# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2014 data_shelxl _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common MP0229 _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C44 H37 Cl Hf N4 O' _chemical_formula_weight 851.72 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Hf Hf -0.5830 6.1852 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 30.972(3) _cell_length_b 15.6087(11) _cell_length_c 18.9592(13) _cell_angle_alpha 90.00 _cell_angle_beta 93.149(4) _cell_angle_gamma 90.00 _cell_volume 9151.7(12) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 9869 _cell_measurement_theta_min 2.37 _cell_measurement_theta_max 25.03 _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.04 _exptl_crystal_size_mid 0.02 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.236 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3408 _exptl_absorpt_coefficient_mu 2.371 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9111 _exptl_absorpt_correction_T_max 0.9767 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_reflns_number 86622 _diffrn_reflns_av_R_equivalents 0.1007 _diffrn_reflns_av_sigmaI/netI 0.0650 _diffrn_reflns_limit_h_min -37 _diffrn_reflns_limit_h_max 37 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.46 _diffrn_reflns_theta_max 25.45 _reflns_number_total 8425 _reflns_number_gt 6167 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution SIR-2004 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics ORTEP-32 _computing_publication_material WinGX _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^)+(0.0572P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 8425 _refine_ls_number_parameters 472 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0685 _refine_ls_R_factor_gt 0.0436 _refine_ls_wR_factor_ref 0.1067 _refine_ls_wR_factor_gt 0.0995 _refine_ls_goodness_of_fit_ref 1.025 _refine_ls_restrained_S_all 1.025 _refine_ls_shift/su_max 0.019 _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 C1 C 0.08778(18) 0.3090(3) 0.1345(3) 0.0311(13) Uani 1 1 d . . . C2 C 0.13189(19) 0.3298(4) 0.1392(3) 0.0383(14) Uani 1 1 d . . . H2 H 0.1442 0.3849 0.1329 0.046 Uiso 1 1 calc R . . C3 C 0.1541(2) 0.2545(4) 0.1547(3) 0.0441(16) Uani 1 1 d . . . H3 H 0.1845 0.2490 0.1625 0.053 Uiso 1 1 calc R . . C4 C 0.12352(19) 0.1871(4) 0.1569(3) 0.0355(14) Uani 1 1 d . . . C5 C 0.1288(2) 0.0978(4) 0.1620(3) 0.0407(16) Uani 1 1 d . . . C6 C 0.0945(2) 0.0398(4) 0.1492(3) 0.0377(15) Uani 1 1 d . . . C7 C 0.0966(3) -0.0509(4) 0.1482(3) 0.0498(18) Uani 1 1 d . . . H7 H 0.1221 -0.0842 0.1569 0.060 Uiso 1 1 calc R . . C8 C 0.0568(2) -0.0822(4) 0.1329(3) 0.0441(17) Uani 1 1 d . . . H8 H 0.0492 -0.1411 0.1294 0.053 Uiso 1 1 calc R . . C9 C 0.0278(2) -0.0112(3) 0.1230(3) 0.0328(14) Uani 1 1 d . . . C10 C -0.0162(2) -0.0133(3) 0.1040(3) 0.0317(14) Uani 1 1 d . . . C11 C -0.04233(19) 0.0583(3) 0.0858(2) 0.0286(13) Uani 1 1 d . . . C12 C -0.0851(2) 0.0585(3) 0.0546(3) 0.0362(15) Uani 1 1 d . . . H12 H -0.1023 0.0092 0.0446 0.043 Uiso 1 1 calc R . . C13 C -0.09734(19) 0.1408(3) 0.0415(3) 0.0344(14) Uani 1 1 d . . . H13 H -0.1244 0.1588 0.0206 0.041 Uiso 1 1 calc R . . C14 C -0.06229(18) 0.1956(3) 0.0647(3) 0.0272(13) Uani 1 1 d . . . C15 C -0.06010(18) 0.2854(3) 0.0600(2) 0.0246(12) Uani 1 1 d . . . C16 C -0.02244(18) 0.3320(3) 0.0789(3) 0.0267(12) Uani 1 1 d . . . C17 C -0.01026(19) 0.4185(3) 0.0631(3) 0.0307(13) Uani 1 1 d . . . H17 H -0.0287 0.4614 0.0425 0.037 Uiso 1 1 calc R . . C18 C 0.0327(2) 0.4281(3) 0.0828(3) 0.0338(14) Uani 1 1 d . . . H18 H 0.0495 0.4781 0.0767 0.041 Uiso 1 1 calc R . . C19 C 0.04746(19) 0.3499(3) 0.1138(3) 0.0291(13) Uani 1 1 d . . . C20 C 0.1743(2) 0.0670(4) 0.1768(3) 0.0462(17) Uani 1 1 d . . . C21 C 0.1899(2) 0.0518(4) 0.2469(3) 0.056(2) Uani 1 1 d . . . C22 C 0.2337(3) 0.0329(5) 0.2588(3) 0.067(2) Uani 1 1 d . . . H22 H 0.2442 0.0216 0.3059 0.080 Uiso 1 1 calc R . . C23 C 0.2626(2) 0.0298(5) 0.2059(4) 0.068(2) Uani 1 1 d . . . C24 C 0.2457(2) 0.0411(5) 0.1383(3) 0.067(2) Uani 1 1 d . . . H24 H 0.2646 0.0367 0.1006 0.081 Uiso 1 1 calc R . . C25 C 0.2018(2) 0.0589(5) 0.1224(3) 0.057(2) Uani 1 1 d . . . C26 C 0.1597(3) 0.0567(5) 0.3060(3) 0.077(3) Uani 1 1 d . . . H26A H 0.1402 0.0072 0.3037 0.115 Uiso 1 1 calc R . . H26B H 0.1427 0.1096 0.3017 0.115 Uiso 1 1 calc R . . H26C H 0.1765 0.0566 0.3514 0.115 Uiso 1 1 calc R . . C27 C 0.3098(2) 0.0150(6) 0.2236(4) 0.085(3) Uani 1 1 d . . . H27A H 0.3256 0.0164 0.1802 0.128 Uiso 1 1 calc R . . H27B H 0.3138 -0.0410 0.2464 0.128 Uiso 1 1 calc R . . H27C H 0.3209 0.0600 0.2558 0.128 Uiso 1 1 calc R . . C28 C 0.1863(2) 0.0697(6) 0.0460(3) 0.079(3) Uani 1 1 d . . . H28A H 0.1628 0.0291 0.0346 0.118 Uiso 1 1 calc R . . H28B H 0.2102 0.0586 0.0156 0.118 Uiso 1 1 calc R . . H28C H 0.1757 0.1283 0.0383 0.118 Uiso 1 1 calc R . . C29 C -0.0607(3) -0.1222(4) 0.1647(3) 0.068(2) Uani 1 1 d . . . H29 H -0.0606 -0.0844 0.2039 0.082 Uiso 1 1 calc R . . C30 C -0.0819(3) -0.1989(4) 0.1685(4) 0.075(3) Uani 1 1 d . . . H30 H -0.0963 -0.2141 0.2097 0.090 Uiso 1 1 calc R . . C31 C -0.0819(3) -0.2536(4) 0.1117(3) 0.058(2) Uani 1 1 d . . . C32 C -0.0609(3) -0.2329(4) 0.0526(3) 0.055(2) Uani 1 1 d . . . H32 H -0.0607 -0.2715 0.0139 0.066 Uiso 1 1 calc R . . C33 C -0.0402(2) -0.1552(4) 0.0500(3) 0.0443(17) Uani 1 1 d . . . H33 H -0.0261 -0.1406 0.0085 0.053 Uiso 1 1 calc R . . C34 C -0.0392(2) -0.0977(3) 0.1050(3) 0.0400(16) Uani 1 1 d . . . C35 C -0.1065(3) -0.3866(5) 0.0619(4) 0.093(3) Uani 1 1 d . . . H35A H -0.1244 -0.3596 0.0238 0.139 Uiso 1 1 calc R . . H35B H -0.1196 -0.4411 0.0749 0.139 Uiso 1 1 calc R . . H35C H -0.0775 -0.3971 0.0456 0.139 Uiso 1 1 calc R . . C36 C -0.09869(18) 0.3335(3) 0.0294(3) 0.0297(13) Uani 1 1 d . . . C37 C -0.10065(19) 0.3595(3) -0.0420(3) 0.0308(13) Uani 1 1 d . . . C38 C -0.13514(19) 0.4080(3) -0.0673(3) 0.0332(14) Uani 1 1 d . . . H38 H -0.1361 0.4267 -0.1151 0.040 Uiso 1 1 calc R . . C39 C -0.16828(19) 0.4303(4) -0.0257(3) 0.0383(15) Uani 1 1 d . . . C40 C -0.1668(2) 0.4018(4) 0.0433(3) 0.0442(16) Uani 1 1 d . . . H40 H -0.1899 0.4158 0.0722 0.053 Uiso 1 1 calc R . . C41 C -0.1325(2) 0.3532(4) 0.0717(3) 0.0366(14) Uani 1 1 d . . . C42 C -0.0655(2) 0.3329(3) -0.0904(3) 0.0416(16) Uani 1 1 d . . . H42A H -0.0751 0.3446 -0.1396 0.062 Uiso 1 1 calc R . . H42B H -0.0597 0.2715 -0.0846 0.062 Uiso 1 1 calc R . . H42C H -0.0391 0.3654 -0.0783 0.062 Uiso 1 1 calc R . . C43 C -0.2062(2) 0.4846(5) -0.0551(4) 0.065(2) Uani 1 1 d . . . H43A H -0.2334 0.4551 -0.0470 0.097 Uiso 1 1 calc R . . H43B H -0.2037 0.4933 -0.1059 0.097 Uiso 1 1 calc R . . H43C H -0.2059 0.5403 -0.0311 0.097 Uiso 1 1 calc R . . C44 C -0.1321(2) 0.3244(4) 0.1481(3) 0.0481(17) Uani 1 1 d . . . H44A H -0.1086 0.3535 0.1754 0.072 Uiso 1 1 calc R . . H44B H -0.1275 0.2623 0.1506 0.072 Uiso 1 1 calc R . . H44C H -0.1598 0.3387 0.1678 0.072 Uiso 1 1 calc R . . N1 N 0.08276(14) 0.2233(3) 0.1468(2) 0.0293(11) Uani 1 1 d . . . N2 N 0.05141(15) 0.0639(3) 0.1340(2) 0.0316(11) Uani 1 1 d . . . N3 N -0.02886(14) 0.1433(2) 0.0928(2) 0.0249(10) Uani 1 1 d . . . N4 N 0.01274(13) 0.2931(3) 0.1119(2) 0.0231(10) Uani 1 1 d . . . O1 O -0.1037(2) -0.3320(3) 0.1209(3) 0.0817(19) Uani 1 1 d . . . Cl1 Cl -0.03580(13) 0.2381(2) 0.22731(18) 0.0979(11) Uani 0.67 1 d P . . Cl2 Cl 0.0000 0.0901(3) 0.2500 0.0960(17) Uani 0.67 2 d SP . . Hf1 Hf 0.020479(7) 0.176218(12) 0.171987(11) 0.02411(9) 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 C1 0.032(4) 0.032(3) 0.029(3) 0.001(2) -0.003(3) -0.002(3) C2 0.036(4) 0.042(4) 0.036(4) -0.001(3) 0.000(3) -0.004(3) C3 0.035(4) 0.060(4) 0.036(4) 0.000(3) -0.005(3) 0.012(3) C4 0.029(3) 0.048(4) 0.029(3) 0.003(3) 0.000(3) 0.005(3) C5 0.055(4) 0.040(4) 0.026(3) -0.001(3) -0.003(3) 0.025(3) C6 0.054(4) 0.036(3) 0.024(3) -0.007(3) 0.003(3) 0.012(3) C7 0.080(6) 0.032(3) 0.036(4) -0.007(3) -0.007(4) 0.031(4) C8 0.080(5) 0.022(3) 0.030(3) -0.009(2) 0.002(3) 0.018(3) C9 0.057(4) 0.019(3) 0.021(3) -0.004(2) -0.001(3) 0.006(3) C10 0.061(5) 0.018(3) 0.017(3) -0.004(2) 0.004(3) 0.003(3) C11 0.048(4) 0.025(3) 0.012(3) -0.001(2) -0.004(3) -0.007(3) C12 0.055(4) 0.025(3) 0.028(3) -0.006(2) -0.006(3) -0.009(3) C13 0.039(4) 0.037(3) 0.027(3) 0.003(3) -0.009(3) -0.008(3) C14 0.036(3) 0.029(3) 0.017(3) 0.003(2) -0.003(2) -0.002(2) C15 0.035(3) 0.024(3) 0.015(3) 0.005(2) 0.002(2) -0.001(2) C16 0.034(3) 0.029(3) 0.017(3) 0.005(2) 0.004(2) 0.003(2) C17 0.043(4) 0.022(3) 0.026(3) 0.003(2) -0.003(3) 0.000(3) C18 0.045(4) 0.028(3) 0.028(3) 0.000(2) -0.003(3) -0.010(3) C19 0.038(4) 0.028(3) 0.021(3) 0.003(2) 0.000(3) -0.003(3) C20 0.047(4) 0.055(4) 0.036(4) -0.003(3) -0.004(3) 0.016(3) C21 0.071(5) 0.068(5) 0.028(4) -0.008(3) -0.009(3) 0.037(4) C22 0.080(6) 0.085(5) 0.033(4) -0.004(4) -0.023(4) 0.040(5) C23 0.065(5) 0.094(6) 0.043(4) -0.022(4) -0.017(4) 0.050(4) C24 0.054(5) 0.108(6) 0.040(4) -0.021(4) -0.006(4) 0.040(4) C25 0.049(5) 0.087(5) 0.035(4) -0.013(3) -0.004(3) 0.032(4) C26 0.096(7) 0.092(6) 0.041(4) 0.007(4) -0.005(4) 0.038(5) C27 0.066(6) 0.120(7) 0.067(5) -0.016(5) -0.023(4) 0.056(5) C28 0.051(5) 0.144(8) 0.040(4) -0.009(4) -0.002(4) 0.040(5) C29 0.134(8) 0.039(4) 0.034(4) -0.013(3) 0.030(4) -0.023(4) C30 0.153(9) 0.029(4) 0.048(5) -0.006(3) 0.039(5) -0.021(4) C31 0.096(6) 0.029(3) 0.050(4) -0.006(3) 0.025(4) -0.015(4) C32 0.112(6) 0.022(3) 0.033(4) -0.014(3) 0.018(4) -0.016(4) C33 0.079(5) 0.034(3) 