# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Aaron Odom' _publ_contact_author_email ODOM@CHEMISTRY.MSU.EDU _publ_section_title ; Zirconium Complexes Bearing a Tetradentate Dipyrrolyl Ligand ; loop_ _publ_author_name 'Aaron Odom' 'Eyal Barnea' # Attachment 'structures.cif' data_06033 _database_code_depnum_ccdc_archive 'CCDC 681307' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H32 N6 Zr' _chemical_formula_weight 423.72 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' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'x+1/4, -y+1/4, z+1/4' '-x+1/4, y+1/4, z+1/4' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' 'x+1/4, -y+3/4, z+3/4' '-x+1/4, y+3/4, z+3/4' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' 'x+3/4, -y+1/4, z+3/4' '-x+3/4, y+1/4, z+3/4' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' 'x+3/4, -y+3/4, z+1/4' '-x+3/4, y+3/4, z+1/4' _cell_length_a 29.985(4) _cell_length_b 10.0574(14) _cell_length_c 13.4896(19) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4068.1(10) _cell_formula_units_Z 8 _cell_measurement_temperature 172(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.33 _exptl_crystal_size_min 0.33 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.384 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1776 _exptl_absorpt_coefficient_mu 0.553 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 172(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8407 _diffrn_reflns_av_R_equivalents 0.0418 _diffrn_reflns_av_sigmaI/netI 0.0263 _diffrn_reflns_limit_h_min -33 _diffrn_reflns_limit_h_max 33 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.62 _diffrn_reflns_theta_max 23.28 _reflns_number_total 1469 _reflns_number_gt 1393 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _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^)+(0.0000P)^2^+53.4370P] 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 SHELXL _refine_ls_extinction_coef 0.00001(6) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.02(10) _refine_ls_number_reflns 1469 _refine_ls_number_parameters 115 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0440 _refine_ls_R_factor_gt 0.0421 _refine_ls_wR_factor_ref 0.0944 _refine_ls_wR_factor_gt 0.0939 _refine_ls_goodness_of_fit_ref 1.367 _refine_ls_restrained_S_all 1.367 _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 Zr Zr 0.0000 0.0000 0.80391(6) 0.0192(3) Uani 1 2 d S . . N1 N -0.03683(18) 0.1868(6) 0.8375(4) 0.0291(14) Uani 1 1 d . . . N2 N 0.04652(17) 0.0856(5) 0.7134(4) 0.0276(13) Uani 1 1 d . . . N11 N -0.0469(2) -0.0377(6) 0.9523(5) 0.0246(15) Uani 1 1 d . . . C11 C -0.0738(3) 0.1755(8) 0.8938(6) 0.027(2) Uani 1 1 d . . . C12 C -0.0930(3) 0.3006(8) 0.9084(5) 0.0366(19) Uani 1 1 d . . . H12A H -0.1185 0.3202 0.9448 0.044 Uiso 1 1 calc R . . C13 C -0.0658(3) 0.3899(8) 0.8570(6) 0.043(2) Uani 1 1 d . . . H13A H -0.0700 0.4814 0.8536 0.051 Uiso 1 1 calc R . . C14 C -0.0320(2) 0.3202(7) 0.8124(7) 0.0417(18) Uani 1 1 d . . . H14A H -0.0098 0.3558 0.7723 0.050 Uiso 1 1 calc R . . C21 C 0.0757(3) 0.2040(9) 0.7041(8) 0.040(2) Uani 1 1 d . . . H21A H 0.0919 0.1995 0.6428 0.060 Uiso 1 1 calc R . . H21B H 0.0964 0.2060 0.7585 0.060 Uiso 1 1 calc R . . H21C H 0.0578 0.2831 0.7051 0.060 Uiso 1 1 calc R . . C22 C 0.0572(3) -0.0044(8) 0.6319(7) 0.045(3) Uani 1 1 d . . . H22A H 0.0791 0.0361 0.5897 0.068 Uiso 1 1 calc R . . H22B H 0.0307 -0.0224 0.5943 0.068 Uiso 1 1 calc R . . H22C H 0.0688 -0.0862 0.6581 0.068 Uiso 1 1 calc R . . C111 C -0.0882(2) 0.0430(7) 0.9303(5) 0.0329(17) Uani 1 1 d . . . H11C H -0.1062 -0.0013 0.8804 0.039 Uiso 1 1 calc R . . H11D H -0.1061 0.0528 0.9899 0.039 Uiso 1 1 calc R . . C112 C -0.0244(2) 0.0216(8) 1.0418(5) 0.0392(18) Uani 1 1 d . . . H11A H -0.0390 -0.0089 1.1018 0.047 Uiso 1 1 calc R . . H11B H -0.0264 0.1179 1.0394 0.047 Uiso 1 1 calc R . . C113 C -0.0591(2) -0.1759(7) 0.9718(6) 0.0406(19) Uani 1 1 d . . . H11E H -0.0772 -0.1802 1.0305 0.061 Uiso 1 1 calc R . . H11F H -0.0326 -0.2279 0.9813 0.061 Uiso 1 1 calc R . . H11G H -0.0756 -0.2104 0.9165 0.061 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 Zr 0.0181(4) 0.0190(4) 0.0206(4) 0.000 0.000 0.0017(6) N1 0.033(3) 0.019(3) 0.035(4) -0.004(2) 0.001(2) 0.002(3) N2 0.025(3) 0.023(3) 0.035(3) 0.008(3) 0.004(3) -0.003(3) N11 0.020(3) 0.024(3) 0.029(4) -0.005(3) 0.007(3) 0.005(3) C11 0.023(4) 0.035(5) 0.023(4) -0.021(4) 0.003(3) 0.007(4) C12 0.037(4) 0.043(5) 0.029(4) -0.006(4) -0.005(3) 0.008(4) C13 0.055(5) 0.029(4) 0.045(5) -0.008(4) -0.018(4) 0.004(4) C14 0.043(4) 0.035(4) 0.047(5) -0.003(4) 0.004(4) 0.004(3) C21 0.044(6) 0.027(5) 0.048(6) 0.010(4) 0.001(5) -0.012(4) C22 0.054(7) 0.031(5) 0.052(6) -0.004(4) 0.034(5) -0.017(4) C111 0.033(4) 0.028(4) 0.038(4) -0.004(3) 0.006(3) 0.010(3) C112 0.048(4) 0.052(5) 0.018(4) -0.012(4) -0.005(3) 0.012(4) C113 0.037(4) 0.034(4) 0.051(5) 0.015(4) 0.015(4) 0.000(3) _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 Zr N2 2.044(5) 2 ? Zr N2 2.044(5) . ? Zr N1 2.226(5) . ? Zr N1 2.226(5) 2 ? Zr N11 2.475(6) 2 ? Zr N11 2.475(6) . ? N1 C11 1.348(10) . ? N1 C14 1.391(9) . ? N2 C22 1.460(10) . ? N2 C21 1.483(10) . ? N11 C113 1.462(9) . ? N11 C112 1.505(9) . ? N11 C111 1.512(9) . ? C11 C12 1.397(11) . ? C11 C111 1.485(11) . ? C12 C13 1.396(11) . ? C13 C14 1.372(10) . ? C112 C112 1.529(13) 2 ? 