glazer, 1986). The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of three sets of exposures with different \f angles for the crystal; each 10 s exposure covered 0.3\% in \w. The crystal-to-detector distance was 5.0 cm. Coverage of the unique Set is over 97% complete to at least 26\% in \q. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 (or 1.5 for methyl H-atoms) times the equivalent isotropic displacement parameter of the atom to which they are attached. ; _diffrn_ambient_temperature 120(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 'Siemens SMART diffractometer' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8.192 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% nil _diffrn_reflns_number 18995 _diffrn_reflns_av_R_equivalents 0.0422 _diffrn_reflns_av_sigmaI/netI 0.0407 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.91 _diffrn_reflns_theta_max 27.48 _reflns_number_total 5939 _reflns_number_gt 5596 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1994)' _computing_cell_refinement 'SAINT (Siemens, 1995)' _computing_data_reduction 'SAINT (Siemens, 1995)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1997)' _computing_publication_material 'SHELXTL (Sheldrick, 1997)' _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^)+(0.0213P)^2^+1.5363P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881, 2590 Fridel pairs' _refine_ls_abs_structure_Flack 0.04(3) _chemical_absolute_configuration rmad _refine_ls_number_reflns 5939 _refine_ls_number_parameters 275 _refine_ls_number_restraints 18 _refine_ls_R_factor_all 0.0342 _refine_ls_R_factor_gt 0.0304 _refine_ls_wR_factor_ref 0.0656 _refine_ls_wR_factor_gt 0.0638 _refine_ls_goodness_of_fit_ref 1.069 _refine_ls_restrained_S_all 1.084 _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 1.01721(2) 0.939718(14) -0.029757(12) 0.01253(6) Uani 1 1 d . . . Si1 Si 0.81330(7) 1.09763(5) -0.00670(4) 0.01975(15) Uani 1 1 d . . . N1 N 0.8898(2) 1.04770(13) -0.08544(11) 0.0160(4) Uani 1 1 d . . . N2 N 0.8844(2) 0.91114(13) -0.12684(12) 0.0176(4) Uani 1 1 d . . . N3 N 0.7265(2) 1.01325(15) -0.18191(13) 0.0236(5) Uani 1 1 d . . . N4 N 1.2078(2) 0.97809(14) -0.06432(13) 0.0193(4) Uani 1 1 d . . . O1 O 1.02645(18) 0.80988(10) -0.04925(9) 0.0179(3) Uani 1 1 d . . . C1 C 0.8867(2) 1.02533(16) 0.06992(14) 0.0155(5) Uani 1 1 d . . . C2 C 0.8465(2) 0.93489(18) 0.07947(14) 0.0197(5) Uani 1 1 d . . . C3 C 0.9578(3) 0.88772(16) 0.10940(14) 0.0242(6) Uani 1 1 d . . . C4 C 1.0679(3) 0.9458(2) 0.11934(14) 0.0255(6) Uani 1 1 d . . . C5 C 1.0244(3) 1.02980(15) 0.09607(13) 0.0189(5) Uani 1 1 d . . . C6 C 0.7091(3) 0.8974(2) 0.06129(19) 0.0365(7) Uani 1 1 d . . . H6A H 0.6427 0.9199 0.0986 0.055 Uiso 1 1 calc R . . H6B H 0.7128 0.8336 0.0649 0.055 Uiso 1 1 calc R . . H6C H 0.6824 0.9144 0.0086 0.055 Uiso 1 1 calc R . . C7 C 0.9615(4) 0.79171(18) 0.12925(18) 0.0420(9) Uani 1 1 d . . . H7A H 0.9945 0.7843 0.1825 0.063 Uiso 1 1 calc R . . H7B H 1.0223 0.7614 0.0932 0.063 Uiso 1 1 calc R . . H7C H 0.8703 0.7672 0.1249 0.063 Uiso 1 1 calc R . . C8 C 1.2039(3) 0.9239(2) 0.15380(18) 0.0449(9) Uani 1 1 d . . . H8A H 1.2107 0.9492 0.2060 0.067 Uiso 1 1 calc R . . H8B H 1.2756 0.9480 0.1208 0.067 Uiso 1 1 calc R . . H8C H 1.2139 0.8604 0.1571 0.067 Uiso 1 1 calc R . . C9 C 1.1111(3) 1.1109(2) 0.1025(2) 0.0360(7) Uani 1 1 d . . . H9A H 1.0726 1.1502 0.1416 0.054 Uiso 1 1 calc R . . H9B H 1.1139 1.1407 0.0521 0.054 Uiso 1 1 calc R . . H9C H 1.2031 1.0944 0.1179 0.054 Uiso 1 1 calc R . . C10 C 0.8668(4) 1.21398(18) 0.0003(2) 0.0504(10) Uani 1 1 d . . . H10A H 