0.021(3) -0.011(2) 0.010(3) -0.013(3) C34 0.068(5) 0.022(3) 0.030(3) -0.003(2) 0.004(3) -0.001(3) C35 0.147(9) 0.049(5) 0.088(6) -0.037(4) 0.052(6) -0.045(5) C36 0.034(3) 0.024(3) 0.030(3) 0.004(2) -0.005(3) -0.002(2) C37 0.041(4) 0.018(3) 0.032(3) -0.003(2) -0.006(3) -0.001(3) C38 0.046(4) 0.030(3) 0.023(3) 0.001(2) -0.007(3) 0.008(3) C39 0.037(4) 0.038(3) 0.038(4) 0.009(3) -0.013(3) 0.005(3) C40 0.039(4) 0.048(4) 0.044(4) 0.003(3) -0.005(3) 0.005(3) C41 0.038(4) 0.037(3) 0.034(4) 0.002(3) -0.005(3) 0.003(3) C42 0.063(5) 0.033(3) 0.029(3) 0.006(3) 0.007(3) 0.010(3) C43 0.053(5) 0.083(5) 0.056(5) 0.010(4) -0.014(4) 0.019(4) C44 0.044(4) 0.069(5) 0.032(4) 0.009(3) 0.006(3) 0.015(3) N1 0.026(3) 0.028(2) 0.034(3) -0.003(2) 0.002(2) 0.008(2) N2 0.041(3) 0.026(2) 0.028(3) -0.0048(19) 0.002(2) 0.013(2) N3 0.038(3) 0.015(2) 0.021(2) 0.0001(18) -0.003(2) -0.0001(19) N4 0.021(3) 0.022(2) 0.027(2) 0.0041(18) 0.000(2) -0.0002(18) O1 0.147(5) 0.029(2) 0.075(4) -0.017(2) 0.060(4) -0.035(3) Cl1 0.109(3) 0.105(3) 0.081(2) 0.012(2) 0.015(2) 0.025(2) Cl2 0.141(5) 0.067(3) 0.082(3) 0.000 0.027(3) 0.000 Hf1 0.03345(15) 0.01794(12) 0.02058(14) -0.00035(9) -0.00175(10) 0.00287(10) _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 C1 N1 1.369(6) . ? C1 C2 1.402(8) . ? C1 C19 1.438(8) . ? C2 C3 1.385(8) . ? C3 C4 1.418(8) . ? C4 N1 1.387(7) . ? C4 C5 1.405(7) . ? C5 C6 1.408(8) . ? C5 C20 1.500(8) . ? C6 N2 1.400(7) . ? C6 C7 1.418(8) . ? C7 C8 1.344(9) . ? C8 C9 1.432(8) . ? C9 C10 1.391(8) . ? C9 N2 1.391(7) . ? C10 C11 1.412(7) . ? C10 C34 1.499(7) . ? C11 N3 1.394(6) . ? C11 C12 1.420(8) . ? C12 C13 1.358(7) . ? C13 C14 1.432(7) . ? C14 N3 1.400(7) . ? C14 C15 1.407(7) . ? C15 C16 1.405(7) . ? C15 C36 1.501(7) . ? C16 N4 1.369(7) . ? C16 C17 1.438(7) . ? C17 C18 1.369(8) . ? C18 C19 1.419(7) . ? C19 N4 1.393(7) . ? C20 C25 1.379(8) . ? C20 C21 1.409(8) . ? C21 C22 1.393(9) . ? C21 C26 1.502(9) . ? C22 C23 1.382(10) . ? C23 C24 1.368(9) . ? C23 C27 1.500(10) . ? C24 C25 1.406(9) . ? C25 C28 1.510(9) . ? C29 C30 1.369(9) . ? C29 C34 1.397(8) . ? C30 C31 1.374(8) . ? C31 C32 1.364(8) . ? C31 O1 1.414(7) . ? C32 C33 1.374(8) . ? C33 C34 1.375(7) . ? C35 O1 1.405(7) . ? C36 C41 1.389(8) . ? C36 C37 1.411(7) . ? C37 C38 1.374(7) . ? C37 C42 1.520(8) . ? C38 C39 1.373(8) . ? C39 C40 1.380(8) . ? C39 C43 1.529(8) . ? C40 C41 1.389(8) . ? C41 C44 1.517(8) . ? N1 Hf1 2.142(4) . ? N2 Hf1 2.141(4) . ? N3 Hf1 2.146(4) . ? N4 Hf1 2.157(4) . ? Cl1 Hf1 2.169(3) 2 ? Cl1 Hf1 2.296(4) . ? Cl1 Cl1 2.334(8) 2 ? Cl2 Hf1 2.121(3) 2 ? Cl2 Hf1 2.121(3) . ? Hf1 Cl1 2.169(3) 2 ? Hf1 Hf1 3.2821(5) 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 N1 C1 C2 109.6(5) . . ? N1 C1 C19 112.1(5) . . ? C2 C1 C19 138.0(5) . . ? C3 C2 C1 106.7(5) . . ? C2 C3 C4 108.2(6) . . ? N1 C4 C5 121.0(5) . . ? N1 C4 C3 107.3(5) . . ? C5 C4 C3 131.5(6) . . ? C4 C5 C6 122.8(6) . . ? C4 C5 C20 115.8(6) . . ? C6 C5 C20 121.2(5) . . ? N2 C6 C5 124.4(5) . . ? N2 C6 C7 108.1(6) . . ? C5 C6 C7 127.5(6) . . ? C8 C7 C6 108.8(6) . . ? C7 C8 C9 108.0(5) . . ? C10 C9 N2 123.9(5) . . ? C10 C9 C8 127.9(5) . . ? N2 C9 C8 108.2(5) . . ? C9 C10 C11 125.8(5) . . ? C9 C10 C34 118.5(5) . . ? C11 C10 C34 115.6(5) . . ? N3 C11 C10 124.4(5) . . ? N3 C11 C12 107.8(5) . . ? C10 C11 C12 127.8(5) . . ? C13 C12 C11 108.9(5) . . ? C12 C13 C14 108.0(5) . . ? N3 C14 C15 124.6(5) . . ? N3 C14 C13 107.5(4) . . ? C15 C14 C13 127.9(5) . . ? C16 C15 C14 122.8(5) . . ? C16 C15 C36 118.2(4) . . ? C14 C15 C36 118.9(5) . . ? N4 C16 C15 121.0(5) . . ? N4 C16 C17 107.5(5) . . ? C15 C16 C17 131.0(5) . . ? C18 C17 C16 107.9(5) . . ? C17 C18 C19 107.8(5) . . ? N4 C19 C18 107.8(5) . . ? N4 C19 C1 112.4(4) . . ? C18 C19 C1 138.6(5) . . ? C25 C20 C21 119.6(6) . . ? C25 C20 C5 120.1(5) . . ? C21 C20 C5 120.1(6) . . ? C22 C21 C20 118.1(6) . . ? C22 C21 C26 122.0(6) . . ? C20 C21 C26 120.0(6) . . ? C23 C22 C21 123.5(6) . . ? C24 C23 C22 116.6(7) . . ? C24 C23 C27 123.1(7) . . ? C22 C23 C27 120.3(6) . . ? C23 C24 C25 122.8(7) . . ? C20 C25 C24 119.3(6) . . ? C20 C25 C28 122.0(6) . . ? C24 C25 C28 118.8(6) . . ? C30 C29 C34 122.2(6) . . ? C29 C30 C31 118.8(6) . . ? C32 C31 C30 121.1(6) . . ? C32 C31 O1 124.0(5) . . ? C30 C31 O1 114.9(6) . . ? C31 C32 C33 118.9(5) . . ? C32 C33 C34 122.7(5) . . ? C33 C34 C29 116.3(5) . . ? C33 C34 C10 123.7(5) . . ? C29 C34 C10 120.0(5) . . ? C41 C36 C37 119.7(5) . . ? C41 C36 C15 119.9(5) . . ? C37 C36 C15 120.4(5) . . ? C38 C37 C36 119.1(5) . . ? C38 C37 C42 120.5(5) . . ? C36 C37 C42 120.4(5) . . ? C39 C38 C37 122.0(5) . . ? C38 C39 C40 118.4(5) . . ? C38 C39 C43 121.0(5) . . ? C40 C39 C43 120.6(6) . . ? C39 C40 C41 121.9(6) . . ? C40 C41 C36 118.8(5) . . ? C40 C41 C44 120.0(6) . . ? C36 C41 C44 121.2(5) . . ? C1 N1 C4 108.1(5) . . ? C1 N1 Hf1 119.0(3) . . ? C4 N1 Hf1 130.8(4) . . ? C9 N2 C6 106.9(4) . . ? C9 N2 Hf1 120.0(4) . . ? C6 N2 Hf1 126.1(4) . . ? C11 N3 C14 107.9(4) . . ? C11 N3 Hf1 119.5(3) . . ? C14 N3 Hf1 127.5(3) . . ? C16 N4 C19 108.8(4) . . ? C16 N4 Hf1 132.8(3) . . ? C19 N4 Hf1 117.5(3) . . ? C35 O1 C31 115.8(5) . . ? Hf1 Cl1 Hf1 94.58(14) 2 . ? Hf1 Cl1 Cl1 61.18(14) 2 2 ? Hf1 Cl1 Cl1 55.85(14) . 2 ? Hf1 Cl2 Hf1 101.38(19) 2 . ? Cl2 Hf1 N2 82.67(15) . . ? Cl2 Hf1 N1 132.84(11) . . ? N2 Hf1 N1 77.33(17) . . ? Cl2 Hf1 N3 96.17(11) . . ? N2 Hf1 N3 83.28(16) . . ? N1 Hf1 N3 122.80(16) . . ? Cl2 Hf1 N4 151.07(14) . . ? N2 Hf1 N4 123.62(16) . . ? N1 Hf1 N4 70.60(16) . . ? N3 Hf1 N4 77.23(15) . . ? Cl2 Hf1 Cl1 74.20(12) . 2 ? N2 Hf1 Cl1 125.48(16) . 2 ? N1 Hf1 Cl1 83.52(15) . 2 ? N3 Hf1 Cl1 146.72(16) . 2 ? N4 Hf1 Cl1 95.77(14) . 2 ? Cl2 Hf1 Cl1 71.61(12) . . ? N2 Hf1 Cl1 149.65(16) . . ? N1 Hf1 Cl1 132.30(15) . . ? N3 Hf1 Cl1 83.76(15) . . ? N4 Hf1 Cl1 79.64(14) . . ? Cl1 Hf1 Cl1 62.96(19) 2 . ? Cl2 Hf1 Hf1 39.31(10) . 2 ? N2 Hf1 Hf1 120.36(11) . 2 ? N1 Hf1 Hf1 126.73(11) . 2 ? N3 Hf1 Hf1 109.59(11) . 2 ? N4 Hf1 Hf1 116.01(11) . 2 ? Cl1 Hf1 Hf1 44.22(9) 2 2 ? Cl1 Hf1 Hf1 41.21(8) . 2 ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 1.679 _refine_diff_density_min -0.921 _refine_diff_density_rms 0.127 # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.500 0.062 0.250 164 59 ' ' 2 0.500 -0.063 0.750 164 59 ' ' 3 0.250 0.250 0.865 493 126 ' ' 4 0.750 0.250 0.631 493 126 ' ' 5 0.000 0.437 0.750 164 59 ' ' 6 0.000 0.562 0.250 164 59 ' ' 7 0.250 0.750 0.631 493 126 ' ' 8 0.750 0.750 0.865 493 126 ' ' _platon_squeeze_details ; ; _database_code_depnum_ccdc_archive 'CCDC 979184' data_shelxl _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common alw072 _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C48 H48 N4 O Si Ti Zr0' _chemical_formula_weight 772.89 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' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 25.7460(12) _cell_length_b 14.2366(7) _cell_length_c 26.5033(13) _cell_angle_alpha 90.00 _cell_angle_beta 106.672(3) _cell_angle_gamma 90.00 _cell_volume 9306.0(8) _cell_formula_units_Z 8 _cell_measurement_temperature 103(2) _cell_measurement_reflns_used 9964 _cell_measurement_theta_min 2.72 _cell_measurement_theta_max 25.34 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.08 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas a _exptl_crystal_density_diffrn 1.103 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3264 _exptl_absorpt_coefficient_mu 0.246 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9806 _exptl_absorpt_correction_T_max 0.9830 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 103(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'QUAZAR multilayer mirrors' _diffrn_measurement_device_type 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_reflns_number 46668 _diffrn_reflns_av_R_equivalents 0.0561 _diffrn_reflns_av_sigmaI/netI 0.0433 _diffrn_reflns_limit_h_min -30 _diffrn_reflns_limit_h_max 31 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -31 _diffrn_reflns_limit_l_max 31 _diffrn_reflns_theta_min 1.60 _diffrn_reflns_theta_max 25.41 _reflns_number_total 8562 _reflns_number_gt 6622 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics ORTEP-32 _computing_publication_material WinGX _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^)+(0.0808P)^2^+5.3581P] 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 8562 _refine_ls_number_parameters 506 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0679 _refine_ls_R_factor_gt 0.0516 _refine_ls_wR_factor_ref 0.1443 _refine_ls_wR_factor_gt 0.1362 _refine_ls_goodness_of_fit_ref 1.057 _refine_ls_restrained_S_all 1.057 _refine_ls_shift/su_max 0.018 _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 C00A C 0.07359(9) 0.73575(16) 0.55081(9) 0.0226(5) Uani 1 1 d . . . C00B C 0.21858(9) 1.04945(17) 0.64633(9) 0.0232(5) Uani 1 1 d . . . C00C C 0.11228(9) 0.59485(17) 0.51891(9) 0.0241(5) Uani 1 1 d . . . C00D C -0.05163(9) 0.96481(17) 0.56530(9) 0.0233(5) Uani 1 1 d . . . C00E C 0.23658(9) 0.81094(17) 0.62172(9) 0.0237(5) Uani 1 1 d . . . C00F C 0.19840(9) 1.21955(17) 0.65115(9) 0.0233(5) Uani 1 1 d . . . C00G C 0.17909(9) 1.12042(16) 0.63963(9) 0.0225(5) Uani 1 1 d . . . C00H C 0.12343(10) 1.10157(17) 0.62233(9) 0.0239(5) Uani 1 1 d . . . C00I C 0.17207(9) 0.71095(17) 0.57901(9) 0.0229(5) Uani 1 1 d . . . C00J C 0.27608(9) 1.05353(18) 0.65864(9) 0.0263(5) Uani 1 1 d . . . H00J H 0.2977 1.1085 0.6677 0.032 Uiso 1 1 calc R . . C00K C 0.11913(9) 0.68146(17) 0.55205(9) 0.0230(5) Uani 