Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 loop_ _publ_author_name 'Lothar Stahl' 'Luke Grocholl' 'Daniel F. Moser' 'Richard J. Staples' _publ_contact_author_name 'Prof Lothar Stahl' _publ_contact_author_address ; Department of Chemistry University of North Dakota Grand Forks, ND 585620 USA ; _publ_contact_author_email lstahl@chem.und.edu _publ_contact_author_fax '(701) 777-2331' _publ_contact_author_phone '(701) 777-2242' # TITLE AND AUTHOR LIST _publ_section_title ; Bis(tert-butylamido)- and bis(arylamido)cyclodiphosph(III)azane complexes of titanium, vanadium, zirconium and hafnium: ligand substituent effects and coordination number ; data_1 _database_code_CSD 197168 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C16 H36 Cl2 N4 P2 Zr' _chemical_formula_weight 508.55 _chemical_melting_point ? _chemical_compound_source ? 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 9.921(2) _cell_length_b 15.129(3) _cell_length_c 16.331(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2451.2(8) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used 200 _cell_measurement_theta_min 4.52 _cell_measurement_theta_max 20.69 _exptl_crystal_description plate _exptl_crystal_colour colorless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.378 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1056 _exptl_absorpt_coefficient_mu 0.805 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.682695 _exptl_absorpt_correction_T_max 0.962314 _exptl_special_details ; Data was collected using a Siemens SMART CCD (charge coupled device) based diffractometer equipped with an LT-2 low-temperature apparatus operating at 213 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.3\% per frame for 10 seconds, such that a hemisphere was collected. A total of 1271 frames were collected with a final resolution of 0.75 \%A. The first 50 frames were recollected at the end of data collection to monitor for decay. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software which corrects for Lp and decay. Absorption corrections were applied using SADABS supplied by George Sheldrick. The structures are solved by the direct method using the SHELX-90 program and refined by least squares method on F2 SHELXL-93, incorporated in SHELXTL-PC V 5.03. Carbon-bound H atoms were placed in idealized positions [C -H = 0.96\%A] and refined as a riding model. ; _diffrn_ambient_temperature 213(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens P4/CCD' _diffrn_measurement_method '\f,(Phi) 0.3 deg' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1 _diffrn_reflns_number 9072 _diffrn_reflns_av_R_equivalents 0.0248 _diffrn_reflns_av_sigmaI/netI 0.0436 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.83 _diffrn_reflns_theta_max 28.07 _reflns_number_total 4921 _reflns_number_observed 4386 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'ASTRO (SIEMENS, V4.033, 1994)' _computing_cell_refinement 'SMART (SIEMENS, V4.033, 1994)' _computing_data_reduction 'SAINT (SIEMENS, V4.035, 1994)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'SHELXTL (SIEMENS, 1994, ver 5.04)' _computing_publication_material 'CIFTAB (Sheldrick, 1993)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0504P)^2^+1.9048P] 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 0.00(13) _refine_ls_number_reflns 4921 _refine_ls_number_parameters 254 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0487 _refine_ls_R_factor_obs 0.0412 _refine_ls_wR_factor_all 0.1073 _refine_ls_wR_factor_obs 0.1017 _refine_ls_goodness_of_fit_all 1.016 _refine_ls_goodness_of_fit_obs 1.023 _refine_ls_restrained_S_all 1.016 _refine_ls_restrained_S_obs 1.023 _refine_ls_shift/esd_max -0.001 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Zr1 