0.8435 1.2368 0.0518 0.076 Uiso 1 1 calc R . . H10B H 0.8202 1.2482 -0.0396 0.076 Uiso 1 1 calc R . . H10C H 0.9648 1.2181 -0.0075 0.076 Uiso 1 1 calc R . . C11 C 0.6244(3) 1.0960(3) -0.01047(19) 0.0518(10) Uani 1 1 d U . . H11A H 0.5922 1.1440 -0.0432 0.078 Uiso 1 1 calc R . . H11B H 0.5880 1.1027 0.0422 0.078 Uiso 1 1 calc R . . H11C H 0.5938 1.0403 -0.0323 0.078 Uiso 1 1 calc R . . C12 C 0.8300(3) 0.98914(16) -0.13506(14) 0.0167(5) Uani 1 1 d . . . C13 C 0.6311(3) 0.9506(2) -0.21493(16) 0.0299(6) Uani 1 1 d . . . H13A H 0.6343 0.8962 -0.1850 0.045 Uiso 1 1 calc R . . H13B H 0.6556 0.9387 -0.2691 0.045 Uiso 1 1 calc R . . H13C H 0.5394 0.9749 -0.2129 0.045 Uiso 1 1 calc R . . C14 C 0.7027(3) 1.1037(2) -0.20235(17) 0.0334(7) Uani 1 1 d . . . H14A H 0.7744 1.1402 -0.1800 0.050 Uiso 1 1 calc R . . H14B H 0.6149 1.1223 -0.1818 0.050 Uiso 1 1 calc R . . H14C H 0.7029 1.1099 -0.2590 0.050 Uiso 1 1 calc R . . C15 C 0.8860(3) 0.82654(17) -0.16555(14) 0.0196(5) Uani 1 1 d . . . H15A H 0.7915 0.8108 -0.1810 0.024 Uiso 1 1 calc R . . C16 C 0.9793(3) 0.82237(18) -0.23871(14) 0.0254(6) Uani 1 1 d . . . C17 C 0.9440(3) 0.7383(2) -0.2829(2) 0.0472(9) Uani 1 1 d U . . H17A H 1.0037 0.7324 -0.3280 0.071 Uiso 1 1 calc R . . H17B H 0.8497 0.7409 -0.3003 0.071 Uiso 1 1 calc R . . H17C H 0.9560 0.6880 -0.2485 0.071 Uiso 1 1 calc R . . C18 C 1.1293(3) 0.8220(2) -0.21794(16) 0.0271(6) Uani 1 1 d . . . H18A H 1.1832 0.8163 -0.2655 0.041 Uiso 1 1 calc R . . H18B H 1.1485 0.7728 -0.1833 0.041 Uiso 1 1 calc R . . H18C H 1.1526 0.8768 -0.1917 0.041 Uiso 1 1 calc R . . C19 C 0.9537(3) 0.9011(2) -0.29187(17) 0.0443(9) Uani 1 1 d U . . H19A H 1.0160 0.8989 -0.3361 0.067 Uiso 1 1 calc R . . H19B H 0.9684 0.9551 -0.2626 0.067 Uiso 1 1 calc R . . H19C H 0.8602 0.8994 -0.3108 0.067 Uiso 1 1 calc R . . C20 C 0.9313(3) 0.76664(16) -0.09794(15) 0.0202(5) Uani 1 1 d . . . H20A H 0.8514 0.7495 -0.0668 0.024 Uiso 1 1 calc R . . H20B H 0.9727 0.7129 -0.1193 0.024 Uiso 1 1 calc R . . C21 C 1.3226(3) 0.91911(19) -0.05631(19) 0.0345(7) Uani 1 1 d . . . H21A H 1.3679 0.9129 -0.1066 0.052 Uiso 1 1 calc R . . H21B H 1.2906 0.8619 -0.0387 0.052 Uiso 1 1 calc R . . H21C H 1.3864 0.9429 -0.0182 0.052 Uiso 1 1 calc R . . C22 C 1.2508(3) 1.0635(2) -0.0898(2) 0.0361(7) Uani 1 1 d . . . H22A H 1.2962 1.0586 -0.1402 0.054 Uiso 1 1 calc R . . H22B H 1.3138 1.0882 -0.0516 0.054 Uiso 1 1 calc R . . H22C H 1.1718 1.1018 -0.0947 0.054 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 Zr1 0.01273(10) 0.01280(9) 0.01206(9) 0.00002(9) -0.00002(9) -0.00023(8) Si1 0.0208(3) 0.0186(3) 0.0199(3) -0.0007(3) -0.0012(3) 0.0075(3) N1 0.0169(9) 0.0148(10) 0.0164(10) 0.0023(8) -0.0014(8) 0.0016(8) N2 0.0175(10) 0.0178(10) 0.0174(10) -0.0023(8) -0.0016(9) 0.0010(8) N3 0.0245(12) 0.0261(12) 0.0201(11) 0.0024(9) -0.0081(10) 0.0051(9) N4 0.0129(10) 0.0217(11) 0.0233(11) 0.0029(9) 0.0023(9) -0.0010(8) O1 0.0209(8) 0.0152(8) 0.0177(8) -0.0005(6) -0.0012(7) -0.0004(7) C1 0.0157(12) 0.0166(11) 0.0143(12) -0.0030(9) 0.0024(10) 0.0002(9) C2 0.0224(12) 0.0188(12) 0.0179(11) -0.0036(11) 0.0081(10) -0.0053(12) C3 0.0407(16) 0.0169(12) 0.0149(11) 0.0025(9) 0.0128(12) 0.0049(11) C4 0.0313(13) 0.0330(15) 0.0123(11) -0.0026(12) -0.0001(10) 0.0151(13) C5 0.0202(12) 0.0211(11) 0.0153(11) -0.0067(9) -0.0062(11) 0.0027(10) C6 0.0334(16) 0.0354(16) 0.0407(17) -0.0140(14) 0.0201(14) -0.0157(13) C7 0.071(2) 0.0222(14) 0.0328(15) 0.0093(12) 0.0231(17) 0.0145(15) C8 0.0443(19) 0.065(2) 0.0258(15) -0.0117(15) -0.0129(14) 0.0313(17) C9 0.0269(15) 0.0343(17) 0.0468(19) -0.0174(15) -0.0054(14) -0.0081(13) C10 