1 1 d . . . C00L C -0.01274(9) 0.78785(17) 0.53212(9) 0.0241(5) Uani 1 1 d . . . H00L H -0.0511 0.7920 0.5189 0.029 Uiso 1 1 calc R . . C00M C 0.19997(10) 1.26097(17) 0.69929(10) 0.0269(5) Uani 1 1 d . . . C00N C 0.22327(9) 0.67116(18) 0.58142(9) 0.0267(5) Uani 1 1 d . . . H00N H 0.2291 0.6122 0.5672 0.032 Uiso 1 1 calc R . . C00O C 0.00765(9) 0.94784(17) 0.57600(9) 0.0224(5) Uani 1 1 d . . . C00P C 0.24951(9) 0.90394(17) 0.64008(9) 0.0235(5) Uani 1 1 d . . . C00Q C -0.16392(9) 0.98360(17) 0.54091(9) 0.0252(5) Uani 1 1 d . . . C00R C 0.29489(9) 0.96423(18) 0.65512(9) 0.0272(6) Uani 1 1 d . . . H00R H 0.3318 0.9463 0.6616 0.033 Uiso 1 1 calc R . . C00S C 0.11127(10) 0.50555(18) 0.54057(10) 0.0279(6) Uani 1 1 d . . . C00T C 0.01836(9) 0.71512(17) 0.52453(9) 0.0244(5) Uani 1 1 d . . . H00T H 0.0054 0.6598 0.5050 0.029 Uiso 1 1 calc R . . C00U C -0.13518(10) 1.03824(18) 0.51517(10) 0.0276(6) Uani 1 1 d . . . H00U H -0.1535 1.0823 0.4892 0.033 Uiso 1 1 calc R . . C00V C 0.03244(10) 1.11806(17) 0.60150(10) 0.0261(5) Uani 1 1 d . . . H00V H -0.0027 1.1442 0.5958 0.031 Uiso 1 1 calc R . . C00W C -0.07916(9) 1.02821(18) 0.52756(10) 0.0264(5) Uani 1 1 d . . . H00W H -0.0595 1.0657 0.5097 0.032 Uiso 1 1 calc R . . C00X C -0.08147(9) 0.91147(17) 0.59102(9) 0.0254(5) Uani 1 1 d . . . H00X H -0.0632 0.8678 0.6172 0.031 Uiso 1 1 calc R . . C00Y C 0.08008(10) 1.16603(18) 0.61718(9) 0.0272(6) Uani 1 1 d . . . H00Y H 0.0838 1.2317 0.6236 0.033 Uiso 1 1 calc R . . C00Z C 0.22225(10) 1.35069(18) 0.71064(10) 0.0311(6) Uani 1 1 d . . . H00Z H 0.2240 1.3785 0.7437 0.037 Uiso 1 1 calc R . . C01A C 0.23738(10) 1.35921(19) 0.62648(11) 0.0324(6) Uani 1 1 d . . . H01F H 0.2491 1.3939 0.6011 0.039 Uiso 1 1 calc R . . C01B C 0.17848(12) 1.2116(2) 0.73977(10) 0.0376(7) Uani 1 1 d . . . H01G H 0.1390 1.2184 0.7301 0.056 Uiso 1 1 calc R . . H01H H 0.1946 1.2398 0.7745 0.056 Uiso 1 1 calc R . . H01I H 0.1879 1.1449 0.7409 0.056 Uiso 1 1 calc R . . C01C C -0.24856(11) 1.0309(2) 0.48310(10) 0.0397(7) Uani 1 1 d . . . H01J H -0.2406 1.0984 0.4857 0.060 Uiso 1 1 calc R . . H01K H -0.2875 1.0211 0.4773 0.060 Uiso 1 1 calc R . . H01L H -0.2377 1.0043 0.4535 0.060 Uiso 1 1 calc R . . C01D C 0.21396(12) 1.2279(2) 0.56055(11) 0.0410(7) Uani 1 1 d . . . H01M H 0.2168 1.2782 0.5362 0.061 Uiso 1 1 calc R . . H01N H 0.1794 1.1948 0.5466 0.061 Uiso 1 1 calc R . . H01O H 0.2440 1.1837 0.5644 0.061 Uiso 1 1 calc R . . C01E C 0.10886(13) 0.7005(2) 0.44029(11) 0.0443(7) Uani 1 1 d . . . H01P H 0.1065 0.6933 0.4029 0.066 Uiso 1 1 calc R . . H01Q H 0.1427 0.7327 0.4584 0.066 Uiso 1 1 calc R . . H01R H 0.0780 0.7376 0.4437 0.066 Uiso 1 1 calc R . . C01F C 0.10723(13) 0.3496(2) 0.42234(12) 0.0492(8) Uani 1 1 d . . . H01S H 0.1245 0.2971 0.4449 0.074 Uiso 1 1 calc R . . H01T H 0.1275 0.3636 0.3971 0.074 Uiso 1 1 calc R . . H01U H 0.0699 0.3327 0.4032 0.074 Uiso 1 1 calc R . . C01H C 0.26710(13) 1.4956(2) 0.68911(14) 0.0525(9) Uani 1 1 d . . . H01$ H 0.3051 1.4936 0.6888 0.079 Uiso 1 1 calc R . . H01V H 0.2653 1.5134 0.7243 0.079 Uiso 1 1 calc R . . H01W H 0.2474 1.5419 0.6633 0.079 Uiso 1 1 calc R . . C008 C 0.02222(9) 0.85695(17) 0.56344(9) 0.0215(5) Uani 1 1 d . . . C009 C 0.04439(9) 1.02170(17) 0.59510(9) 0.0225(5) Uani 1 1 d . . . C010 C 0.21653(9) 1.26953(18) 0.61360(10) 0.0270(6) Uani 1 1 d . . . C011 C 0.26291(10) 0.73253(18) 0.60790(9) 0.0265(5) Uani 1 1 d . . . H011 H 0.3010 0.7237 0.6155 0.032 Uiso 1 1 calc R . . C012 C 0.12473(10) 0.86180(19) 0.70090(9) 0.0302(6) Uani 1 1 d . . . H01A H 0.1587 0.8825 0.7269 0.036 Uiso 1 1 calc R . . H01B H 0.0958 0.9045 0.7049 0.036 Uiso 1 1 calc R . . C013 C 0.10955(10) 0.42726(19) 0.50846(10) 0.0323(6) Uani 1 1 d . . . H013 H 0.1102 0.3664 0.5234 0.039 Uiso 1 1 calc R . . C014 C -0.13703(10) 0.92056(18) 0.57937(10) 0.0279(6) Uani 1 1 d . . . H014 H -0.1567 0.8839 0.5976 0.033 Uiso 1 1 calc R . . C015 C 0.10789(10) 0.60399(18) 0.46485(10) 0.0296(6) Uani 1 1 d . . . C016 C 0.10691(10) 0.4348(2) 0.45592(11) 0.0343(6) Uani 1 1 d . . . C017 C 0.10456(10) 0.5235(2) 0.43466(10) 0.0337(6) Uani 1 1 d . . . H017 H 0.1005 0.5297 0.3980 0.040 Uiso 1 1 calc R . . C018 C 0.11228(12) 0.49364(19) 0.59694(11) 0.0380(7) Uani 1 1 d . . . H01C H 0.1445 0.5247 0.6197 0.057 Uiso 1 1 calc R . . H01D H 0.1134 0.4266 0.6055 0.057 Uiso 1 1 calc R . . H01E H 0.0796 0.5218 0.6025 0.057 Uiso 1 1 calc R . . C019 C 0.24171(10) 1.39975(18) 0.67501(11) 0.0343(6) Uani 1 1 d . . . C101 C 0.03998(12) 0.7060(3) 0.68227(13) 0.0565(9) Uani 1 1 d . . . H10G H 0.0130 0.7519 0.6861 0.085 Uiso 1 1 calc R . . H10H H 0.0317 0.6444 0.6945 0.085 Uiso 1 1 calc R . . H10I H 0.0392 0.7019 0.6451 0.085 Uiso 1 1 calc R . . C102 C 0.11055(13) 0.7488(2) 0.79322(12) 0.0481(8) Uani 1 1 d . . . H10A H 0.1476 0.7624 0.8148 0.072 Uiso 1 1 calc R . . H10B H 0.0989 0.6882 0.8037 0.072 Uiso 1 1 calc R . . H10C H 0.0861 0.7984 0.7983 0.072 Uiso 1 1 calc R . . C103 C 0.16117(12) 0.6596(2) 0.71440(11) 0.0412(7) Uani 1 1 d . . . H10D H 0.1612 0.6583 0.6774 0.062 Uiso 1 1 calc R . . H10E H 0.1529 0.5967 0.7250 0.062 Uiso 1 1 calc R . . H10F H 0.1969 0.6793 0.7365 0.062 Uiso 1 1 calc R . . N004 N 0.18135(7) 0.79523(14) 0.60544(7) 0.0222(4) Uani 1 1 d . . . N005 N 0.07518(7) 0.82335(13) 0.57503(7) 0.0209(4) Uani 1 1 d . . . N006 N 0.10076(7) 1.01271(13) 0.60847(8) 0.0225(4) Uani 1 1 d . . . N007 N 0.20370(7) 0.95677(14) 0.63653(8) 0.0239(4) Uani 1 1 d . . . O003 O -0.21924(6) 0.98589(13) 0.53065(7) 0.0316(4) Uani 1 1 d . . . Si02 Si 0.10881(3) 0.74403(6) 0.72243(3) 0.0332(2) Uani 1 1 d . . . Ti1 Ti 0.134010(16) 0.88794(3) 0.628637(16) 0.02071(13) 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 C00A 0.0259(12) 0.0210(13) 0.0222(12) 0.0000(10) 0.0091(10) -0.0021(10) C00B 0.0261(12) 0.0248(13) 0.0200(12) -0.0023(10) 0.0087(10) -0.0050(10) C00C 0.0199(12) 0.0258(14) 0.0273(13) -0.0047(10) 0.0079(10) 0.0017(10) C00D 0.0219(12) 0.0252(13) 0.0248(12) -0.0023(10) 0.0097(10) 0.0006(10) C00E 0.0201(12) 0.0303(14) 0.0219(12) 0.0011(10) 0.0081(10) 0.0032(10) C00F 0.0204(12) 0.0250(13) 0.0245(12) 0.0002(10) 0.0064(10) -0.0001(10) C00G 0.0251(12) 0.0235(13) 0.0207(12) -0.0015(10) 0.0097(10) -0.0031(10) C00H 0.0282(13) 0.0231(13) 0.0223(12) 0.0003(10) 0.0104(10) -0.0015(10) C00I 0.0282(13) 0.0209(13) 0.0217(12) 0.0024(10) 0.0105(10) 0.0018(10) C00J 0.0239(12) 0.0292(14) 0.0257(13) -0.0012(10) 0.0072(10) -0.0039(10) C00K 0.0242(12) 0.0250(13) 0.0217(12) 0.0008(10) 0.0098(10) 0.0003(10) C00L 0.0186(12) 0.0296(14) 0.0251(12) -0.0007(10) 0.0081(10) -0.0022(10) C00M 0.0281(13) 0.0252(14) 0.0271(13) 0.0004(10) 0.0075(10) 0.0000(10) C00N 0.0268(13) 0.0305(14) 0.0231(12) -0.0010(10) 0.0079(10) 0.0064(11) C00O 0.0208(12) 0.0256(13) 0.0224(12) 0.0021(10) 0.0090(10) 0.0009(10) C00P 0.0200(12) 0.0297(14) 0.0214(12) 0.0006(10) 0.0070(10) 0.0014(10) C00Q 0.0210(12) 0.0293(14) 0.0271(13) -0.0045(10) 0.0099(10) 0.0010(10) C00R 0.0200(12) 0.0346(15) 0.0271(13) -0.0002(11) 0.0070(10) 0.0003(11) C00S 0.0239(12) 0.0295(14) 0.0306(13) -0.0046(11) 0.0083(10) -0.0009(10) C00T 0.0220(12) 0.0251(13) 0.0274(13) -0.0033(10) 0.0090(10) -0.0036(10) C00U 0.0276(13) 0.0282(14) 0.0260(13) 0.0039(11) 0.0060(10) 0.0047(11) C00V 0.0230(12) 0.0262(14) 0.0311(13) 0.0006(11) 0.0109(10) 0.0024(10) C00W 0.0262(13) 0.0265(14) 0.0296(13) 0.0033(11) 0.0128(11) -0.0014(10) C00X 0.0235(12) 0.0283(14) 0.0254(12) 0.0023(10) 0.0085(10) 0.0029(10) C00Y 0.0314(13) 0.0231(13) 0.0288(13) -0.0017(10) 0.0111(11) 0.0022(11) C00Z 0.0340(14) 0.0271(14) 0.0292(14) -0.0033(11) 0.0040(11) 0.0006(11) C01A 0.0253(13) 0.0319(15) 0.0439(16) 0.0141(12) 0.0161(12) 0.0026(11) C01B 0.0533(17) 0.0337(16) 0.0293(14) -0.0006(12) 0.0172(13) -0.0028(13) C01C 0.0280(14) 0.059(2) 0.0301(14) 0.0007(13) 0.0048(11) 0.0063(13) C01D 0.0512(18) 0.0448(18) 0.0341(15) 0.0071(13) 0.0234(14) 0.0076(14) C01E 0.063(2) 0.0437(18) 0.0318(15) 0.0023(13) 0.0219(14) 0.0031(15) C01F 0.0562(19) 0.0483(19) 0.0501(19) -0.0240(15) 0.0265(16) -0.0140(16) C01H 0.0500(19) 0.0300(17) 0.070(2) 0.0054(15) 0.0057(16) -0.0068(14) C008 0.0184(11) 0.0260(13) 0.0221(12) 0.0033(10) 0.0088(9) 0.0001(10) C009 0.0216(12) 0.0260(13) 0.0227(12) 0.0018(10) 0.0107(10) 0.0034(10) C010 0.0233(12) 0.0294(14) 0.0310(14) 0.0071(11) 0.0119(10) 0.0050(10) C011 0.0214(12) 0.0323(14) 0.0256(13) 0.0004(11) 0.0061(10) 0.0051(10) C012 0.0325(14) 0.0354(15) 0.0234(13) -0.0015(11) 0.0093(11) 0.0025(11) C013 0.0287(14) 0.0295(15) 0.0389(15) -0.0065(12) 0.0098(12) -0.0050(11) C014 0.0273(13) 0.0303(14) 0.0298(13) 0.0031(11) 0.0142(11) 0.0009(11) C015 0.0274(13) 0.0340(15) 0.0293(13) -0.0031(11) 0.0111(11) -0.0006(11) C016 0.0280(14) 0.0357(16) 0.0409(16) -0.0154(13) 0.0124(12) -0.0079(12) C017 0.0313(14) 0.0463(18) 0.0262(13) -0.0081(12) 0.0124(11) -0.0027(12) C018 0.0525(18) 0.0262(15) 0.0369(15) -0.0023(12) 0.0155(13) 0.0003(13) C019 0.0286(14) 0.0232(14) 0.0465(17) 0.0032(12) 0.0036(12) -0.0017(11) C101 0.0359(17) 0.076(3) 0.052(2) 0.0204(18) 0.0040(14) -0.0157(16) C102 0.0528(19) 0.060(2) 0.0386(17) 0.0111(15) 0.0243(15) 0.0134(16) C103 0.0557(18) 0.0389(17) 0.0305(15) -0.0007(12) 0.0150(13) 0.0037(14) N004 0.0199(10) 0.0234(11) 0.0244(10) -0.0016(8) 0.0079(8) 0.0000(8) N005 0.0197(10) 0.0203(11) 0.0238(10) -0.0004(8) 0.0082(8) -0.0001(8) N006 0.0207(10) 0.0217(11) 0.0267(11) -0.0016(8) 0.0093(8) -0.0004(8) N007 0.0208(10) 0.0239(11) 0.0279(11) -0.0040(9) 0.0086(8) -0.0006(8) O003 