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 N2 Zr N2 106.6(3) 2 . ? N2 Zr N1 98.0(2) 2 . ? N2 Zr N1 96.0(2) . . ? N2 Zr N1 96.0(2) 2 2 ? N2 Zr N1 98.0(2) . 2 ? N1 Zr N1 156.5(3) . 2 ? N2 Zr N11 159.3(2) 2 2 ? N2 Zr N11 91.8(2) . 2 ? N1 Zr N11 89.3(2) . 2 ? N1 Zr N11 71.5(2) 2 2 ? N2 Zr N11 91.8(2) 2 . ? N2 Zr N11 159.3(2) . . ? N1 Zr N11 71.5(2) . . ? N1 Zr N11 89.3(2) 2 . ? N11 Zr N11 72.1(3) 2 . ? C11 N1 C14 107.7(6) . . ? C11 N1 Zr 116.8(5) . . ? C14 N1 Zr 135.4(5) . . ? C22 N2 C21 107.8(6) . . ? C22 N2 Zr 109.8(4) . . ? C21 N2 Zr 142.3(6) . . ? C113 N11 C112 110.2(6) . . ? C113 N11 C111 109.8(6) . . ? C112 N11 C111 108.1(5) . . ? C113 N11 Zr 115.8(5) . . ? C112 N11 Zr 109.5(4) . . ? C111 N11 Zr 103.0(4) . . ? N1 C11 C12 109.9(7) . . ? N1 C11 C111 120.2(7) . . ? C12 C11 C111 129.9(7) . . ? C13 C12 C11 105.7(7) . . ? C14 C13 C12 108.7(7) . . ? C13 C14 N1 107.9(7) . . ? C11 C111 N11 107.9(6) . . ? N11 C112 C112 108.4(5) . 2 ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 23.28 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.409 _refine_diff_density_min -1.316 _refine_diff_density_rms 0.099 #===END data_ebzrenpphnh2_0m _database_code_depnum_ccdc_archive 'CCDC 681308' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C26 H32 N6 Zr' _chemical_formula_weight 519.80 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' 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 Pccn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y, -z+1/2' '-x, y+1/2, -z+1/2' '-x+1/2, -y+1/2, z' '-x, -y, -z' '-x-1/2, y, z-1/2' 'x, -y-1/2, z-1/2' 'x-1/2, y-1/2, -z' _cell_length_a 12.0136(2) _cell_length_b 12.4957(2) _cell_length_c 16.9666(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2547.00(7) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 7346 _cell_measurement_theta_min 2.35 _cell_measurement_theta_max 27.41 _exptl_crystal_description ? _exptl_crystal_colour colourless _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.356 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1080 _exptl_absorpt_coefficient_mu 0.456 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 24698 _diffrn_reflns_av_R_equivalents 0.0619 _diffrn_reflns_av_sigmaI/netI 0.0475 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.35 _diffrn_reflns_theta_max 28.00 _reflns_number_total 3014 _reflns_number_gt 1859 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0375P)^2^+1.4748P] 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 SHELXL _refine_ls_extinction_coef 0.00017(17) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3014 _refine_ls_number_parameters 151 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0802 _refine_ls_R_factor_gt 0.0360 _refine_ls_wR_factor_ref 