0.094(3) 0.0173(14) 0.0396(17) -0.0035(13) -0.0102(19) 0.0129(17) C11 0.0304(16) 0.095(3) 0.0298(17) 0.0076(17) 0.0027(14) 0.0248(17) C12 0.0144(12) 0.0222(13) 0.0136(11) 0.0021(9) 0.0004(10) -0.0026(10) C13 0.0188(13) 0.0429(18) 0.0279(14) -0.0041(13) -0.0085(11) 0.0009(13) C14 0.0392(18) 0.0344(16) 0.0266(15) 0.0076(13) -0.0083(14) 0.0106(14) C15 0.0180(12) 0.0213(13) 0.0195(12) -0.0061(10) -0.0015(10) -0.0014(10) C16 0.0234(13) 0.0379(15) 0.0150(11) -0.0063(10) 0.0023(12) 0.0018(13) C17 0.0383(18) 0.066(2) 0.0369(17) -0.0316(16) 0.0070(15) -0.0085(16) C18 0.0244(15) 0.0380(16) 0.0190(13) -0.0034(12) 0.0054(12) 0.0001(12) C19 0.0397(19) 0.072(2) 0.0214(13) 0.0101(14) 0.0080(13) 0.0152(16) C20 0.0247(13) 0.0154(12) 0.0204(12) -0.0051(10) 0.0000(11) -0.0036(10) C21 0.0157(12) 0.0337(17) 0.0540(19) 0.0134(13) 0.0043(13) 0.0014(11) C22 0.0247(13) 0.0267(14) 0.0568(19) 0.0092(16) 0.0063(13) -0.0042(14) _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 O1 2.0195(15) . ? Zr1 N4 2.061(2) . ? Zr1 N2 2.169(2) . ? Zr1 N1 2.2896(19) . ? Zr1 C1 2.516(2) . ? Zr1 C2 2.527(2) . ? Zr1 C5 2.569(2) . ? Zr1 C3 2.591(2) . ? Zr1 C4 2.616(2) . ? Zr1 C12 2.698(2) . ? Si1 N1 1.730(2) . ? Si1 C10 1.863(3) . ? Si1 C11 1.869(3) . ? Si1 C1 1.869(3) . ? N1 C12 1.372(3) . ? N2 C12 1.318(3) . ? N2 C15 1.457(3) . ? N3 C12 1.354(3) . ? N3 C14 1.450(3) . ? N3 C13 1.460(4) . ? N4 C22 1.445(3) . ? N4 C21 1.457(3) . ? O1 C20 1.423(3) . ? C1 C5 1.435(4) . ? C1 C2 1.451(4) . ? C2 C3 1.413(4) . ? C2 C6 1.507(4) . ? C3 C4 1.416(4) . ? C3 C7 1.511(4) . ? C4 C5 1.414(4) . ? C4 C8 1.507(4) . ? C5 C9 1.514(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 H8A 0.9800 . ? C8 H8B 0.9800 . ? C8 H8C 0.9800 . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? 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 C20 1.548(4) . ? C15 C16 1.562(3) . ? C15 H15A 1.0000 . ? C16 C18 1.526(4) . ? C16 C19 1.535(4) . ? C16 C17 1.536(4) . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? C18 H18C 0.9800 . ? C19 H19A 0.9800 . ? C19 H19B 0.9800 . ? C19 H19C 0.9800 . ? C20 H20A 0.9900 . ? C20 H20B 0.9900 . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 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 O1 Zr1 N4 101.06(8) . . ? O1 Zr1 N2 72.58(7) . . ? N4 Zr1 N2 112.85(8) . . ? O1 Zr1 N1 131.85(7) . . ? N4 Zr1 N1 100.13(8) . . ? N2 Zr1 N1 59.38(7) . . ? O1 Zr1 C1 130.55(7) . . ? N4 Zr1 C1 121.12(8) . . ? N2 Zr1 C1 108.68(8) . . ? N1 Zr1 C1 68.07(8) . . ? O1 Zr1 C2 97.18(8) . . ? N4 Zr1 C2 146.44(8) . . ? N2 Zr1 C2 99.38(8) . . ? N1 Zr1 C2 88.00(8) . . ? C1 Zr1 C2 33.44(8) . . ? O1 Zr1 C5 131.92(7) . . ? N4 Zr1 C5 93.72(9) . . ? N2 Zr1 C5 140.74(8) . . ? N1 Zr1 C5 88.84(7) . . ? C1 Zr1 C5 32.76(8) . . ? C2 Zr1 C5 53.63(8) . . ? O1 Zr1 C3 82.01(7) . . ? N4 Zr1 C3 124.17(9) . . ? N2 Zr1 C3 120.84(9) . . ? N1 Zr1 C3 118.97(8) . . ? C1 Zr1 C3 54.11(8) . . ? C2 Zr1 C3 32.03(8) . . ? C5 Zr1 C3 52.58(8) . . ? O1 Zr1 C4 100.93(8) . . ? N4 Zr1 C4 95.62(9) . . ? N2 Zr1 C4 151.46(9) . . ? N1 Zr1 C4 119.34(8) . . ? C1 Zr1 C4 53.88(8) . . ? C2 Zr1 C4 53.08(8) . . ? C5 Zr1 C4 31.64(8) . . ? C3 Zr1 C4 31.56(9) . . ? O1 Zr1 C12 101.30(7) . . ? N4 Zr1 C12 110.66(8) . . ? N2 Zr1 C12 28.90(7) . . ? N1 Zr1 C12 30.56(7) . . ? C1 Zr1 C12 87.71(8) . . ? C2 Zr1 C12 92.86(8) . . ? C5 Zr1 C12 115.74(8) . . ? C3 Zr1 C12 123.48(8) . . ? C4 Zr1 C12 141.26(8) . . ? O1 Zr1 Si1 143.17(5) . . ? N4 Zr1 Si1 113.51(6) . . ? N2 Zr1 Si1 82.30(6) . . ? C1 Zr1 Si1 36.06(6) . . ? C2 Zr1 Si1 60.35(6) . . ? C5 Zr1 Si1 60.17(6) . . ? C3 Zr1 Si1 88.56(6) . . ? C4 Zr1 Si1 