0.0197(9) 0.0431(11) 0.0319(10) 0.0039(8) 0.0072(7) 0.0041(8) Si02 0.0303(4) 0.0433(5) 0.0265(4) 0.0044(3) 0.0090(3) 0.0006(3) Ti1 0.0192(2) 0.0217(2) 0.0226(2) -0.00152(17) 0.00834(17) 0.00021(17) _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 C00A C00K 1.397(3) . ? C00A N005 1.398(3) . ? C00A C00T 1.423(3) . ? C00B N007 1.378(3) . ? C00B C00G 1.408(3) . ? C00B C00J 1.423(3) . ? C00C C00S 1.398(3) . ? C00C C015 1.411(3) . ? C00C C00K 1.495(3) . ? C00D C00W 1.382(3) . ? C00D C00X 1.390(3) . ? C00D C00O 1.490(3) . ? C00E N004 1.381(3) . ? C00E C011 1.408(3) . ? C00E C00P 1.417(3) . ? C00F C00M 1.395(3) . ? C00F C010 1.408(3) . ? C00F C00G 1.498(3) . ? C00G C00H 1.400(3) . ? C00H N006 1.397(3) . ? C00H C00Y 1.421(3) . ? C00I N004 1.375(3) . ? C00I C00K 1.409(3) . ? C00I C00N 1.419(3) . ? C00J C00R 1.373(4) . ? C00J H00J 0.9500 . ? C00L C00T 1.359(3) . ? C00L C008 1.428(3) . ? C00L H00L 0.9500 . ? C00M C00Z 1.397(4) . ? C00M C01B 1.514(4) . ? C00N C011 1.373(3) . ? C00N H00N 0.9500 . ? C00O C009 1.408(3) . ? C00O C008 1.413(3) . ? C00P N007 1.379(3) . ? C00P C00R 1.412(3) . ? C00Q O003 1.372(3) . ? C00Q C00U 1.381(3) . ? C00Q C014 1.385(3) . ? C00R H00R 0.9500 . ? C00S C013 1.395(4) . ? C00S C018 1.496(4) . ? C00T H00T 0.9500 . ? C00U C00W 1.392(3) . ? C00U H00U 0.9500 . ? C00V C00Y 1.361(3) . ? C00V C009 1.427(3) . ? C00V H00V 0.9500 . ? C00W H00W 0.9500 . ? C00X C014 1.380(3) . ? C00X H00X 0.9500 . ? C00Y H00Y 0.9500 . ? C00Z C019 1.379(4) . ? C00Z H00Z 0.9500 . ? C01A C019 1.385(4) . ? C01A C010 1.389(4) . ? C01A H01F 0.9500 . ? C01B H01G 0.9800 . ? C01B H01H 0.9800 . ? C01B H01I 0.9800 . ? C01C O003 1.422(3) . ? C01C H01J 0.9800 . ? C01C H01K 0.9800 . ? C01C H01L 0.9800 . ? C01D C010 1.510(4) . ? C01D H01M 0.9800 . ? C01D H01N 0.9800 . ? C01D H01O 0.9800 . ? C01E C015 1.524(4) . ? C01E H01P 0.9800 . ? C01E H01Q 0.9800 . ? C01E H01R 0.9800 . ? C01F C016 1.506(4) . ? C01F H01S 0.9800 . ? C01F H01T 0.9800 . ? C01F H01U 0.9800 . ? C01H C019 1.513(4) . ? C01H H01$ 0.9800 . ? C01H H01V 0.9800 . ? C01H H01W 0.9800 . ? C008 N005 1.394(3) . ? C009 N006 1.397(3) . ? C011 H011 0.9500 . ? C012 Si02 1.855(3) . ? C012 Ti1 2.031(2) . ? C012 H01A 0.9900 . ? C012 H01B 0.9900 . ? C013 C016 1.379(4) . ? C013 H013 0.9500 . ? C014 H014 0.9500 . ? C015 C017 1.386(4) . ? C016 C017 1.377(4) . ? C017 H017 0.9500 . ? C018 H01C 0.9800 . ? C018 H01D 0.9800 . ? C018 H01E 0.9800 . ? C101 Si02 1.866(3) . ? C101 H10G 0.9800 . ? C101 H10H 0.9800 . ? C101 H10I 0.9800 . ? C102 Si02 1.865(3) . ? C102 H10A 0.9800 . ? C102 H10B 0.9800 . ? C102 H10C 0.9800 . ? C103 Si02 1.863(3) . ? C103 H10D 0.9800 . ? C103 H10E 0.9800 . ? C103 H10F 0.9800 . ? N004 Ti1 2.0089(19) . ? N005 Ti1 1.9808(19) . ? N006 Ti1 1.9777(19) . ? N007 Ti1 2.0020(19) . ? 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 C00K C00A N005 124.7(2) . . ? C00K C00A C00T 127.7(2) . . ? N005 C00A C00T 107.6(2) . . ? N007 C00B C00G 120.8(2) . . ? N007 C00B C00J 107.3(2) . . ? C00G C00B C00J 131.7(2) . . ? C00S C00C C015 119.7(2) . . ? C00S C00C C00K 121.5(2) . . ? C015 C00C C00K 118.8(2) . . ? C00W C00D C00X 118.1(2) . . ? C00W C00D C00O 121.9(2) . . ? C00X C00D C00O 119.9(2) . . ? N004 C00E C011 108.7(2) . . ? N004 C00E C00P 112.2(2) . . ? C011 C00E C00P 138.3(2) . . ? C00M C00F C010 120.3(2) . . ? C00M C00F C00G 120.3(2) . . ? C010 C00F C00G 119.3(2) . . ? C00H C00G C00B 122.6(2) . . ? C00H C00G C00F 119.7(2) . . ? C00B C00G C00F 117.7(2) . . ? N006 C00H C00G 124.8(2) . . ? N006 C00H C00Y 107.6(2) . . ? C00G C00H C00Y 127.6(2) . . ? N004 C00I C00K 121.3(2) . . ? N004 C00I C00N 107.6(2) . . ? C00K C00I C00N 130.9(2) . . ? C00R C00J C00B 108.1(2) . . ? C00R C00J H00J 126.0 . . ? C00B C00J H00J 126.0 . . ? C00A C00K C00I 122.0(2) . . ? C00A C00K C00C 119.1(2) . . ? C00I C00K C00C 118.5(2) . . ? C00T C00L C008 108.1(2) . . ? C00T C00L H00L 125.9 . . ? C008 C00L H00L 125.9 . . ? C00F C00M C00Z 119.1(2) . . ? C00F C00M C01B 122.1(2) . . ? C00Z C00M C01B 118.8(2) . . ? C011 C00N C00I 108.3(2) . . ? C011 C00N H00N 125.9 . . ? C00I C00N H00N 125.9 . . ? C009 C00O C008 124.9(2) . . ? C009 C00O C00D 119.6(2) . . ? C008 C00O C00D 115.5(2) . . ? N007 C00P C00R 108.1(2) . . ? N007 C00P C00E 112.0(2) . . ? C00R C00P C00E 139.4(2) . . ? O003 C00Q C00U 124.2(2) . . ? O003 C00Q C014 115.6(2) . . ? C00U C00Q C014 120.2(2) . . ? C00J C00R C00P 107.6(2) . . ? C00J C00R H00R 126.2 . . ? C00P C00R H00R 126.2 . . ? C013 C00S C00C 118.5(2) . . ? C013 C00S C018 120.4(2) . . ? C00C C00S C018 121.1(2) . . ? C00L C00T C00A 108.6(2) . . ? C00L C00T H00T 125.7 . . ? C00A C00T H00T 125.7 . . ? C00Q C00U C00W 119.4(2) . . ? C00Q C00U H00U 120.3 . . ? C00W C00U H00U 120.3 . . ? C00Y C00V C009 108.2(2) . . ? C00Y C00V H00V 125.9 . . ? C009 C00V H00V 125.9 . . ? C00D C00W C00U 121.3(2) . . ? C00D C00W H00W 119.4 . . ? C00U C00W H00W 119.4 . . ? C014 C00X C00D 121.5(2) . . ? C014 C00X H00X 119.3 . . ? C00D C00X H00X 119.3 . . ? C00V C00Y C00H 108.6(2) . . ? C00V C00Y H00Y 125.7 . . ? C00H C00Y H00Y 125.7 . . ? C019 C00Z C00M 121.5(2) . . ? C019 C00Z H00Z 119.2 . . ? C00M C00Z H00Z 119.2 . . ? C019 C01A C010 122.3(2) . . ? C019 C01A H01F 118.9 . . ? C010 C01A H01F 118.9 . . ? C00M C01B H01G 109.5 . . ? C00M C01B H01H 109.5 . . ? H01G C01B H01H 109.5 . . ? C00M C01B H01I 109.5 . . ? H01G C01B H01I 109.5 . . ? H01H C01B H01I 109.5 . . ? O003 C01C H01J 109.5 . . ? O003 C01C H01K 109.5 . . ? H01J C01C H01K 109.5 . . ? O003 C01C H01L 109.5 . . ? H01J C01C H01L 109.5 . . ? H01K C01C H01L 109.5 . . ? C010 C01D H01M 109.5 . . ? C010 C01D H01N 109.5 . . ? H01M C01D H01N 109.5 . . ? C010 C01D H01O 109.5 . . ? H01M C01D H01O 109.5 . . ? H01N C01D H01O 109.5 . . ? C015 C01E H01P 109.5 . . ? C015 C01E H01Q 109.5 . . ? H01P C01E H01Q 109.5 . . ? C015 C01E H01R 109.5 . . ? H01P C01E H01R 109.5 . . ? H01Q C01E H01R 109.5 . . ? C016 C01F H01S 109.5 . . ? C016 C01F H01T 109.5 . . ? H01S C01F H01T 109.5 . . ? C016 C01F H01U 109.5 . . ? H01S C01F H01U 109.5 . . ? H01T C01F H01U 109.5 . . ? C019 C01H H01$ 109.5 . . ? C019 C01H H01V 109.5 . . ? H01$ C01H H01V 109.5 . . ? C019 C01H H01W 109.5 . . ? H01$ C01H H01W 109.5 . . ? H01V C01H H01W 109.5 . . ? N005 C008 C00O 124.8(2) . . ? N005 C008 C00L 107.8(2) . . ? C00O C008 C00L 127.0(2) . . ? N006 C009 C00O 124.4(2) . . ? N006 C009 C00V 107.6(2) . . ? C00O C009 C00V 128.0(2) . . ? C01A C010 C00F 118.3(2) . . ? C01A C010 C01D 120.0(2) . . ? C00F C010 C01D 121.7(2) . . ? C00N C011 C00E 107.1(2) . . ? C00N C011 H011 126.4 . . ? C00E C011 H011 126.4 . . ? Si02 C012 Ti1 123.50(14) . . ? Si02 C012 H01A 106.5 . . ? Ti1 C012 H01A 106.5 . . ? Si02 C012 H01B 106.5 . . ? Ti1 C012 H01B 106.5 . . ? H01A C012 H01B 106.5 . . ? C016 C013 C00S 122.5(3) . . ? C016 C013 H013 118.8 . . ? C00S C013 H013 118.8 . . ? C00X C014 C00Q 119.5(2) . . ? C00X C014 H014 120.2 . . ? C00Q C014 H014 120.2 . . ? C017 C015 C00C 118.9(2) . . ? C017 C015 C01E 120.3(2) . . ? C00C C015 C01E 120.7(2) . . ? C017 C016 C013 118.0(2) . . ? C017 C016 C01F 120.3(3) . . ? C013 C016 C01F 121.8(3) . . ? C016 C017 C015 122.2(2) . . ? C016 C017 H017 118.9 . . ? C015 C017 H017 118.9 . . ? C00S C018 H01C 109.5 . . ? C00S C018 H01D 109.5 . . ? H01C C018 H01D 109.5 . . ? C00S C018 H01E 109.5 . . ? H01C C018 H01E 109.5 . . ? H01D C018 H01E 109.5 . . ? C00Z C019 C01A 118.5(2) . . ? C00Z C019 C01H 120.2(3) . . ? C01A C019 C01H 121.3(3) . . ? Si02 C101 H10G 109.5 . . ? Si02 C101 H10H 109.5 . . ? H10G C101 H10H 109.5 . . ? Si02 C101 H10I 109.5 . . ? H10G C101 H10I 109.5 . . ? H10H C101 H10I 109.5 . . ? Si02 C102 H10A 109.5 . . ? Si02 C102 H10B 109.5 . . ? H10A C102 H10B 109.5 . . ? Si02 C102 H10C 109.5 . . ? H10A C102 H10C 109.5 . . ? H10B C102 H10C 109.5 . . ? Si02 C103 H10D 109.5 . . ? Si02 C103 H10E 109.5 . . ? H10D C103 H10E 109.5 . . ? Si02 C103 H10F 109.5 . . ? H10D C103 H10F 109.5 . . ? H10E C103 H10F 109.5 . . ? C00I N004 C00E 108.26(19) . . ? C00I N004 Ti1 134.20(15) . . ? C00E N004 Ti1 117.31(15) . . ? C008 N005 C00A 107.88(18) . . ? C008 N005 Ti1 119.82(15) . . ? C00A N005 Ti1 131.24(15) . . ? C009 N006 C00H 107.98(19) . . ? C009 N006 Ti1 119.23(15) . . ? C00H N006 Ti1 128.77(15) . . ? C00B N007 C00P 108.88(19) . . ? C00B N007 Ti1 132.90(16) . . ? C00P N007 Ti1 117.61(16) . . ? C00Q O003 C01C 116.32(19) . . ? C012 Si02 C103 108.48(13) . . ? C012 Si02 C102 109.44(14) . . ? C103 Si02 C102 109.22(13) . . ? C012 Si02 C101 110.12(14) . . ? C103 Si02 C101 110.33(16) . . ? C102 Si02 C101 109.22(15) . . ? N006 Ti1 N005 92.32(8) . . ? N006 Ti1 N007 83.92(8) . . ? N005 Ti1 N007 141.28(8) . . ? N006 Ti1 N004 139.55(8) . . ? N005 Ti1 N004 83.20(8) . . ? N007 Ti1 N004 75.48(8) . . ? N006 Ti1 C012 105.10(9) . . ? N005 Ti1 C012 108.58(9) . . ? N007 Ti1 C012 109.60(9) . . ? N004 Ti1 C012 114.46(9) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.452 _refine_diff_density_min -0.328 _refine_diff_density_rms 0.063 # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.500 0.244 0.250 422 77 ' ' 2 0.000 -0.256 0.250 422 77 ' ' 3 0.500 -0.244 0.750 422 77 ' ' 4 0.000 0.256 0.750 422 77 ' ' _platon_squeeze_details ; ; _database_code_depnum_ccdc_archive 'CCDC 979185' data_shelxl _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common MP0235 _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C44 H37 Cl N4 O Ti' _chemical_formula_weight 721.13 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' Cl Cl 