0.0899 _refine_ls_wR_factor_gt 0.0756 _refine_ls_goodness_of_fit_ref 0.993 _refine_ls_restrained_S_all 0.993 _refine_ls_shift/su_max 0.028 _refine_ls_shift/su_mean 0.002 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 0.2500 0.2500 0.465427(19) 0.02586(12) Uani 1 2 d S . . N1 N 0.2500(2) 0.38524(19) 0.39284(13) 0.0394(5) Uani 1 1 d . . . H1A H 0.1879 0.4223 0.3962 0.047 Uiso 1 1 calc R . . N2 N 0.42663(17) 0.22726(17) 0.48838(13) 0.0329(6) Uani 1 1 d . . . N3 N 0.29817(18) 0.35586(18) 0.57865(13) 0.0310(5) Uani 1 1 d . . . C9 C 0.6095(3) 0.1919(3) 0.4914(3) 0.0810(14) Uani 1 1 d . . . H9A H 0.6793 0.1583 0.4824 0.097 Uiso 1 1 calc R . . C8 C 0.5911(3) 0.2871(3) 0.5340(2) 0.0662(11) Uani 1 1 d . . . H8A H 0.6458 0.3293 0.5598 0.079 Uiso 1 1 calc R . . C4 C 0.4866(4) 0.5167(4) 0.23874(19) 0.0650(12) Uani 1 1 d . . . H4A H 0.5413 0.5464 0.2047 0.078 Uiso 1 1 calc R . . C5 C 0.4989(3) 0.4160(4) 0.26694(18) 0.0604(10) Uani 1 1 d . . . H5A H 0.5622 0.3751 0.2522 0.072 Uiso 1 1 calc R . . C3 C 0.3944(3) 0.5761(3) 0.25952(19) 0.0610(11) Uani 1 1 d . . . H3A H 0.3853 0.6464 0.2393 0.073 Uiso 1 1 calc R . . C13 C 0.2233(2) 0.4487(2) 0.5917(2) 0.0507(9) Uani 1 1 d . . . H13A H 0.2476 0.4881 0.6386 0.076 Uiso 1 1 calc R . . H13B H 0.1469 0.4233 0.5994 0.076 Uiso 1 1 calc R . . H13C H 0.2260 0.4961 0.5457 0.076 Uiso 1 1 calc R . . C10 C 0.5091(2) 0.1574(3) 0.46571(19) 0.0507(9) Uani 1 1 d . . . H10A H 0.4973 0.0938 0.4362 0.061 Uiso 1 1 calc R . . C2 C 0.3135(3) 0.5328(3) 0.31066(18) 0.0492(9) Uani 1 1 d . . . H2A H 0.2503 0.5741 0.3249 0.059 Uiso 1 1 calc R . . C6 C 0.4203(3) 0.3723(3) 0.31690(17) 0.0476(8) Uani 1 1 d . . . H6A H 0.4303 0.3014 0.3358 0.057 Uiso 1 1 calc R . . C12 C 0.2996(2) 0.2867(2) 0.64989(16) 0.0407(7) Uani 1 1 d . . . H12A H 0.2982 0.3320 0.6978 0.049 Uiso 1 1 calc R . . H12B H 0.3689 0.2438 0.6507 0.049 Uiso 1 1 calc R . . C1 C 0.3263(2) 0.4301(2) 0.34018(16) 0.0380(7) Uani 1 1 d . . . C11 C 0.4122(2) 0.3966(2) 0.56142(17) 0.0370(7) Uani 1 1 d . . . H11A H 0.4085 0.4545 0.5217 0.044 Uiso 1 1 calc R . . H11B H 0.4461 0.4260 0.6100 0.044 Uiso 1 1 calc R . . C7 C 0.4807(2) 0.3066(2) 0.53109(16) 0.0362(7) Uani 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 0.02277(16) 0.0340(2) 0.02085(17) 0.000 0.000 -0.00148(18) N1 0.0329(11) 0.0500(15) 0.0352(12) 0.0127(11) 0.0010(12) -0.0013(13) N2 0.0262(11) 0.0412(15) 0.0314(12) -0.0110(10) -0.0025(9) 0.0044(10) N3 0.0301(11) 0.0347(14) 0.0282(12) -0.0094(10) 0.0031(10) 0.0043(11) C9 0.0262(16) 0.086(3) 0.131(4) -0.059(3) -0.010(2) 0.0150(19) C8 0.0309(16) 0.074(3) 0.094(3) -0.047(2) -0.0060(18) -0.0020(16) C4 0.071(3) 0.093(4) 0.031(2) 0.000(2) -0.0018(19) -0.039(3) C5 