88.37(6) . . ? C12 Zr1 Si1 55.57(5) . . ? N1 Si1 C10 110.49(14) . . ? N1 Si1 C11 113.79(14) . . ? C10 Si1 C11 107.38(19) . . ? N1 Si1 C1 96.95(10) . . ? C10 Si1 C1 114.28(14) . . ? C11 Si1 C1 113.84(14) . . ? N1 Si1 Zr1 44.56(7) . . ? C10 Si1 Zr1 123.87(13) . . ? C11 Si1 Zr1 128.30(13) . . ? C1 Si1 Zr1 52.40(7) . . ? C12 N1 Si1 126.05(17) . . ? C12 N1 Zr1 91.42(14) . . ? Si1 N1 Zr1 103.42(9) . . ? C12 N2 C15 139.6(2) . . ? C12 N2 Zr1 98.41(15) . . ? C15 N2 Zr1 121.68(16) . . ? C12 N3 C14 121.9(2) . . ? C12 N3 C13 122.7(2) . . ? C14 N3 C13 115.5(2) . . ? C22 N4 C21 111.2(2) . . ? C22 N4 Zr1 127.98(17) . . ? C21 N4 Zr1 120.50(17) . . ? C20 O1 Zr1 121.77(14) . . ? C5 C1 C2 105.7(2) . . ? C5 C1 Si1 124.13(19) . . ? C2 C1 Si1 122.67(18) . . ? C5 C1 Zr1 75.67(13) . . ? C2 C1 Zr1 73.71(13) . . ? Si1 C1 Zr1 91.54(10) . . ? C3 C2 C1 108.5(2) . . ? C3 C2 C6 125.6(3) . . ? C1 C2 C6 125.9(2) . . ? C3 C2 Zr1 76.49(14) . . ? C1 C2 Zr1 72.85(13) . . ? C6 C2 Zr1 117.28(17) . . ? C2 C3 C4 108.7(2) . . ? C2 C3 C7 126.8(3) . . ? C4 C3 C7 124.5(3) . . ? C2 C3 Zr1 71.48(13) . . ? C4 C3 Zr1 75.18(14) . . ? C7 C3 Zr1 120.19(17) . . ? C5 C4 C3 107.7(2) . . ? C5 C4 C8 125.8(3) . . ? C3 C4 C8 126.4(3) . . ? C5 C4 Zr1 72.35(13) . . ? C3 C4 Zr1 73.26(14) . . ? C8 C4 Zr1 123.28(18) . . ? C4 C5 C1 109.5(2) . . ? C4 C5 C9 123.6(2) . . ? C1 C5 C9 126.8(2) . . ? C4 C5 Zr1 76.01(14) . . ? C1 C5 Zr1 71.57(13) . . ? C9 C5 Zr1 121.21(19) . . ? 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 . . ? C3 C7 H7A 109.5 . . ? C3 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C3 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C4 C8 H8A 109.5 . . ? C4 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C4 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C5 C9 H9A 109.5 . . ? C5 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C5 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? Si1 C10 H10A 109.5 . . ? Si1 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? Si1 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? Si1 C11 H11A 109.5 . . ? Si1 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? Si1 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? N2 C12 N3 128.3(2) . . ? N2 C12 N1 110.5(2) . . ? N3 C12 N1 121.2(2) . . ? N2 C12 Zr1 52.69(12) . . ? N3 C12 Zr1 174.06(18) . . ? N1 C12 Zr1 58.03(12) . . ? N3 C13 H13A 109.5 . . ? N3 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? N3 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? N3 C14 H14A 109.5 . . ? N3 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? N3 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? N2 C15 C20 100.76(19) . . ? N2 C15 C16 114.3(2) . . ? C20 C15 C16 114.2(2) . . ? N2 C15 H15A 109.1 . . ? C20 C15 H15A 109.1 . . ? C16 C15 H15A 109.1 . . ? C18 C16 C19 107.6(2) . . ? C18 C16 C17 109.5(2) . . ? C19 C16 C17 109.1(3) . . ? C18 C16 C15 112.7(2) . . ? C19 C16 C15 110.6(2) . . ? C17 C16 C15 107.4(2) . . ? C16 C17 H17A 109.5 . . ? C16 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C16 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C16 C18 H18A 109.5 . . ? C16 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C16 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C16 C19 H19A 109.5 . . ? C16 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C16 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? O1 C20 C15 110.97(19) . . ? O1 C20 H20A 109.4 . . ? C15 C20 H20A 109.4 . . ? O1 C20 H20B 109.4 . . ? C15 C20 H20B 109.4 . . ? H20A C20 H20B 108.0 . . ? N4 C21 H21A 109.5 . . ? N4 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? N4 