0.1484 0.1585 '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' Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' _cell_length_a 31.206(3) _cell_length_b 7.8852(7) _cell_length_c 17.2435(15) _cell_angle_alpha 90.00 _cell_angle_beta 117.308(3) _cell_angle_gamma 90.00 _cell_volume 3770.2(6) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 9815 _cell_measurement_theta_min 2.61 _cell_measurement_theta_max 25.37 _exptl_crystal_description block _exptl_crystal_colour black _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.270 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1504 _exptl_absorpt_coefficient_mu 0.337 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9671 _exptl_absorpt_correction_T_max 0.9801 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_reflns_number 59945 _diffrn_reflns_av_R_equivalents 0.0337 _diffrn_reflns_av_sigmaI/netI 0.0238 _diffrn_reflns_limit_h_min -37 _diffrn_reflns_limit_h_max 37 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.46 _diffrn_reflns_theta_max 25.42 _reflns_number_total 6940 _reflns_number_gt 6678 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution SUPERFLIP _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics ORTEP-32 _computing_publication_material WinGX _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^)+(0.1642P)^2^+10.5610P] 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' _refine_ls_abs_structure_Flack 0.017(19) _refine_ls_number_reflns 6940 _refine_ls_number_parameters 467 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0346 _refine_ls_R_factor_gt 0.0330 _refine_ls_wR_factor_ref 0.1033 _refine_ls_wR_factor_gt 0.0999 _refine_ls_goodness_of_fit_ref 0.501 _refine_ls_restrained_S_all 0.501 _refine_ls_shift/su_max 0.044 _refine_ls_shift/su_mean 0.001 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 C1 C 0.93867(7) 0.6517(3) 0.39214(13) 0.0180(4) Uani 1 1 d . . . C2 C 0.97087(7) 0.7772(3) 0.39333(14) 0.0198(4) Uani 1 1 d . . . H2 H 0.9734 0.8896 0.4149 0.024 Uiso 1 1 calc R . . C3 C 0.99811(7) 0.7067(3) 0.35729(14) 0.0201(5) Uani 1 1 d . . . H3 H 1.0228 0.7623 0.3492 0.024 Uiso 1 1 calc R . . C4 C 0.98280(7) 0.5358(3) 0.33446(14) 0.0189(4) Uani 1 1 d . . . C5 C 0.99439(8) 0.4179(3) 0.28722(14) 0.0202(4) Uani 1 1 d . . . C6 C 0.96950(7) 0.2651(3) 0.25840(14) 0.0194(5) Uani 1 1 d . . . C7 C 0.97870(8) 0.1343(3) 0.21060(15) 0.0224(5) Uani 1 1 d . . . H7 H 1.0048 0.1315 0.1966 0.027 Uiso 1 1 calc R . . C8 C 0.94376(8) 0.0147(3) 0.18867(15) 0.0219(5) Uani 1 1 d . . . H8 H 0.9416 -0.0872 0.1576 0.026 Uiso 1 1 calc R . . C9 C 0.91074(7) 0.0681(3) 0.22035(14) 0.0183(4) Uani 1 1 d . . . C10 C 0.86633(8) -0.0068(3) 0.20263(14) 0.0180(4) Uani 1 1 d . . . C11 C 0.83389(7) 0.0605(3) 0.23065(13) 0.0168(4) Uani 1 1 d . . . C12 C 0.78574(7) 0.0063(3) 0.20481(13) 0.0204(4) Uani 1 1 d . . . H12 H 0.7700 -0.0872 0.1679 0.024 Uiso 1 1 calc R . . C13 C 0.76613(8) 0.1121(3) 0.24239(14) 0.0207(5) Uani 1 1 d . . . H13 H 0.7344 0.1035 0.2367 0.025 Uiso 1 1 calc R . . C14 C 0.80035(7) 0.2364(3) 0.29105(14) 0.0169(4) Uani 1 1 d . . . C15 C 0.79347(7) 0.3742(3) 0.33493(14) 0.0177(4) Uani 1 1 d . . . C16 C 0.82789(7) 0.5018(3) 0.37288(14) 0.0182(4) Uani 1 1 d . . . C17 C 0.82521(8) 0.6651(3) 0.40554(15) 0.0211(4) Uani 1 1 d . . . H17 H 0.7990 0.7073 0.4135 0.025 Uiso 1 1 calc R . . C18 C 0.86703(8) 0.7516(3) 0.42357(14) 0.0206(5) Uani 1 1 d . . . H18 H 0.8749 0.8637 0.4459 0.025 Uiso 1 1 calc R . . C19 C 0.89615(7) 0.6420(3) 0.40255(13) 0.0172(4) Uani 1 1 d . . . C20 C 1.02962(7) 0.4642(3) 0.25354(15) 0.0195(4) Uani 1 1 d . . . C21 C 1.07949(8) 0.4478(3) 0.30562(15) 0.0220(5) Uani 1 1 d . . . C22 C 1.11013(8) 0.4861(3) 0.26917(16) 0.0268(5) Uani 1 1 d . . . H22 H 1.1439 0.4701 0.3034 0.032 Uiso 1 1 calc R . . C23 C 1.09308(9) 0.5458(4) 0.18558(16) 0.0338(6) Uani 1 1 d . . . C24 C 1.04345(9) 0.5668(4) 0.13560(16) 0.0338(6) Uani 1 1 d . . . H24 H 1.0311 0.6094 0.0778 0.041 Uiso 1 1 calc R . . C25 C 1.01159(8) 0.5263(4) 0.16871(15) 0.0271(5) Uani 1 1 d . . . C26 C 1.09994(9) 0.3915(4) 0.39851(17) 0.0324(6) Uani 1 1 d . . . H26A H 1.1348 0.3750 0.4222 0.049 Uiso 1 1 calc R . . H26B H 1.0848 0.2845 0.4015 0.049 Uiso 1 1 calc R . . H26C H 1.0936 0.4781 0.4327 0.049 Uiso 1 1 calc R . . C27 C 1.12704(10) 0.5909(6) 0.1484(2) 0.0540(10) Uani 1 1 d . . . H27A H 1.1509 0.6733 0.1867 0.081 Uiso 1 1 calc R . . H27B H 1.1087 0.6403 0.0902 0.081 Uiso 1 1 calc R . . H27C H 1.1436 0.4884 0.1443 0.081 Uiso 1 1 calc R . . C28 C 0.95778(8) 0.5486(4) 0.11095(17) 0.0342(6) Uani 1 1 d . . . H28A H 0.9435 0.4393 0.0847 0.051 Uiso 1 1 calc R . . H28B H 0.9525 0.6307 0.0648 0.051 Uiso 1 1 calc R . . H28C H 0.9427 0.5899 0.1462 0.051 Uiso 1 1 calc R . . C29 C 0.85110(7) -0.1602(3) 0.14688(14) 0.0185(4) Uani 1 1 d . . . C30 C 0.84571(8) -0.1590(3) 0.06150(15) 0.0205(5) Uani 1 1 d . . . H30 H 0.8525 -0.0580 0.0391 0.025 Uiso 1 1 calc R . . C31 C 0.83088(8) -0.3009(3) 0.00960(14) 0.0211(5) Uani 1 1 d . . . H31 H 0.8270 -0.2964 -0.0483 0.025 Uiso 1 1 calc R . . C32 C 0.82151(7) -0.4505(3) 0.04113(14) 0.0188(4) Uani 1 1 d . . . C33 C 0.82639(8) -0.4558(3) 0.12575(14) 0.0212(5) Uani 1 1 d . . . H33 H 0.8200 -0.5575 0.1482 0.025 Uiso 1 1 calc R . . C34 C 0.84063(8) -0.3105(3) 0.17653(14) 0.0219(5) Uani 1 1 d . . . H34 H 0.8433 -0.3138 0.2337 0.026 Uiso 1 1 calc R . . C35 C 0.79407(10) -0.7354(3) 0.01351(18) 0.0328(6) Uani 1 1 d . . . H35A H 0.8215 -0.7765 0.0668 0.049 Uiso 1 1 calc R . . H35B H 0.7846 -0.8222 -0.0320 0.049 Uiso 1 1 calc R . . H35C H 0.7669 -0.7111 0.0256 0.049 Uiso 1 1 calc R . . C36 C 0.74548(7) 0.3911(3) 0.33510(14) 0.0176(4) Uani 1 1 d . . . C37 C 0.73514(7) 0.2899(3) 0.39155(14) 0.0207(4) Uani 1 1 d . . . C38 C 0.68992(8) 0.3075(3) 0.38952(15) 0.0239(5) Uani 1 1 d . . . H38 H 0.6827 0.2393 0.4274 0.029 Uiso 1 1 calc R . . C39 C 0.65560(8) 0.4201(3) 0.33465(17) 0.0281(5) Uani 1 1 d . . . C40 C 0.66671(9) 0.5200(4) 0.27965(19) 0.0343(6) Uani 1 1 d . . . H40 H 0.6438 0.6001 0.2424 0.041 Uiso 1 1 calc R . . C41 C 0.71097(8) 0.5046(3) 0.27826(17) 0.0284(5) Uani 1 1 d . . . C42 C 0.77026(9) 0.1618(4) 0.45220(17) 0.0324(6) Uani 1 1 d . . . H42A H 0.7668 0.0548 0.4209 0.049 Uiso 1 1 calc R . . H42B H 0.7636 0.1424 0.5018 0.049 Uiso 1 1 calc R . . H42C H 0.8032 0.2045 0.4734 0.049 Uiso 1 1 calc R . . C43 C 0.60670(10) 0.4326(4) 0.3317(2) 0.0417(7) Uani 1 1 d . . . H43A H 0.5846 0.3519 0.2887 0.063 Uiso 1 1 calc R . . H43B H 0.5941 0.5480 0.3150 0.063 Uiso 1 1 calc R . . H43C H 0.6095 0.4061 0.3894 0.063 Uiso 1 1 calc R . . C44 C 0.72007(10) 0.6075(5) 0.2133(2) 0.0494(9) Uani 1 1 d . . . H44A H 0.6894 0.6514 0.1680 0.074 Uiso 1 1 calc R . . H44B H 0.7351 0.5353 0.1864 0.074 Uiso 1 1 calc R . . H44C H 0.7416 0.7024 0.2434 0.074 Uiso 1 1 calc R . . Cl1 Cl 0.940062(18) 0.14835(7) 0.47634(3) 0.02254(13) Uani 1 1 d . . . N1 N 0.94702(6) 0.5037(2) 0.35871(12) 0.0191(4) Uani 1 1 d . . . N2 N 0.92800(6) 0.2194(2) 0.26594(11) 0.0167(4) Uani 1 1 d . . . N3 N 0.84277(6) 0.2029(2) 0.28384(12) 0.0171(4) Uani 1 1 d . . . N4 N 0.87245(6) 0.4905(2) 0.37364(12) 0.0186(4) Uani 1 1 d . . . O2 O 0.80746(6) -0.5853(2) -0.01516(10) 0.0266(4) Uani 1 1 d . . . Ti1 Ti 0.908097(12) 0.29958(5) 0.35414(2) 0.01778(11) 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 C1 0.0167(9) 0.0184(10) 0.0186(10) -0.0047(9) 0.0079(8) -0.0019(9) C2 0.0183(9) 0.0187(11) 0.0226(11) -0.0051(9) 0.0096(8) -0.0045(9) C3 0.0158(9) 0.0241(12) 0.0202(10) -0.0016(9) 0.0082(8) -0.0039(9) C4 0.0150(9) 0.0228(11) 0.0209(10) -0.0019(9) 0.0100(8) -0.0039(8) C5 0.0156(10) 0.0268(12) 0.0206(10) -0.0033(9) 0.0104(8) -0.0009(9) C6 0.0151(9) 0.0222(12) 0.0241(11) -0.0011(9) 0.0117(8) -0.0011(8) C7 0.0201(10) 0.0241(12) 0.0278(11) -0.0050(10) 0.0150(9) -0.0016(9) C8 0.0208(10) 0.0226(11) 0.0266(11) -0.0044(10) 0.0146(9) -0.0010(9) C9 0.0189(10) 0.0186(11) 0.0187(10) -0.0041(8) 0.0097(8) -0.0017(8) C10 0.0178(10) 0.0191(11) 0.0178(10) 0.0001(9) 0.0088(8) -0.0004(8) C11 0.0169(9) 0.0183(11) 0.0158(10) -0.0003(8) 0.0080(8) -0.0046(8) C12 0.0181(10) 0.0241(12) 0.0182(10) -0.0035(9) 0.0077(8) -0.0063(9) C13 0.0156(10) 0.0249(12) 0.0222(11) 0.0006(9) 0.0092(9) -0.0036(8) C14 0.0125(9) 0.0220(11) 0.0181(10) 0.0054(8) 0.0085(8) -0.0008(8) C15 0.0136(9) 0.0215(11) 0.0198(11) 0.0023(8) 0.0093(8) 0.0012(8) C16 0.0162(10) 0.0214(11) 0.0216(10) 0.0005(9) 0.0125(8) -0.0001(8) C17 0.0194(10) 0.0203(11) 0.0291(11) -0.0001(9) 0.0160(9) 0.0022(9) C18 0.0238(11) 0.0205(11) 0.0218(11) -0.0010(9) 0.0142(9) -0.0029(9) C19 0.0177(10) 0.0195(10) 0.0179(10) -0.0039(9) 0.0112(8) -0.0052(8) C20 0.0173(10) 0.0200(11) 0.0260(11) -0.0060(9) 0.0141(9) -0.0037(8) C21 0.0190(10) 0.0210(11) 0.0278(11) -0.0063(9) 0.0124(9) -0.0040(9) C22 0.0145(10) 0.0341(14) 0.0331(12) -0.0097(11) 0.0122(9) -0.0060(9) C23 0.0251(12) 0.0536(17) 0.0306(13) -0.0094(12) 0.0196(10) -0.0133(12) C24 0.0233(11) 0.0592(18) 0.0223(12) 0.0004(12) 0.0135(10) -0.0083(12) C25 0.0177(10) 0.0396(14) 0.0266(11) -0.0036(11) 0.0124(9) -0.0058(10) C26 0.0236(12) 0.0421(16) 0.0311(13) 0.0023(11) 0.0122(11) 0.0018(11) C27 0.0281(14) 0.108(3) 0.0334(14) -0.0096(17) 0.0202(12) -0.0216(16) C28 0.0174(11) 0.0545(18) 0.0288(12) 0.0050(12) 0.0089(10) -0.0002(11) C29 0.0160(9) 0.0193(11) 0.0217(11) -0.0013(9) 0.0100(8) -0.0004(8) C30 0.0202(10) 0.0211(12) 0.0225(11) -0.0023(9) 0.0117(9) -0.0013(8) C31 0.0218(10) 0.0258(12) 0.0188(10) -0.0043(9) 0.0119(9) 