0.059(2) 0.085(3) 0.036(2) -0.0014(19) 0.0103(16) -0.020(2) C3 0.087(3) 0.060(2) 0.0368(19) 0.0184(17) -0.0237(19) -0.041(2) C13 0.046(2) 0.045(2) 0.061(2) -0.0231(17) 0.0092(15) 0.0102(14) C10 0.0331(15) 0.052(2) 0.067(2) -0.0301(18) 0.0007(16) 0.0081(14) C2 0.059(2) 0.053(2) 0.0357(17) 0.0069(16) -0.0167(15) -0.0194(18) C6 0.055(2) 0.057(2) 0.0318(16) -0.0031(15) 0.0073(15) -0.0183(17) C12 0.0403(15) 0.058(2) 0.0234(14) -0.0040(13) -0.0022(13) -0.0004(14) C1 0.0451(16) 0.0473(19) 0.0215(14) 0.0035(14) -0.0080(13) -0.0163(15) C11 0.0333(15) 0.0378(18) 0.0398(16) -0.0116(14) 0.0027(13) -0.0068(13) C7 0.0294(13) 0.0424(17) 0.0369(16) -0.0128(15) 0.0019(13) -0.0025(13) _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 N1 2.091(2) . ? Zr1 N1 2.091(2) 4 ? Zr1 N2 2.176(2) . ? Zr1 N2 2.176(2) 4 ? Zr1 N3 2.403(2) . ? Zr1 N3 2.403(2) 4 ? N1 C1 1.398(3) . ? N1 H1A 0.8800 . ? N2 C10 1.376(3) . ? N2 C7 1.390(3) . ? N3 C12 1.486(3) . ? N3 C11 1.491(3) . ? N3 C13 1.485(3) . ? C9 C10 1.353(4) . ? C9 C8 1.409(5) . ? C9 H9A 0.9500 . ? C8 C7 1.349(4) . ? C8 H8A 0.9500 . ? C4 C5 1.354(5) . ? C4 C3 1.378(5) . ? C4 H4A 0.9500 . ? C5 C6 1.382(4) . ? C5 H5A 0.9500 . ? C3 C2 1.410(5) . ? C3 H3A 0.9500 . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C10 H10A 0.9500 . ? C2 C1 1.385(4) . ? C2 H2A 0.9500 . ? C6 C1 1.398(4) . ? C6 H6A 0.9500 . ? C12 C12 1.504(6) 4 ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C11 C7 1.485(4) . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? 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 N1 Zr1 N1 107.83(13) . 4 ? N1 Zr1 N2 102.18(9) . . ? N1 Zr1 N2 89.99(9) 4 . ? N1 Zr1 N2 89.99(9) . 4 ? N1 Zr1 N2 102.19(9) 4 4 ? N2 Zr1 N2 159.38(12) . 4 ? N1 Zr1 N3 91.49(8) . . ? N1 Zr1 N3 156.29(9) 4 . ? N2 Zr1 N3 72.18(7) . . ? N2 Zr1 N3 91.14(8) 4 . ? N1 Zr1 N3 156.29(9) . 4 ? N1 Zr1 N3 91.49(8) 4 4 ? N2 Zr1 N3 91.14(8) . 4 ? N2 Zr1 N3 72.18(7) 4 4 ? N3 Zr1 N3 73.86(11) . 4 ? C1 N1 Zr1 134.5(2) . . ? C1 N1 H1A 112.8 . . ? Zr1 N1 H1A 112.8 . . ? C10 N2 C7 105.2(2) . . ? C10 N2 Zr1 137.35(18) . . ? C7 N2 Zr1 117.13(17) . . ? C12 N3 C11 110.3(2) . . ? C12 N3 C13 109.9(2) . . ? C11 N3 C13 108.6(2) . . ? C12 N3 Zr1 109.45(16) . . ? C11 N3 Zr1 104.64(15) . . ? C13 N3 Zr1 113.81(17) . . ? C10 C9 C8 107.1(3) . . ? C10 C9 H9A 126.5 . . ? C8 C9 H9A 126.5 . . ? C7 C8 C9 106.8(3) . . ? C7 C8 H8A 126.6 . . ? C9 C8 H8A 126.6 . . ? C5 C4 C3 119.8(4) . . ? C5 C4 H4A 120.1 . . ? C3 C4 H4A 120.1 . . ? C4 C5 C6 120.6(4) . . ? C4 C5 H5A 119.7 . . ? C6 C5 H5A 119.7 . . ? C4 C3 C2 120.3(4) . . ? C4 C3 H3A 119.8 . . ? C2 C3 H3A 119.8 . . ? 