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? N4 C22 H22A 109.5 . . ? N4 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? N4 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.270 _refine_diff_density_min -0.599 _refine_diff_density_rms 0.062 # Attachment 'cr1m.cif' data_cr1m _database_code_depnum_ccdc_archive 'CCDC 680409' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H34 N4 Si Zr' _chemical_formula_weight 449.82 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 P2(1)/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 10.0781(4) _cell_length_b 17.2011(7) _cell_length_c 12.9809(5) _cell_angle_alpha 90.00 _cell_angle_beta 92.5630(10) _cell_angle_gamma 90.00 _cell_volume 2248.05(15) _cell_formula_units_Z 4 _cell_measurement_temperature 220(2) _cell_measurement_reflns_used 4756 _cell_measurement_theta_min 2.4 _cell_measurement_theta_max 25.00 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.329 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 944 _exptl_absorpt_coefficient_mu 0.553 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7980 _exptl_absorpt_correction_T_max 0.8927 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cooler (Cosier & Glazer, 1986). The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of three sets of exposures with different \f angles for the crystal; each 10 s exposure covered 0.3\% in \w. The crystal-to-detector distance was 5.0 cm. Coverage of the unique Set is over 97% complete to at least 26\% in \q. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 (or 1.5 for methyl H-atoms) times the equivalent isotropic displacement parameter of the atom to which they are attached. ; _diffrn_ambient_temperature 220(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 'Siemens SMART diffractometer' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8.192 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% nil _diffrn_reflns_number 11491 _diffrn_reflns_av_R_equivalents 0.1004 _diffrn_reflns_av_sigmaI/netI 0.0818 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.34 _diffrn_reflns_theta_max 25.03 _reflns_number_total 3944 _reflns_number_gt 2923 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1994)' _computing_cell_refinement 'SAINT (Siemens, 1995)' _computing_data_reduction 'SAINT (Siemens, 1995)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1997)' _computing_publication_material 'SHELXTL (Sheldrick, 1997)' _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. The residual electron density peaks, Q1 and Q2 are rather large, 4.6 and 3.48e.A^-3 and are just less than 1 Angstrom from the Zirconium. These are probably due to some unresolved twinning or from using an inadequate absorption model to refine the data from the poorly diffracting crystal. ; _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^)+(0.1935P)^2^+16.2059P] 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 3944 _refine_ls_number_parameters 245 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1403 _refine_ls_R_factor_gt 0.1124 _refine_ls_wR_factor_ref 0.3184 _refine_ls_wR_factor_gt 0.2914 _refine_ls_goodness_of_fit_ref 1.085 _refine_ls_restrained_S_all 1.085 _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 Zr1 Zr 0.27111(9) 0.21088(5) 0.25427(7) 0.0281(4) Uani 1 1 d . . . Si1 Si 0.0377(3) 0.08416(14) 0.2523(2) 0.0281(6) Uani 1 1 d . . . N1 N 0.0888(9) 0.3110(5) 0.2478(7) 0.039(2) Uani 1 1 d . . . C1 C 0.0431(14) 0.3844(6) 0.2476(10) 0.054(3) Uani 1 1 d . . . H1A H 0.1058 0.4249 0.2488 0.065 Uiso 1 1 calc R . . N2 N 0.0609(9) 0.1824(5) 