0.0004(9) C32 0.0148(9) 0.0185(11) 0.0209(10) -0.0063(9) 0.0062(8) 0.0006(8) C33 0.0202(10) 0.0187(11) 0.0207(11) -0.0013(9) 0.0060(8) -0.0021(9) C34 0.0212(10) 0.0252(12) 0.0162(10) -0.0009(9) 0.0059(8) -0.0016(9) C35 0.0432(14) 0.0201(13) 0.0291(12) -0.0050(10) 0.0115(11) -0.0051(11) C36 0.0155(10) 0.0191(11) 0.0233(11) -0.0023(9) 0.0133(9) -0.0026(8) C37 0.0200(10) 0.0224(11) 0.0214(10) -0.0012(10) 0.0109(8) -0.0062(9) C38 0.0232(10) 0.0284(12) 0.0278(11) -0.0063(10) 0.0184(9) -0.0118(10) C39 0.0232(11) 0.0275(13) 0.0424(14) -0.0067(11) 0.0226(11) -0.0043(10) C40 0.0242(12) 0.0302(13) 0.0528(16) 0.0094(13) 0.0213(11) 0.0081(11) C41 0.0236(11) 0.0279(13) 0.0401(13) 0.0101(11) 0.0201(10) 0.0030(10) C42 0.0259(11) 0.0394(15) 0.0315(12) 0.0134(12) 0.0129(10) -0.0021(11) C43 0.0284(13) 0.0450(17) 0.0665(19) -0.0052(15) 0.0346(14) -0.0002(12) C44 0.0296(14) 0.059(2) 0.064(2) 0.0406(17) 0.0248(14) 0.0129(13) Cl1 0.0217(3) 0.0236(3) 0.0222(3) 0.0015(2) 0.0100(2) 0.0046(2) N1 0.0188(8) 0.0199(10) 0.0258(9) -0.0061(8) 0.0164(7) -0.0058(7) N2 0.0160(8) 0.0185(9) 0.0191(8) -0.0053(7) 0.0110(7) -0.0043(7) N3 0.0143(8) 0.0202(9) 0.0195(8) -0.0034(7) 0.0099(7) -0.0026(7) N4 0.0151(8) 0.0200(9) 0.0239(9) -0.0039(8) 0.0116(7) -0.0025(7) O2 0.0315(9) 0.0227(8) 0.0219(8) -0.0087(7) 0.0090(7) -0.0020(7) Ti1 0.01587(18) 0.0190(2) 0.0206(2) -0.00227(16) 0.01024(15) -0.00161(15) _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 C1 N1 1.379(3) . ? C1 C2 1.404(3) . ? C1 C19 1.420(3) . ? C2 C3 1.380(3) . ? C2 H2 0.9500 . ? C3 C4 1.424(3) . ? C3 H3 0.9500 . ? C4 C5 1.389(3) . ? C4 N1 1.383(3) . ? C5 C6 1.396(3) . ? C5 C20 1.505(3) . ? C6 N2 1.407(3) . ? C6 C7 1.429(3) . ? C7 C8 1.357(3) . ? C7 H7 0.9500 . ? C8 C9 1.433(3) . ? C8 H8 0.9500 . ? C9 N2 1.394(3) . ? C9 C10 1.405(3) . ? C10 C11 1.410(3) . ? C10 C29 1.481(3) . ? C11 N3 1.395(3) . ? C11 C12 1.423(3) . ? C12 C13 1.362(3) . ? C12 H12 0.9500 . ? C13 C14 1.408(3) . ? C13 H13 0.9500 . ? C14 C15 1.396(3) . ? C14 N3 1.410(3) . ? C15 C16 1.396(3) . ? C15 C36 1.505(3) . ? C16 N4 1.387(3) . ? C16 C17 1.424(3) . ? C17 C18 1.375(3) . ? C17 H17 0.9500 . ? C18 C19 1.417(3) . ? C18 H18 0.9500 . ? C19 N4 1.372(3) . ? C20 C25 1.393(3) . ? C20 C21 1.401(3) . ? C21 C22 1.397(3) . ? C21 C26 1.494(4) . ? C22 C23 1.371(4) . ? C22 H22 0.9500 . ? C23 C24 1.394(4) . ? C23 C27 1.511(3) . ? C24 C25 1.391(3) . ? C24 H24 0.9500 . ? C25 C28 1.519(3) . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? 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 C34 1.387(3) . ? C29 C30 1.403(3) . ? C30 C31 1.373(3) . ? C30 H30 0.9500 . ? C31 C32 1.385(3) . ? C31 H31 0.9500 . ? C32 O2 1.369(3) . ? C32 C33 1.396(3) . ? C33 C34 1.386(3) . ? C33 H33 0.9500 . ? C34 H34 0.9500 . ? C35 O2 1.417(3) . ? C35 H35A 0.9800 . ? C35 H35B 0.9800 . ? C35 H35C 0.9800 . ? C36 C41 1.397(3) . ? C36 C37 1.406(3) . ? C37 C38 1.402(3) . ? C37 C42 1.505(3) . ? C38 C39 1.379(4) . ? C38 H38 0.9500 . ? C39 C40 1.393(4) . ? C39 C43 1.507(3) . ? C40 C41 1.398(3) . ? C40 H40 0.9500 . ? C41 C44 1.512(4) . ? C42 H42A 0.9800 . ? C42 H42B 0.9800 . ? C42 H42C 0.9800 . ? C43 H43A 0.9800 . ? C43 H43B 0.9800 . ? C43 H43C 0.9800 . ? C44 H44A 0.9800 . ? C44 H44B 0.9800 . ? C44 H44C 0.9800 . ? Cl1 Ti1 2.2201(6) . ? N1 Ti1 1.9958(19) . ? N2 Ti1 1.9915(17) . ? N3 Ti1 1.9846(18) . ? N4 Ti1 1.9902(19) . ? 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 C1 C2 109.38(18) . . ? N1 C1 C19 111.93(19) . . ? C2 C1 C19 137.8(2) . . ? C1 C2 C3 107.1(2) . . ? C1 C2 H2 126.5 . . ? C3 C2 H2 126.5 . . ? C2 C3 C4 107.96(19) . . ? C2 C3 H3 126.0 . . ? C4 C3 H3 126.0 . . ? C5 C4 N1 121.2(2) . . ? C5 C4 C3 130.6(2) . . ? N1 C4 C3 107.7(2) . . ? C4 C5 C6 122.31(19) . . ? C4 C5 C20 119.8(2) . . ? C6 C5 C20 117.24(19) . . ? N2 C6 C5 125.03(19) . . ? N2 C6 C7 107.77(18) . . ? C5 C6 C7 127.03(19) . . ? C8 C7 C6 108.31(19) . . ? C8 C7 H7 125.8 . . ? C6 C7 H7 125.8 . . ? C7 C8 C9 108.4(2) . . ? C7 C8 H8 125.8 . . ? C9 C8 H8 125.8 . . ? N2 C9 C10 124.76(19) . . ? N2 C9 C8 107.89(18) . . ? C10 C9 C8 127.1(2) . . ? C11 C10 C9 123.9(2) . . ? C11 C10 C29 117.57(19) . . ? C9 C10 C29 118.38(18) . . ? N3 C11 C10 124.81(19) . . ? N3 C11 C12 108.10(18) . . ? C10 C11 C12 126.9(2) . . ? C13 C12 C11 107.9(2) . . ? C13 C12 H12 126.1 . . ? C11 C12 H12 126.1 . . ? C12 C13 C14 109.07(19) . . ? C12 C13 H13 125.5 . . ? C14 C13 H13 125.5 . . ? C15 C14 C13 126.99(19) . . ? C15 C14 N3 125.27(19) . . ? C13 C14 N3 107.65(19) . . ? C16 C15 C14 122.57(18) . . ? C16 C15 C36 119.2(2) . . ? C14 C15 C36 118.07(19) . . ? C15 C16 N4 120.7(2) . . ? C15 C16 C17 131.68(19) . . ? N4 C16 C17 107.13(18) . . ? C18 C17 C16 108.42(19) . . ? C18 C17 H17 125.8 . . ? C16 C17 H17 125.8 . . ? C17 C18 C19 107.1(2) . . ? C17 C18 H18 126.5 . . ? C19 C18 H18 126.5 . . ? N4 C19 C18 108.77(17) . . ? N4 C19 C1 112.36(19) . . ? C18 C19 C1 138.2(2) . . ? C25 C20 C21 120.0(2) . . ? C25 C20 C5 118.42(19) . . ? C21 C20 C5 121.6(2) . . ? C22 C21 C20 118.7(2) . . ? C22 C21 C26 120.2(2) . . ? C20 C21 C26 121.1(2) . . ? C23 C22 C21 122.1(2) . . ? C23 C22 H22 118.9 . . ? C21 C22 H22 118.9 . . ? C22 C23 C24 118.4(2) . . ? C22 C23 C27 121.1(2) . . ? C24 C23 C27 120.4(2) . . ? C23 C24 C25 121.3(2) . . ? C23 C24 H24 119.4 . . ? C25 C24 H24 119.4 . . ? C20 C25 C24 119.4(2) . . ? C20 C25 C28 121.4(2) . . ? C24 C25 C28 119.2(2) . . ? C21 C26 H26A 109.5 . . ? C21 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C21 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C23 C27 H27A 109.5 . . ? C23 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? C23 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? C25 C28 H28A 109.5 . . ? C25 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C25 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? C34 C29 C30 117.2(2) . . ? C34 C29 C10 121.18(19) . . ? C30 C29 C10 121.58(19) . . ? C31 C30 C29 121.4(2) . . ? C31 C30 H30 119.3 . . ? C29 C30 H30 119.3 . . ? C30 C31 C32 120.4(2) . . ? C30 C31 H31 119.8 . . ? C32 C31 H31 119.8 . . ? O2 C32 C33 124.3(2) . . ? O2 C32 C31 116.08(19) . . ? C33 C32 C31 119.6(2) . . ? C32 C33 C34 119.0(2) . . ? C32 C33 H33 120.5 . . ? C34 C33 H33 120.5 . . ? C33 C34 C29 122.3(2) . . ? C33 C34 H34 118.8 . . ? C29 C34 H34 118.8 . . ? O2 C35 H35A 109.5 . . ? O2 C35 H35B 109.5 . . ? H35A C35 H35B 109.5 . . ? O2 C35 H35C 109.5 . . ? H35A C35 H35C 109.5 . . ? H35B C35 H35C 109.5 . . ? C41 C36 C37 120.10(19) . . ? C41 C36 C15 120.2(2) . . ? C37 C36 C15 119.7(2) . . ? C38 C37 C36 118.3(2) . . ? C38 C37 C42 119.2(2) . . ? C36 C37 C42 122.49(19) . . ? C39 C38 C37 122.5(2) . . ? C39 C38 H38 118.8 . . ? C37 C38 H38 118.8 . . ? C38 C39 C40 118.3(2) . . ? C38 C39 C43 121.4(2) . . ? C40 C39 C43 120.3(2) . . ? C41 C40 C39 121.3(2) . . ? C41 C40 H40 119.4 . . ? C39 C40 H40 119.4 . . ? C40 C41 C36 119.5(2) . . ? C40 C41 C44 119.3(2) . . ? C36 C41 C44 121.1(2) . . ? C37 C42 H42A 109.5 . . ? C37 C42 H42B 109.5 . . ? H42A C42 H42B 109.5 . . ? C37 C42 H42C 109.5 . . ? H42A C42 H42C 109.5 . . ? H42B C42 H42C 109.5 . . ? C39 C43 H43A 109.5 . . ? C39 C43 H43B 109.5 . . ? H43A C43 H43B 109.5 . . ? C39 C43 H43C 109.5 . . ? H43A C43 H43C 109.5 . . ? H43B C43 H43C 109.5 . . ? C41 C44 H44A 109.5 . . ? C41 C44 H44B 109.5 . . ? H44A C44 H44B 109.5 . . ? C41 C44 H44C 109.5 . . ? H44A C44 H44C 109.5 . . ? H44B C44 H44C 109.5 . . ? C1 N1 C4 107.75(18) . . ? C1 N1 Ti1 118.09(13) . . ? C4 N1 Ti1 134.16(16) . . ? C9 N2 C6 107.54(17) . . ? C9 N2 Ti1 121.82(14) . . ? C6 N2 Ti1 127.74(14) . . ? C11 N3 C14 107.28(17) . . ? C11 N3 Ti1 123.33(14) . . ? C14 N3 Ti1 128.10(14) . . ? C19 N4 C16 108.59(18) . . ? C19 N4 Ti1 118.02(13) . . ? C16 N4 Ti1 133.01(15) . . ? C32 O2 C35 116.79(18) . . ? N3 Ti1 N4 84.07(7) . . ? N3 Ti1 N1 140.33(8) . . ? N4 Ti1 N1 76.15(8) . . ? N3 Ti1 N2 90.25(7) . . ? N4 Ti1 N2 139.79(8) . . ? N1 Ti1 N2 83.61(7) . . ? N3 Ti1 Cl1 105.18(6) . . ? N4 Ti1 Cl1 106.77(6) . . ? N1 Ti1 Cl1 113.29(6) . . ? N2 Ti1 Cl1 113.11(6) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.272 _refine_diff_density_min -0.495 _refine_diff_density_rms 0.051 # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.000 0.082 0.000 167 39 ' ' 2 0.500 0.582 1.000 167 39 ' ' _platon_squeeze_details ; ; _database_code_depnum_ccdc_archive 'CCDC 979186' data_shelxl _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common crmpp0214 _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C48 H45 Cl N4 O2 Zr' _chemical_formula_weight 836.55 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' Cl Cl 0.1484 0.1585 '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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 12.6629(9) _cell_length_b 14.2309(10) _cell_length_c 14.4202(11) _cell_angle_alpha 62.452(4) _cell_angle_beta 66.032(4) _cell_angle_gamma 88.472(4) _cell_volume 2063.2(3) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 9987 _cell_measurement_theta_min 2.67 _cell_measurement_theta_max 25.56 _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.08 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.347 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 868 _exptl_absorpt_coefficient_mu 0.375 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9706 _exptl_absorpt_correction_T_max 0.9925 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX-II CCD' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_reflns_number 35563 _diffrn_reflns_av_R_equivalents 