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 . . ? C9 C10 N2 110.5(3) . . ? C9 C10 H10A 124.8 . . ? N2 C10 H10A 124.8 . . ? C1 C2 C3 120.1(4) . . ? C1 C2 H2A 120.0 . . ? C3 C2 H2A 120.0 . . ? C5 C6 C1 121.4(3) . . ? C5 C6 H6A 119.3 . . ? C1 C6 H6A 119.3 . . ? N3 C12 C12 110.2(2) . 4 ? N3 C12 H12A 109.6 . . ? C12 C12 H12A 109.6 4 . ? N3 C12 H12B 109.6 . . ? C12 C12 H12B 109.6 4 . ? H12A C12 H12B 108.1 . . ? C2 C1 C6 117.8(3) . . ? C2 C1 N1 122.0(3) . . ? C6 C1 N1 120.2(3) . . ? C7 C11 N3 108.6(2) . . ? C7 C11 H11A 110.0 . . ? N3 C11 H11A 110.0 . . ? C7 C11 H11B 110.0 . . ? N3 C11 H11B 110.0 . . ? H11A C11 H11B 108.4 . . ? C8 C7 N2 110.5(3) . . ? C8 C7 C11 132.0(3) . . ? N2 C7 C11 117.5(2) . . ? 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 N1 Zr1 N1 C1 -66.9(2) 4 . . . ? N2 Zr1 N1 C1 27.1(3) . . . . ? N2 Zr1 N1 C1 -169.7(3) 4 . . . ? N3 Zr1 N1 C1 99.2(3) . . . . ? N3 Zr1 N1 C1 150.0(2) 4 . . . ? N1 Zr1 N2 C10 -106.9(3) . . . . ? N1 Zr1 N2 C10 1.3(3) 4 . . . ? N2 Zr1 N2 C10 128.1(3) 4 . . . ? N3 Zr1 N2 C10 165.4(3) . . . . ? N3 Zr1 N2 C10 92.8(3) 4 . . . ? N1 Zr1 N2 C7 65.1(2) . . . . ? N1 Zr1 N2 C7 173.4(2) 4 . . . ? N2 Zr1 N2 C7 -59.84(19) 4 . . . ? N3 Zr1 N2 C7 -22.50(19) . . . . ? N3 Zr1 N2 C7 -95.1(2) 4 . . . ? N1 Zr1 N3 C12 176.05(18) . . . . ? N1 Zr1 N3 C12 -38.7(3) 4 . . . ? N2 Zr1 N3 C12 -81.63(17) . . . . ? N2 Zr1 N3 C12 86.03(17) 4 . . . ? N3 Zr1 N3 C12 14.96(13) 4 . . . ? N1 Zr1 N3 C11 -65.70(17) . . . . ? N1 Zr1 N3 C11 79.5(3) 4 . . . ? N2 Zr1 N3 C11 36.62(16) . . . . ? N2 Zr1 N3 C11 -155.72(16) 4 . . . ? N3 Zr1 N3 C11 133.2(2) 4 . . . ? N1 Zr1 N3 C13 52.7(2) . . . . ? N1 Zr1 N3 C13 -162.1(2) 4 . . . ? N2 Zr1 N3 C13 155.0(2) . . . . ? N2 Zr1 N3 C13 -37.3(2) 4 . . . ? N3 Zr1 N3 C13 -108.4(2) 4 . . . ? C10 C9 C8 C7 -1.0(5) . . . . ? C3 C4 C5 C6 -0.5(5) . . . . ? C5 C4 C3 C2 0.7(5) . . . . ? C8 C9 C10 N2 1.3(5) . . . . ? C7 N2 C10 C9 -1.1(4) . . . . ? Zr1 N2 C10 C9 171.6(3) . . . . ? C4 C3 C2 C1 -0.1(5) . . . . ? C4 C5 C6 C1 -0.3(5) . . . . ? C11 N3 C12 C12 -158.1(3) . . . 4 ? C13 N3 C12 C12 82.2(3) . . . 4 ? Zr1 N3 C12 C12 -43.5(3) . . . 4 ? C3 C2 C1 C6 -0.6(4) . . . . ? C3 C2 C1 N1 178.0(3) . . . . ? C5 C6 C1 C2 0.8(4) . . . . ? C5 C6 C1 N1 -177.9(3) . . . . ? Zr1 N1 C1 C2 -167.1(2) . . . . ? Zr1 N1 C1 C6 11.5(4) . . . . ? C12 N3 C11 C7 72.0(3) . . . . ? C13 N3 C11 C7 -167.6(2) . . . . ? Zr1 N3 C11 C7 -45.7(2) . . . . ? C9 C8 C7 N2 0.3(5) . . . . ? C9 C8 C7 C11 -176.8(4) . . . . ? C10 N2 C7 C8 0.5(4) . . . . ? Zr1 N2 C7 C8 -174.0(2) . . . . ? C10 N2 C7 C11 178.0(3) . . . . ? Zr1 N2 C7 C11 3.6(3) . . . . ? N3 C11 C7 C8 -151.8(4) . . . . ? N3 C11 C7 N2 31.3(3) . . . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.326 _refine_diff_density_min -0.386 _refine_diff_density_rms 0.066