0.2462(7) 0.041(2) Uani 1 1 d . . . C2 C -0.0847(15) 0.4037(7) 0.2457(10) 0.059(3) Uani 1 1 d . . . H2A H -0.1113 0.4561 0.2451 0.071 Uiso 1 1 calc R . . N3 N 0.3408(10) 0.2691(5) 0.1282(7) 0.043(2) Uani 1 1 d . . . C3 C -0.1789(14) 0.3436(8) 0.2448(10) 0.061(4) Uani 1 1 d . . . H3A H -0.2700 0.3553 0.2448 0.074 Uiso 1 1 calc R . . C4 C -0.1377(11) 0.2677(6) 0.2440(9) 0.041(3) Uani 1 1 d . . . H4A H -0.2000 0.2270 0.2429 0.049 Uiso 1 1 calc R . . N4 N 0.3439(10) 0.2728(5) 0.3793(7) 0.042(2) Uani 1 1 d . . . C5 C -0.0018(10) 0.2517(6) 0.2448(7) 0.032(2) Uani 1 1 d . . . C6 C -0.0548(11) 0.0501(7) 0.3654(9) 0.048(3) Uani 1 1 d . . . H6A H -0.1474 0.0650 0.3564 0.071 Uiso 1 1 calc R . . H6B H -0.0166 0.0735 0.4279 0.071 Uiso 1 1 calc R . . H6C H -0.0484 -0.0061 0.3706 0.071 Uiso 1 1 calc R . . C7 C -0.0561(11) 0.0433(8) 0.1387(10) 0.052(3) Uani 1 1 d . . . H7A H -0.1497 0.0551 0.1434 0.078 Uiso 1 1 calc R . . H7B H -0.0440 -0.0127 0.1371 0.078 Uiso 1 1 calc R . . H7C H -0.0236 0.0659 0.0762 0.078 Uiso 1 1 calc R . . C8 C 0.2208(10) 0.0659(6) 0.2580(7) 0.030(2) Uani 1 1 d . . . C9 C 0.3050(11) 0.0816(5) 0.3467(7) 0.034(2) Uani 1 1 d . . . C10 C 0.4336(10) 0.1003(6) 0.3134(9) 0.041(3) Uani 1 1 d . . . C11 C 0.4310(9) 0.0970(6) 0.2064(8) 0.034(2) Uani 1 1 d . . . C12 C 0.3014(10) 0.0773(5) 0.1704(8) 0.034(2) Uani 1 1 d . . . C13 C 0.2606(13) 0.0571(8) 0.0603(8) 0.053(3) Uani 1 1 d . . . H13A H 0.2347 0.0029 0.0562 0.079 Uiso 1 1 calc R . . H13B H 0.3346 0.0661 0.0166 0.079 Uiso 1 1 calc R . . H13C H 0.1862 0.0895 0.0373 0.079 Uiso 1 1 calc R . . C14 C 0.5551(12) 0.1088(7) 0.1426(11) 0.058(4) Uani 1 1 d . . . H14A H 0.6044 0.0605 0.1402 0.087 Uiso 1 1 calc R . . H14B H 0.6110 0.1488 0.1744 0.087 Uiso 1 1 calc R . . H14C H 0.5279 0.1245 0.0731 0.087 Uiso 1 1 calc R . . C15 C 0.5539(12) 0.1118(8) 0.3837(10) 0.055(3) Uani 1 1 d . . . H15A H 0.5988 0.0625 0.3946 0.082 Uiso 1 1 calc R . . H15B H 0.5270 0.1321 0.4493 0.082 Uiso 1 1 calc R . . H15C H 0.6136 0.1484 0.3528 0.082 Uiso 1 1 calc R . . C16 C 0.2651(14) 0.0777(8) 0.4565(9) 0.057(3) Uani 1 1 d . . . H16A H 0.2237 0.0279 0.4689 0.085 Uiso 1 1 calc R . . H16B H 0.2027 0.1191 0.4693 0.085 Uiso 1 1 calc R . . H16C H 0.3432 0.0836 0.5022 0.085 Uiso 1 1 calc R . . C17 C 0.260(2) 0.2972(10) 0.4604(11) 0.081(5) Uani 1 1 d . . . H17A H 0.2824 0.2677 0.5225 0.122 Uiso 1 1 calc R . . H17B H 0.1678 0.2882 0.4394 0.122 Uiso 1 1 calc R . . H17C H 0.2737 0.3521 0.4740 0.122 Uiso 1 1 calc R . . C18 C 0.4787(17) 0.3005(10) 0.3991(14) 0.088(5) Uani 1 1 d . . . H18A H 0.5151 0.2778 0.4626 0.132 Uiso 1 1 calc R . . H18B H 0.4781 0.3567 0.4053 0.132 Uiso 1 1 calc R . . H18C H 0.5330 0.2856 0.3425 0.132 Uiso 1 1 calc R . . C19 C 0.3570(17) 0.2502(9) 0.0213(10) 0.068(4) Uani 1 1 d . . . H19A H 0.4491 0.2576 0.0049 0.102 Uiso 1 1 calc R . . H19B H 0.3008 0.2838 -0.0219 0.102 Uiso 1 1 calc R . . H19C H 0.3321 0.1964 0.0091 0.102 Uiso 1 1 calc R . . C20 C 0.363(2) 0.3523(8) 0.1411(13) 0.083(5) Uani 1 1 d . . . H20A H 0.4508 0.3655 0.1184 0.125 Uiso 1 1 calc R . . H20B H 0.3571 0.3660 0.2132 0.125 Uiso 1 1 calc R . . H20C H 0.2966 0.3808 0.1001 0.125 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 Zr1 0.0293(6) 0.0183(6) 0.0371(6) -0.0009(4) 0.0053(4) -0.0039(4) Si1 0.0292(14) 0.0193(13) 0.0360(15) 0.0010(10) 0.0034(10) -0.0001(10) N1 0.033(5) 0.018(4) 0.064(6) 0.000(4) -0.001(4) 0.003(3) C1 0.062(8) 0.017(5) 0.083(9) -0.002(5) 0.005(6) 0.000(5) N2 0.040(5) 0.017(4) 0.065(6) -0.001(4) 0.005(4) -0.001(4) C2 0.075(10) 0.025(6) 0.079(9) -0.002(6) 0.012(7) 0.008(6) N3 0.056(6) 