0.0572 _diffrn_reflns_av_sigmaI/netI 0.0657 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.65 _diffrn_reflns_theta_max 25.57 _reflns_number_total 7536 _reflns_number_gt 5505 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker APEX2' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution SIR2004 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics ORTEP-32 _computing_publication_material WinGX _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^+5.9326P] 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 7536 _refine_ls_number_parameters 512 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0838 _refine_ls_R_factor_gt 0.0583 _refine_ls_wR_factor_ref 0.1354 _refine_ls_wR_factor_gt 0.1244 _refine_ls_goodness_of_fit_ref 1.116 _refine_ls_restrained_S_all 1.116 _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 C1 C 0.4042(4) 1.0129(3) 0.7749(4) 0.0225(10) Uani 1 1 d . . . C2 C 0.4443(4) 1.0818(3) 0.6535(4) 0.0259(11) Uani 1 1 d . . . H2 H 0.4033 1.1315 0.6172 0.031 Uiso 1 1 calc R . . C3 C 0.5526(4) 1.0640(3) 0.5980(4) 0.0236(10) Uani 1 1 d . . . H3 H 0.6005 1.0990 0.5160 0.028 Uiso 1 1 calc R . . C4 C 0.5811(4) 0.9832(3) 0.6856(3) 0.0207(10) Uani 1 1 d . . . C5 C 0.6716(4) 0.9253(3) 0.6752(3) 0.0185(9) Uani 1 1 d . . . C6 C 0.6728(4) 0.8343(3) 0.7726(3) 0.0199(9) Uani 1 1 d . . . C7 C 0.7566(4) 0.7656(3) 0.7688(4) 0.0238(10) Uani 1 1 d . . . H7 H 0.8260 0.7781 0.7015 0.029 Uiso 1 1 calc R . . C8 C 0.7204(4) 0.6791(4) 0.8781(4) 0.0236(10) Uani 1 1 d . . . H8 H 0.7607 0.6216 0.9005 0.028 Uiso 1 1 calc R . . C9 C 0.6113(4) 0.6903(3) 0.9527(4) 0.0206(10) Uani 1 1 d . . . C10 C 0.5346(4) 0.6131(3) 1.0673(3) 0.0194(9) Uani 1 1 d . . . C11 C 0.4179(4) 0.6180(3) 1.1299(3) 0.0203(10) Uani 1 1 d . . . C12 C 0.3277(4) 0.5308(4) 1.2303(4) 0.0233(10) Uani 1 1 d . . . H12 H 0.3384 0.4601 1.2740 0.028 Uiso 1 1 calc R . . C13 C 0.2246(4) 0.5644(4) 1.2537(4) 0.0258(11) Uani 1 1 d . . . H13 H 0.1501 0.5217 1.3159 0.031 Uiso 1 1 calc R . . C14 C 0.2466(4) 0.6758(3) 1.1686(3) 0.0219(10) Uani 1 1 d . . . C15 C 0.1590(4) 0.7359(3) 1.1546(4) 0.0225(10) Uani 1 1 d . . . C16 C 0.1839(4) 0.8388(3) 1.0566(3) 0.0218(10) Uani 1 1 d . . . C17 C 0.1079(4) 0.8999(4) 1.0147(4) 0.0272(11) Uani 1 1 d . . . H17 H 0.0244 0.8863 1.0561 0.033 Uiso 1 1 calc R . . C18 C 0.1764(4) 0.9832(4) 0.9030(4) 0.0264(11) Uani 1 1 d . . . H18 H 0.1492 1.0373 0.8533 0.032 Uiso 1 1 calc R . . C19 C 0.2955(4) 0.9720(3) 0.8768(3) 0.0218(10) Uani 1 1 d . . . C20 C 0.7614(4) 0.9490(3) 0.5564(4) 0.0212(10) Uani 1 1 d . . . C21 C 0.8545(4) 1.0384(3) 0.4886(4) 0.0237(10) Uani 1 1 d . . . C22 C 0.9383(4) 1.0554(4) 0.3795(4) 0.0295(11) Uani 1 1 d . . . H22 H 1.0017 1.1160 0.3330 0.035 Uiso 1 1 calc R . . C23 C 0.9324(4) 0.9879(4) 0.3369(4) 0.0272(11) Uani 1 1 d . . . C24 C 0.8389(4) 0.9016(4) 0.4035(4) 0.0252(10) Uani 1 1 d . . . H24 H 0.8334 0.8551 0.3745 0.030 Uiso 1 1 calc R . . C25 C 0.7511(4) 0.8803(3) 0.5136(4) 0.0226(10) Uani 1 1 d . . . C26 C 0.8655(4) 1.1145(4) 0.5304(5) 0.0385(13) Uani 1 1 d . . . H26A H 0.8209 1.1712 0.5076 0.058 Uiso 1 1 calc R . . H26B H 0.9488 1.1475 0.4952 0.058 Uiso 1 1 calc R . . H26C H 0.8342 1.0747 0.6156 0.058 Uiso 1 1 calc R . . C27 C 1.0275(4) 1.0085(5) 0.2203(4) 0.0411(14) Uani 1 1 d . . . H27A H 1.0162 0.9477 0.2086 0.062 Uiso 1 1 calc R . . H27B H 1.1050 1.0161 0.2188 0.062 Uiso 1 1 calc R . . H27C H 1.0232 1.0752 0.1579 0.062 Uiso 1 1 calc R . . C28 C 0.6477(4) 0.7880(4) 0.5808(4) 0.0274(11) Uani 1 1 d . . . H28A H 0.6442 0.7384 0.6574 0.041 Uiso 1 1 calc R . . H28B H 0.6569 0.7493 0.5376 0.041 Uiso 1 1 calc R . . H28C H 0.5748 0.8162 0.5912 0.041 Uiso 1 1 calc R . . C29 C 0.5754(3) 0.5105(3) 1.1265(3) 0.0187(9) Uani 1 1 d . . . C30 C 0.6081(4) 0.4422(3) 1.0819(4) 0.0259(11) Uani 1 1 d . . . H30 H 0.6031 0.4583 1.0122 0.031 Uiso 1 1 calc R . . C31 C 0.6487(4) 0.3494(3) 1.1359(4) 0.0231(10) Uani 1 1 d . . . H31 H 0.6715 0.3031 1.1034 0.028 Uiso 1 1 calc R . . C32 C 0.6552(4) 0.3260(3) 1.2386(4) 0.0240(10) Uani 1 1 d . . . C33 C 0.6191(4) 0.3921(3) 1.2868(4) 0.0233(10) Uani 1 1 d . . . H33 H 0.6221 0.3750 1.3575 0.028 Uiso 1 1 calc R . . C34 C 0.5786(4) 0.4828(3) 1.2326(4) 0.0213(10) Uani 1 1 d . . . H34 H 0.5526 0.5273 1.2670 0.026 Uiso 1 1 calc R . . C35 C 0.7215(5) 0.1629(4) 1.2580(4) 0.0401(13) Uani 1 1 d . . . H35A H 0.6522 0.1372 1.2555 0.060 Uiso 1 1 calc R . . H35B H 0.7431 0.1015 1.3108 0.060 Uiso 1 1 calc R . . H35C H 0.7875 0.1980 1.1795 0.060 Uiso 1 1 calc R . . C36 C 0.0320(4) 0.6807(4) 1.2405(4) 0.0248(10) Uani 1 1 d . . . C37 C -0.0158(4) 0.6746(4) 1.3497(4) 0.0260(10) Uani 1 1 d . . . C38 C -0.1331(4) 0.6206(4) 1.4287(4) 0.0307(12) Uani 1 1 d . . . H38 H -0.1670 0.6179 1.5021 0.037 Uiso 1 1 calc R . . C39 C -0.2004(4) 0.5714(4) 1.4026(4) 0.0325(12) Uani 1 1 d . . . C40 C -0.1504(4) 0.5765(4) 1.2949(4) 0.0330(12) Uani 1 1 d . . . H40 H -0.1964 0.5426 1.2764 0.040 Uiso 1 1 calc R . . C41 C -0.0346(4) 0.6297(4) 1.2127(4) 0.0305(11) Uani 1 1 d . . . C42 C 0.0556(4) 0.7200(4) 1.3861(4) 0.0341(12) Uani 1 1 d . . . H42A H 0.1040 0.6689 1.4127 0.051 Uiso 1 1 calc R . . H42B H 0.0027 0.7319 1.4498 0.051 Uiso 1 1 calc R . . H42C H 0.1069 0.7888 1.3195 0.051 Uiso 1 1 calc R . . C43 C -0.3253(4) 0.5101(5) 1.4909(4) 0.0454(15) Uani 1 1 d . . . H43A H -0.3238 0.4456 1.5572 0.068 Uiso 1 1 calc R . . H43B H -0.3627 0.4885 1.4542 0.068 Uiso 1 1 calc R . . H43C H -0.3704 0.5567 1.5184 0.068 Uiso 1 1 calc R . . C44 C 0.0154(5) 0.6308(5) 1.0975(4) 0.0441(14) Uani 1 1 d . . . H44A H 0.0313 0.7049 1.0341 0.066 Uiso 1 1 calc R . . H44B H -0.0415 0.5846 1.0985 0.066 Uiso 1 1 calc R . . H44C H 0.0890 0.6035 1.0854 0.066 Uiso 1 1 calc R . . C45 C 0.7076(4) 0.8408(4) 1.0214(4) 0.0240(10) Uani 1 1 d . . . H45A H 0.7391 0.9124 1.0053 0.029 Uiso 1 1 calc R . . H45B H 0.7397 0.8390 0.9472 0.029 Uiso 1 1 calc R . . C46 C 0.7377(4) 0.7518(4) 1.1094(4) 0.0270(11) Uani 1 1 d . . . H46A H 0.8174 0.7733 1.0985 0.032 Uiso 1 1 calc R . . H46B H 0.7339 0.6850 1.1046 0.032 Uiso 1 1 calc R . . C47 C 0.6426(4) 0.7363(4) 1.2256(4) 0.0268(11) Uani 1 1 d . . . H47A H 0.6271 0.6611 1.2890 0.032 Uiso 1 1 calc R . . H47B H 0.6668 0.7864 1.2466 0.032 Uiso 1 1 calc R . . C48 C 0.5337(4) 0.7612(3) 1.2051(3) 0.0234(10) Uani 1 1 d . . . H48A H 0.4765 0.6937 1.2426 0.028 Uiso 1 1 calc R . . H48B H 0.4949 0.8078 1.2375 0.028 Uiso 1 1 calc R . . N1 N 0.4908(3) 0.9565(3) 0.7932(3) 0.0212(8) Uani 1 1 d . . . N2 N 0.5850(3) 0.7890(3) 0.8892(3) 0.0192(8) Uani 1 1 d . . . N3 N 0.3679(3) 0.7097(3) 1.0949(3) 0.0182(8) Uani 1 1 d . . . N4 N 0.2996(3) 0.8868(3) 0.9721(3) 0.0215(8) Uani 1 1 d . . . O1 O 0.6948(3) 0.2386(2) 1.2990(3) 0.0303(8) Uani 1 1 d . . . O2 O 0.5772(2) 0.8180(2) 1.0770(2) 0.0212(7) Uani 1 1 d . . . Cl1 Cl 0.37662(9) 0.94571(8) 1.12223(8) 0.0209(2) Uani 1 1 d . . . Zr1 Zr 0.47058(4) 0.87212(3) 0.97055(3) 0.01999(14) 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 C1 0.023(2) 0.018(2) 0.021(2) -0.0054(19) -0.0092(19) 0.0105(18) C2 0.032(3) 0.021(2) 0.018(2) -0.0044(19) -0.011(2) 0.011(2) C3 0.026(2) 0.022(2) 0.014(2) -0.0044(19) -0.0067(19) 0.0076(19) C4 0.020(2) 0.020(2) 0.011(2) -0.0020(18) -0.0033(18) 0.0015(18) C5 0.019(2) 0.021(2) 0.011(2) -0.0057(18) -0.0062(18) 0.0052(18) C6 0.017(2) 0.020(2) 0.015(2) -0.0054(18) -0.0040(18) 0.0058(18) C7 0.020(2) 0.028(2) 0.019(2) -0.010(2) -0.0064(19) 0.0095(19) C8 0.024(2) 0.024(2) 0.018(2) -0.008(2) -0.0088(19) 0.0099(19) C9 0.021(2) 0.019(2) 0.019(2) -0.0076(19) -0.0094(19) 0.0098(18) C10 0.025(2) 0.018(2) 0.014(2) -0.0065(18) -0.0090(18) 0.0069(18) C11 0.022(2) 0.020(2) 0.012(2) -0.0042(18) -0.0067(18) 0.0119(18) C12 0.023(2) 0.022(2) 0.020(2) -0.007(2) -0.010(2) 0.0068(19) C13 0.017(2) 0.027(2) 0.015(2) 0.0007(19) -0.0041(18) 0.0004(19) C14 0.017(2) 0.028(2) 0.012(2) -0.0049(19) -0.0035(18) 0.0038(19) C15 0.020(2) 0.023(2) 0.014(2) -0.0042(19) -0.0051(18) 0.0051(19) C16 0.018(2) 0.023(2) 0.015(2) -0.0058(19) -0.0037(18) 0.0040(18) C17 0.020(2) 0.034(3) 0.020(2) -0.009(2) -0.0062(19) 0.013(2) C18 0.026(3) 0.028(3) 0.018(2) -0.008(2) -0.009(2) 0.011(2) C19 0.021(2) 0.025(2) 0.013(2) -0.0063(19) -0.0061(18) 0.0064(19) C20 0.018(2) 0.025(2) 0.017(2) -0.0071(19) -0.0075(18) 0.0105(18) C21 0.023(2) 0.024(2) 0.021(2) -0.009(2) -0.010(2) 0.0072(19) C22 0.021(2) 0.032(3) 0.024(2) -0.005(2) -0.009(2) -0.001(2) C23 0.020(2) 0.039(3) 0.018(2) -0.011(2) -0.0076(19) 0.007(2) C24 0.024(2) 0.033(3) 0.018(2) -0.011(2) -0.012(2) 0.012(2) C25 0.023(2) 0.021(2) 0.017(2) -0.0044(19) -0.0096(19) 0.0086(19) C26 0.031(3) 0.042(3) 0.043(3) -0.025(3) -0.012(2) 0.003(2) C27 0.026(3) 0.064(4) 0.022(3) -0.020(3) -0.001(2) -0.001(3) C28 0.031(3) 0.024(2) 0.024(2) -0.011(2) -0.010(2) 0.007(2) C29 0.016(2) 0.012(2) 0.018(2) -0.0049(18) -0.0024(18) 0.0052(17) C30 0.027(3) 0.026(2) 0.018(2) -0.006(2) -0.010(2) 0.009(2) C31 0.023(2) 0.022(2) 0.019(2) -0.0076(19) -0.0085(19) 0.0099(19) C32 0.023(2) 0.018(2) 0.019(2) -0.0020(19) -0.0073(19) 0.0050(19) C33 0.026(2) 0.021(2) 0.015(2) -0.0047(19) -0.0078(19) 0.0069(19) C34 0.028(2) 0.016(2) 0.017(2) -0.0065(18) -0.0084(19) 0.0098(18) C35 0.064(4) 0.026(3) 0.033(3) -0.017(2) -0.022(3) 0.026(3) C36 0.017(2) 0.026(2) 0.015(2) -0.0009(19) -0.0037(18) 0.0062(19) C37 0.021(2) 0.025(2) 0.023(2) -0.007(2) -0.008(2) 0.0073(19) C38 0.023(3) 0.036(3) 0.017(2) -0.008(2) -0.002(2) 0.009(2) C39 0.021(3) 0.041(3) 0.021(2) -0.005(2) -0.009(2) 