0.022(4) 0.051(6) 0.010(4) 0.015(4) -0.002(4) C3 0.046(7) 0.051(8) 0.088(10) 0.007(7) 0.006(6) 0.031(7) C4 0.038(6) 0.026(5) 0.059(7) 0.002(5) 0.003(5) -0.002(4) N4 0.041(5) 0.030(5) 0.056(6) -0.014(4) 0.002(4) -0.001(4) C5 0.033(6) 0.028(5) 0.036(5) -0.001(4) 0.009(4) 0.007(4) C6 0.036(6) 0.045(7) 0.063(8) 0.014(6) 0.013(5) 0.005(5) C7 0.030(6) 0.065(8) 0.061(8) -0.014(6) -0.007(5) -0.004(5) C8 0.036(5) 0.021(5) 0.035(5) 0.001(4) 0.006(4) 0.001(4) C9 0.045(6) 0.025(5) 0.033(5) 0.007(4) 0.000(4) 0.006(4) C10 0.028(5) 0.028(5) 0.066(8) 0.007(5) -0.005(5) 0.002(4) C11 0.015(5) 0.027(5) 0.060(7) -0.005(4) 0.004(4) 0.001(4) C12 0.034(6) 0.016(5) 0.052(6) 0.001(4) 0.012(4) 0.005(4) C13 0.060(8) 0.063(8) 0.037(6) -0.014(6) 0.010(5) 0.012(7) C14 0.031(6) 0.043(7) 0.104(11) 0.002(7) 0.027(6) -0.002(5) C15 0.038(7) 0.057(8) 0.067(8) 0.000(6) -0.017(5) 0.000(6) C16 0.063(8) 0.067(9) 0.040(6) 0.016(6) -0.004(5) -0.005(7) C17 0.116(15) 0.088(12) 0.041(8) -0.014(7) 0.021(8) -0.001(10) C18 0.070(11) 0.082(12) 0.110(14) -0.030(10) -0.006(10) -0.020(9) C19 0.082(11) 0.072(10) 0.052(8) 0.014(7) 0.010(7) -0.003(8) C20 0.125(15) 0.041(8) 0.087(11) 0.006(7) 0.033(10) -0.006(9) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zr1 N4 2.049(9) . ? Zr1 N3 2.067(8) . ? Zr1 N2 2.173(9) . ? Zr1 N1 2.517(8) . ? Zr1 C9 2.542(9) . ? Zr1 C8 2.545(10) . ? Zr1 C12 2.567(9) . ? Zr1 C10 2.603(10) . ? Zr1 C11 2.628(9) . ? Zr1 C5 2.836(10) . ? Zr1 Si1 3.206(3) . ? Si1 N2 1.708(8) . ? Si1 C7 1.854(11) . ? Si1 C6 1.868(11) . ? Si1 C8 1.869(10) . ? N1 C1 1.344(13) . ? N1 C5 1.369(13) . ? C1 C2 1.330(19) . ? C1 H1A 0.9400 . ? N2 C5 1.350(13) . ? C2 C3 1.404(19) . ? C2 H2A 0.9400 . ? N3 C19 1.442(16) . ? N3 C20 1.457(16) . ? C3 C4 1.369(17) . ? C3 H3A 0.9400 . ? C4 C5 1.397(15) . ? C4 H4A 0.9400 . ? N4 C17 1.442(17) . ? N4 C18 1.452(19) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C6 H6C 0.9700 . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C7 H7C 0.9700 . ? C8 C9 1.425(14) . ? C8 C12 1.440(13) . ? C9 C10 1.422(15) . ? C9 C16 1.499(15) . ? C10 C11 1.388(16) . ? C10 C15 1.498(15) . ? C11 C12 1.409(14) . ? C11 C14 1.544(14) . ? C12 C13 1.510(15) . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C13 H13C 0.9700 . ? C14 H14A 0.9700 . ? C14 H14B 0.9700 . ? C14 H14C 0.9700 . ? C15 H15A 0.9700 . ? C15 H15B 0.9700 . ? C15 H15C 0.9700 . ? C16 H16A 0.9700 . ? C16 H16B 0.9700 . ? C16 H16C 0.9700 . ? C17 H17A 0.9700 . ? C17 H17B 0.9700 . ? C17 H17C 0.9700 . ? C18 H18A 0.9700 . ? C18 H18B 0.9700 . ? C18 H18C 0.9700 . ? C19 H19A 0.9700 . ? C19 H19B 0.9700 . ? C19 H19C 0.9700 . ? C20 H20A 0.9700 . ? C20 H20B 0.9700 . ? C20 H20C 0.9700 . ? 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 N4 Zr1 N3 104.7(4) . . ? N4 Zr1 N2 118.0(4) . . ? N3 Zr1 N2 115.8(4) . . ? N4 Zr1 N1 84.6(3) . . ? N3 Zr1 N1 85.2(3) . . ? N2 Zr1 N1 56.2(3) . . ? N4 Zr1 C9 92.6(3) . . ? N3 Zr1 C9 138.9(3) . . ? N2 Zr1 C9 86.3(3) . . ? N1 Zr1 C9 134.1(3) . . ? N4 Zr1 C8 123.9(3) . . ? N3 Zr1 C8 124.4(3) . . ? N2 Zr1 C8 65.5(3) . . ? N1 Zr1 C8 121.7(3) . . ? C9 Zr1 C8 32.5(3) . . ? N4 Zr1 C12 139.1(4) . . ? N3 Zr1 C12 92.7(3) . . ? N2 Zr1 C12 84.9(3) . . ? N1 Zr1 C12 134.4(3) . . ? C9 Zr1 C12 53.2(3) . . ? C8 Zr1 C12 32.7(3) . . ? N4 Zr1 C10 87.0(4) . . ? N3 Zr1 C10 110.8(4) . . ? N2 Zr1 C10 116.7(3) . . ? N1 Zr1 C10 163.4(3) . . ? C9 Zr1 C10 32.1(3) . . ? C8 Zr1 C10 53.3(3) . . ? C12 Zr1 C10 52.1(4) . . ? N4 Zr1 C11 111.9(3) . . ? N3 Zr1 C11 86.6(3) . . ? N2 Zr1 C11 115.3(3) . . ? N1 Zr1 C11 163.0(3) . . ? C9 Zr1 C11 52.3(3) . . ? C8 Zr1 C11 53.1(3) . . ? C12 Zr1 C11 