0.004(2) C40 0.024(3) 0.043(3) 0.019(2) -0.006(2) -0.009(2) 0.001(2) C41 0.023(3) 0.038(3) 0.025(2) -0.010(2) -0.012(2) 0.007(2) C42 0.032(3) 0.039(3) 0.023(2) -0.012(2) -0.009(2) 0.007(2) C43 0.024(3) 0.066(4) 0.023(3) -0.010(3) -0.003(2) -0.003(3) C44 0.033(3) 0.062(4) 0.026(3) -0.017(3) -0.008(2) 0.003(3) C45 0.019(2) 0.025(2) 0.018(2) -0.0043(19) -0.0072(19) 0.0081(19) C46 0.022(2) 0.026(2) 0.028(2) -0.010(2) -0.011(2) 0.0102(19) C47 0.032(3) 0.021(2) 0.023(2) -0.008(2) -0.013(2) 0.011(2) C48 0.025(2) 0.020(2) 0.014(2) -0.0038(19) -0.0052(19) 0.0080(19) N1 0.0204(19) 0.0186(19) 0.0157(18) -0.0042(15) -0.0056(15) 0.0084(15) N2 0.0155(18) 0.0197(19) 0.0128(17) -0.0014(15) -0.0058(15) 0.0057(15) N3 0.0175(19) 0.0198(19) 0.0196(18) -0.0082(16) -0.0123(16) 0.0077(15) N4 0.021(2) 0.026(2) 0.0081(16) -0.0036(15) -0.0036(15) 0.0099(16) O1 0.043(2) 0.0189(16) 0.0256(17) -0.0080(14) -0.0165(15) 0.0183(15) O2 0.0150(15) 0.0236(16) 0.0124(14) -0.0034(13) -0.0017(12) 0.0065(12) Cl1 0.0193(5) 0.0203(5) 0.0140(5) -0.0049(4) -0.0038(4) 0.0070(4) Zr1 0.0175(2) 0.0205(2) 0.0127(2) -0.00403(18) -0.00386(17) 0.00879(17) _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 C1 N1 1.381(5) . ? C1 C2 1.414(6) . ? C1 C19 1.415(6) . ? C2 C3 1.365(6) . ? C2 H2 0.9500 . ? C3 C4 1.433(6) . ? C3 H3 0.9500 . ? C4 N1 1.377(5) . ? C4 C5 1.393(6) . ? C5 C6 1.409(5) . ? C5 C20 1.499(6) . ? C6 N2 1.413(5) . ? C6 C7 1.425(6) . ? C7 C8 1.363(6) . ? C7 H7 0.9500 . ? C8 C9 1.424(6) . ? C8 H8 0.9500 . ? C9 C10 1.398(6) . ? C9 N2 1.399(5) . ? C10 C11 1.404(6) . ? C10 C29 1.514(5) . ? C11 N3 1.402(5) . ? C11 C12 1.418(6) . ? C12 C13 1.344(6) . ? C12 H12 0.9500 . ? C13 C14 1.428(6) . ? C13 H13 0.9500 . ? C14 N3 1.400(5) . ? C14 C15 1.406(6) . ? C15 C16 1.411(6) . ? C15 C36 1.512(6) . ? C16 N4 1.390(5) . ? C16 C17 1.410(6) . ? C17 C18 1.380(6) . ? C17 H17 0.9500 . ? C18 C19 1.422(6) . ? C18 H18 0.9500 . ? C19 N4 1.370(5) . ? C20 C21 1.399(6) . ? C20 C25 1.409(6) . ? C21 C22 1.403(6) . ? C21 C26 1.494(7) . ? C22 C23 1.376(7) . ? C22 H22 0.9500 . ? C23 C24 1.376(6) . ? C23 C27 1.510(6) . ? C24 C25 1.409(6) . ? C24 H24 0.9500 . ? C25 C28 1.503(6) . ? C26 H26A 0.9800 . ? C26 H26B 0.9800 . ? C26 H26C 0.9800 . ? 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 C30 1.368(6) . ? C29 C34 1.410(6) . ? C30 C31 1.397(6) . ? C30 H30 0.9500 . ? C31 C32 1.398(6) . ? C31 H31 0.9500 . ? C32 O1 1.370(5) . ? C32 C33 1.378(6) . ? C33 C34 1.378(6) . ? C33 H33 0.9500 . ? C34 H34 0.9500 . ? C35 O1 1.425(6) . ? C35 H35A 0.9800 . ? C35 H35B 0.9800 . ? C35 H35C 0.9800 . ? C36 C37 1.398(6) . ? C36 C41 1.406(7) . ? C37 C38 1.405(6) . ? C37 C42 1.496(7) . ? C38 C39 1.375(7) . ? C38 H38 0.9500 . ? C39 C40 1.385(7) . ? C39 C43 1.515(6) . ? C40 C41 1.395(6) . ? C40 H40 0.9500 . ? C41 C44 1.510(7) . ? C42 H42A 0.9800 . ? C42 H42B 0.9800 . ? C42 H42C 0.9800 . ? C43 H43A 0.9800 . ? C43 H43B 0.9800 . ? C43 H43C 0.9800 . ? C44 H44A 0.9800 . ? C44 H44B 0.9800 . ? C44 H44C 0.9800 . ? C45 O2 1.479(5) . ? C45 C46 1.497(6) . ? C45 H45A 0.9900 . ? C45 H45B 0.9900 . ? C46 C47 1.528(6) . ? C46 H46A 0.9900 . ? C46 H46B 0.9900 . ? C47 C48 1.523(6) . ? C47 H47A 0.9900 . ? C47 H47B 0.9900 . ? C48 O2 1.478(5) . ? C48 H48A 0.9900 . ? C48 H48B 0.9900 . ? N1 Zr1 2.166(3) . ? N2 Zr1 2.164(3) . ? N3 Zr1 2.164(3) . ? N4 Zr1 2.161(3) . ? O2 Zr1 2.304(3) . ? Cl1 Zr1 2.6852(12) 2_677 ? Cl1 Zr1 2.6897(11) . ? Zr1 Cl1 2.6852(12) 2_677 ? 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 C1 C2 108.8(4) . . ? N1 C1 C19 112.7(3) . . ? C2 C1 C19 137.1(4) . . ? C3 C2 C1 107.6(4) . . ? C3 C2 H2 126.2 . . ? C1 C2 H2 126.2 . . ? C2 C3 C4 107.6(4) . . ? C2 C3 H3 126.2 . . ? C4 C3 H3 126.2 . . ? N1 C4 C5 121.1(4) . . ? N1 C4 C3 108.0(4) . . ? C5 C4 C3 130.4(4) . . ? C4 C5 C6 122.1(4) . . ? C4 C5 C20 119.6(3) . . ? C6 C5 C20 117.7(4) . . ? C5 C6 N2 126.0(4) . . ? C5 C6 C7 125.7(4) . . ? N2 C6 C7 108.1(3) . . ? C8 C7 C6 108.5(4) . . ? C8 C7 H7 125.8 . . ? C6 C7 H7 125.8 . . ? C7 C8 C9 107.9(4) . . ? C7 C8 H8 126.1 . . ? C9 C8 H8 126.1 . . ? C10 C9 N2 123.6(4) . . ? C10 C9 C8 127.2(4) . . ? N2 C9 C8 108.9(3) . . ? C9 C10 C11 125.4(4) . . ? C9 C10 C29 118.1(4) . . ? C11 C10 C29 116.3(3) . . ? N3 C11 C10 124.6(4) . . ? N3 C11 C12 108.2(3) . . ? C10 C11 C12 126.9(4) . . ? C13 C12 C11 108.9(4) . . ? C13 C12 H12 125.6 . . ? C11 C12 H12 125.6 . . ? C12 C13 C14 108.0(4) . . ? C12 C13 H13 126.0 . . ? C14 C13 H13 126.0 . . ? N3 C14 C15 126.4(4) . . ? N3 C14 C13 108.3(4) . . ? C15 C14 C13 124.9(4) . . ? C14 C15 C16 122.6(4) . . ? C14 C15 C36 117.7(4) . . ? C16 C15 C36 119.3(4) . . ? N4 C16 C17 108.7(4) . . ? N4 C16 C15 119.9(4) . . ? C17 C16 C15 130.5(4) . . ? C18 C17 C16 107.8(4) . . ? C18 C17 H17 126.1 . . ? C16 C17 H17 126.1 . . ? C17 C18 C19 106.7(4) . . ? C17 C18 H18 126.6 . . ? C19 C18 H18 126.6 . . ? N4 C19 C1 113.2(4) . . ? N4 C19 C18 109.4(4) . . ? C1 C19 C18 136.2(4) . . ? C21 C20 C25 120.4(4) . . ? C21 C20 C5 120.4(4) . . ? C25 C20 C5 119.3(4) . . ? C20 C21 C22 118.2(4) . . ? C20 C21 C26 121.5(4) . . ? C22 C21 C26 120.3(4) . . ? C23 C22 C21 122.7(4) . . ? C23 C22 H22 118.6 . . ? C21 C22 H22 118.6 . . ? C22 C23 C24 118.3(4) . . ? C22 C23 C27 120.1(4) . . ? C24 C23 C27 121.6(5) . . ? C23 C24 C25 122.0(4) . . ? C23 C24 H24 119.0 . . ? C25 C24 H24 119.0 . . ? C20 C25 C24 118.4(4) . . ? C20 C25 C28 121.6(4) . . ? C24 C25 C28 120.0(4) . . ? C21 C26 H26A 109.5 . . ? C21 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C21 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C23 C27 H27A 109.5 . . ? C23 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? C23 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? C25 C28 H28A 109.5 . . ? C25 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C25 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? C30 C29 C34 118.3(4) . . ? C30 C29 C10 122.5(4) . . ? C34 C29 C10 119.2(4) . . ? C29 C30 C31 121.8(4) . . ? C29 C30 H30 119.1 . . ? C31 C30 H30 119.1 . . ? C30 C31 C32 118.7(4) . . ? C30 C31 H31 120.6 . . ? C32 C31 H31 120.6 . . ? O1 C32 C33 115.3(4) . . ? O1 C32 C31 124.4(4) . . ? C33 C32 C31 120.3(4) . . ? C34 C33 C32 120.1(4) . . ? C34 C33 H33 120.0 . . ? C32 C33 H33 120.0 . . ? C33 C34 C29 120.8(4) . . ? C33 C34 H34 119.6 . . ? C29 C34 H34 119.6 . . ? O1 C35 H35A 109.5 . . ? O1 C35 H35B 109.5 . . ? H35A C35 H35B 109.5 . . ? O1 C35 H35C 109.5 . . ? H35A C35 H35C 109.5 . . ? H35B C35 H35C 109.5 . . ? C37 C36 C41 120.5(4) . . ? C37 C36 C15 119.9(4) . . ? C41 C36 C15 119.4(4) . . ? C36 C37 C38 118.5(4) . . ? C36 C37 C42 122.0(4) . . ? C38 C37 C42 119.4(4) . . ? C39 C38 C37 121.8(4) . . ? C39 C38 H38 119.1 . . ? C37 C38 H38 119.1 . . ? C38 C39 C40 118.6(4) . . ? C38 C39 C43 120.9(4) . . ? C40 C39 C43 120.5(5) . . ? C39 C40 C41 122.0(5) . . ? C39 C40 H40 119.0 . . ? C41 C40 H40 119.0 . . ? C40 C41 C36 118.4(4) . . ? C40 C41 C44 119.5(5) . . ? C36 C41 C44 122.1(4) . . ? C37 C42 H42A 109.5 . . ? C37 C42 H42B 109.5 . . ? H42A C42 H42B 109.5 . . ? C37 C42 H42C 109.5 . . ? H42A C42 H42C 109.5 . . ? H42B C42 H42C 109.5 . . ? C39 C43 H43A 109.5 . . ? C39 C43 H43B 109.5 . . ? H43A C43 H43B 109.5 . . ? C39 C43 H43C 109.5 . . ? H43A C43 H43C 109.5 . . ? H43B C43 H43C 109.5 . . ? C41 C44 H44A 109.5 . . ? C41 C44 H44B 109.5 . . ? H44A C44 H44B 109.5 . . ? C41 C44 H44C 109.5 . . ? H44A C44 H44C 109.5 . . ? H44B C44 H44C 109.5 . . ? O2 C45 C46 104.0(3) . . ? O2 C45 H45A 111.0 . . ? C46 C45 H45A 111.0 . . ? O2 C45 H45B 111.0 . . ? C46 C45 H45B 111.0 . . ? H45A C45 H45B 109.0 . . ? C45 C46 C47 103.0(3) . . ? C45 C46 H46A 111.2 . . ? C47 C46 H46A 111.2 . . ? C45 C46 H46B 111.2 . . ? C47 C46 H46B 111.2 . . ? H46A C46 H46B 109.1 . . ? C48 C47 C46 104.8(3) . . ? C48 C47 H47A 110.8 . . ? C46 C47 H47A 110.8 . . ? C48 C47 H47B 110.8 . . ? C46 C47 H47B 110.8 . . ? H47A C47 H47B 108.9 . . ? O2 C48 C47 105.6(3) . . ? O2 C48 H48A 110.6 . . ? C47 C48 H48A 110.6 . . ? O2 C48 H48B 110.6 . . ? C47 C48 H48B 110.6 . . ? H48A C48 H48B 108.8 . . ? C4 N1 C1 107.7(3) . . ? C4 N1 Zr1 134.7(3) . . ? C1 N1 Zr1 116.7(3) . . ? C9 N2 C6 106.4(3) . . ? C9 N2 Zr1 123.0(3) . . ? C6 N2 Zr1 127.5(3) . . ? C14 N3 C11 106.5(3) . . ? C14 N3 Zr1 129.2(3) . . ? C11 N3 Zr1 123.6(3) . . ? C19 N4 C16 107.2(3) . . ? C19 N4 Zr1 117.2(3) . . ? C16 N4 Zr1 134.8(3) . . ? C32 O1 C35 116.6(4) . . ? C48 O2 C45 108.6(3) . . ? C48 O2 Zr1 128.9(2) . . ? C45 O2 Zr1 122.5(2) . . ? Zr1 Cl1 Zr1 104.42(3) 2_677 . ? N4 Zr1 N3 76.89(12) . . ? N4 Zr1 N2 121.09(13) . . ? N3 Zr1 N2 82.06(13) . . ? N4 Zr1 N1 70.19(12) . . ? N3 Zr1 N1 122.01(13) . . ? N2 Zr1 N1 76.34(12) . . ? N4 Zr1 O2 147.37(11) . . ? N3 Zr1 O2 82.95(11) . . ? N2 Zr1 O2 80.40(11) . . ? N1 Zr1 O2 142.27(11) . . ? N4 Zr1 Cl1 118.00(10) . 2_677 ? N3 Zr1 Cl1 158.92(9) . 2_677 ? N2 Zr1 Cl1 100.28(9) . 2_677 ? N1 Zr1 Cl1 78.57(10) . 2_677 ? O2 Zr1 Cl1 76.86(7) . 2_677 ? N4 Zr1 Cl1 79.45(10) . . ? N3 Zr1 Cl1 94.02(10) . . ? N2 Zr1 Cl1 157.02(9) . . ? N1 Zr1 Cl1 123.68(9) . . ? O2 Zr1 Cl1 76.65(7) . . ? Cl1 Zr1 Cl1 75.58(3) 2_677 . ? _diffrn_measured_fraction_theta_max 0.973 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.861 _refine_diff_density_min -1.007 _refine_diff_density_rms 0.105 # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 -0.007 0.365 0.202 87 16 ' ' 2 0.007 0.642 0.788 81 15 ' ' 3 0.341 0.724 0.452 11 1 ' ' 4 0.659 0.275 0.548 11 1 ' ' _platon_squeeze_details ; ; _database_code_depnum_ccdc_archive 'CCDC 979187'