31.4(3) . . ? C10 Zr1 C11 30.8(3) . . ? N4 Zr1 C5 102.6(3) . . ? N3 Zr1 C5 102.1(3) . . ? N2 Zr1 C5 27.4(3) . . ? N1 Zr1 C5 28.8(3) . . ? C9 Zr1 C5 110.3(3) . . ? C8 Zr1 C5 92.8(3) . . ? C12 Zr1 C5 109.7(3) . . ? C10 Zr1 C5 142.2(3) . . ? C11 Zr1 C5 141.1(3) . . ? N4 Zr1 Si1 126.6(3) . . ? N3 Zr1 Si1 126.7(3) . . ? N2 Zr1 Si1 29.9(2) . . ? N1 Zr1 Si1 86.0(2) . . ? C9 Zr1 Si1 59.5(3) . . ? C8 Zr1 Si1 35.6(2) . . ? C12 Zr1 Si1 59.3(2) . . ? C10 Zr1 Si1 87.5(2) . . ? C11 Zr1 Si1 87.1(2) . . ? C5 Zr1 Si1 57.2(2) . . ? N2 Si1 C7 113.8(6) . . ? N2 Si1 C6 114.9(5) . . ? C7 Si1 C6 104.5(6) . . ? N2 Si1 C8 91.8(4) . . ? C7 Si1 C8 115.8(5) . . ? C6 Si1 C8 116.3(5) . . ? N2 Si1 Zr1 39.3(3) . . ? C7 Si1 Zr1 127.7(4) . . ? C6 Si1 Zr1 126.8(4) . . ? C8 Si1 Zr1 52.5(3) . . ? C1 N1 C5 118.2(9) . . ? C1 N1 Zr1 153.2(8) . . ? C5 N1 Zr1 88.6(6) . . ? C2 C1 N1 124.5(12) . . ? C2 C1 H1A 117.7 . . ? N1 C1 H1A 117.7 . . ? C5 N2 Si1 144.1(8) . . ? C5 N2 Zr1 104.8(6) . . ? Si1 N2 Zr1 110.9(5) . . ? C1 C2 C3 118.1(11) . . ? C1 C2 H2A 121.0 . . ? C3 C2 H2A 121.0 . . ? C19 N3 C20 107.9(10) . . ? C19 N3 Zr1 135.2(8) . . ? C20 N3 Zr1 116.2(8) . . ? C4 C3 C2 119.8(12) . . ? C4 C3 H3A 120.1 . . ? C2 C3 H3A 120.1 . . ? C3 C4 C5 119.0(11) . . ? C3 C4 H4A 120.5 . . ? C5 C4 H4A 120.5 . . ? C17 N4 C18 110.4(12) . . ? C17 N4 Zr1 122.0(10) . . ? C18 N4 Zr1 127.6(9) . . ? N2 C5 N1 110.3(9) . . ? N2 C5 C4 129.3(10) . . ? N1 C5 C4 120.4(9) . . ? N2 C5 Zr1 47.8(5) . . ? N1 C5 Zr1 62.5(5) . . ? C4 C5 Zr1 176.4(8) . . ? Si1 C6 H6A 109.5 . . ? Si1 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? Si1 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? Si1 C7 H7A 109.5 . . ? Si1 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? Si1 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C9 C8 C12 106.0(9) . . ? C9 C8 Si1 123.5(7) . . ? C12 C8 Si1 122.5(7) . . ? C9 C8 Zr1 73.6(6) . . ? C12 C8 Zr1 74.5(5) . . ? Si1 C8 Zr1 91.8(4) . . ? C10 C9 C8 108.4(9) . . ? C10 C9 C16 125.9(10) . . ? C8 C9 C16 125.7(10) . . ? C10 C9 Zr1 76.3(6) . . ? C8 C9 Zr1 73.9(5) . . ? C16 C9 Zr1 116.9(7) . . ? C11 C10 C9 108.6(9) . . ? C11 C10 C15 126.4(10) . . ? C9 C10 C15 124.6(11) . . ? C11 C10 Zr1 75.6(6) . . ? C9 C10 Zr1 71.6(6) . . ? C15 C10 Zr1 124.4(8) . . ? C10 C11 C12 108.5(9) . . ? C10 C11 C14 123.5(10) . . ? C12 C11 C14 127.9(10) . . ? C10 C11 Zr1 73.6(6) . . ? C12 C11 Zr1 71.9(5) . . ? C14 C11 Zr1 123.3(7) . . ? C11 C12 C8 108.6(9) . . ? C11 C12 C13 125.3(9) . . ? C8 C12 C13 125.2(10) . . ? C11 C12 Zr1 76.7(6) . . ? C8 C12 Zr1 72.8(5) . . ? C13 C12 Zr1 125.0(7) . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 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 . . ? C10 C15 H15A 109.5 . . ? C10 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C10 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C9 C16 H16A 109.5 . . ? C9 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C9 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? N4 C17 H17A 109.5 . . ? N4 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? N4 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? N4 C18 H18A 109.5 . . ? N4 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? N4 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? N3 C19 H19A 109.5 . . ? N3 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? N3 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? N3 C20 H20A 109.5 . . ? N3 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? N3 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 4.613 _refine_diff_density_min -2.509 _refine_diff_density_rms 0.231