Zr 0.27934(5) 0.34421(3) 0.28453(3) 0.05147(15) Uani 1 d . . P1 P 0.35832(10) 0.27716(7) 0.12667(6) 0.0341(2) Uani 1 d . . P2 P 0.39609(10) 0.17224(6) 0.25853(6) 0.0333(2) Uani 1 d . . Cl1 Cl 0.3958(2) 0.46032(10) 0.35214(9) 0.0897(6) Uani 1 d . . Cl2 Cl 0.0483(2) 0.36382(14) 0.32341(12) 0.1083(8) Uani 1 d . . N1 N 0.4622(3) 0.2715(2) 0.2161(2) 0.0317(6) Uani 1 d . . N2 N 0.2805(5) 0.1930(3) 0.1806(2) 0.0639(12) Uani 1 d . . N3 N 0.2734(3) 0.3663(2) 0.1601(2) 0.0397(7) Uani 1 d . . N4 N 0.3239(3) 0.2240(2) 0.3383(2) 0.0357(7) Uani 1 d . . C1 C 0.6104(4) 0.2886(3) 0.2118(3) 0.0415(9) Uani 1 d . . C2 C 0.6315(5) 0.3796(3) 0.1753(3) 0.0524(11) Uani 1 d . . H2A H 0.5941(5) 0.3812(3) 0.1204(3) 0.079 Uiso 1 calc R . H2B H 0.7271(5) 0.3926(3) 0.1730(3) 0.079 Uiso 1 calc R . H2C H 0.5866(5) 0.4234(3) 0.2091(3) 0.079 Uiso 1 calc R . C3 C 0.6678(4) 0.2831(4) 0.2985(3) 0.0593(13) Uani 1 d . . H3A H 0.6529(4) 0.2243(4) 0.3203(3) 0.089 Uiso 1 calc R . H3B H 0.6232(4) 0.3262(4) 0.3331(3) 0.089 Uiso 1 calc R . H3C H 0.7638(4) 0.2954(4) 0.2971(3) 0.089 Uiso 1 calc R . C4 C 0.6764(4) 0.2186(4) 0.1570(3) 0.0584(12) Uani 1 d . . H4A H 0.6626(4) 0.1605(4) 0.1807(3) 0.088 Uiso 1 calc R . H4B H 0.7722(4) 0.2303(4) 0.1527(3) 0.088 Uiso 1 calc R . H4C H 0.6360(4) 0.2206(4) 0.1029(3) 0.088 Uiso 1 calc R . C5 C 0.1798(7) 0.1300(4) 0.1481(4) 0.072(2) Uani 1 d . . C6 C 0.0656(10) 0.1877(8) 0.1007(7) 0.074(4) Uani 0.541(12) d P 1 H6A H 0.0311(10) 0.2330(8) 0.1372(7) 0.110 Uiso 0.541(12) calc PR 1 H6B H -0.0075(10) 0.1492(8) 0.0839(7) 0.110 Uiso 0.541(12) calc PR 1 H6C H 0.1052(10) 0.2154(8) 0.0528(7) 0.110 Uiso 0.541(12) calc PR 1 C7 C 0.0890(13) 0.0950(9) 0.2253(9) 0.086(4) Uani 0.541(12) d P 1 H7A H 0.0530(13) 0.1452(9) 0.2550(9) 0.128 Uiso 0.541(12) calc PR 1 H7B H 0.1449(13) 0.0600(9) 0.2617(9) 0.128 Uiso 0.541(12) calc PR 1 H7C H 0.0153(13) 0.0590(9) 0.2050(9) 0.128 Uiso 0.541(12) calc PR 1 C8 C 0.2338(13) 0.0661(8) 0.1034(9) 0.084(5) Uani 0.541(12) d P 1 H8A H 0.3006(13) 0.0348(8) 0.1357(9) 0.126 Uiso 0.541(12) calc PR 1 H8B H 0.2765(13) 0.0913(8) 0.0554(9) 0.126 Uiso 0.541(12) calc PR 1 H8C H 0.1638(13) 0.0252(8) 0.0865(9) 0.126 Uiso 0.541(12) calc PR 1 C9 C 0.2192(6) 0.4373(3) 0.1052(3) 0.0604(13) Uani 1 d . . C10 C 0.0726(7) 0.4165(6) 0.0820(5) 0.111(3) Uani 1 d . . H10A H 0.0695(7) 0.3620(6) 0.0509(5) 0.167 Uiso 1 calc R . H10B H 0.0366(7) 0.4644(6) 0.0490(5) 0.167 Uiso 1 calc R . H10C H 0.0191(7) 0.4102(6) 0.1313(5) 0.167 Uiso 1 calc R . C11 C 0.2248(8) 0.5229(4) 0.1540(4) 0.084(2) Uani 1 d . . H11A H 0.1711(8) 0.5167(4) 0.2033(4) 0.125 Uiso 1 calc R . H11B H 0.1895(8) 0.5709(4) 0.1210(4) 0.125 Uiso 1 calc R . H11C H 0.3175(8) 0.5355(4) 0.1688(4) 0.125 Uiso 1 calc R . C12 C 0.3031(7) 0.4454(4) 0.0273(3) 0.073(2) Uani 1 d . . H12A H 0.2985(7) 0.3904(4) -0.0031(3) 0.109 Uiso 1 calc R . H12B H 0.3960(7) 0.4578(4) 0.0417(3) 0.109 Uiso 1 calc R . H12C H 0.2680(7) 0.4932(4) -0.0061(3) 0.109 Uiso 1 calc R . C13 C 0.3090(5) 0.1857(3) 0.4216(3) 0.0537(12) Uani 1 d . . C14 C 0.4242(8) 0.1232(4) 0.4411(3) 0.087(2) Uani 1 d . . H14A H 0.4243(8) 0.0749(4) 0.4021(3) 0.131 Uiso 1 calc R . H14B H 0.4129(8) 0.1000(4) 0.4960(3) 0.131 Uiso 1 calc R . H14C H 0.5090(8) 0.1549(4) 0.4376(3) 0.131 Uiso 1 calc R . C15 C 0.1758(9) 0.1362(6) 0.4261(5) 0.118(3) Uani 1 d . . H15A H 0.1767(9) 0.0876(6) 0.3874(5) 0.177 Uiso 1 calc R . H15B H 0.1025(9) 0.1761(6) 0.4129(5) 0.177 Uiso 1 calc R . H15C H 0.1633(9) 0.1132(6) 0.4811(5) 0.177 Uiso 1 calc R . C16 C 0.3077(9) 0.2612(4) 0.4818(3) 0.091(2) Uani 1 d . . H16A H 0.2338(9) 0.3009(4) 0.4690(3) 0.136 Uiso 1 calc R . H16B H 0.3923(9) 0.2932(4) 0.4785(3) 0.136 Uiso 1 calc R . H16C H 0.2962(9) 0.2382(4) 0.5368(3) 0.136 Uiso 1 calc R . C8A C 0.1989(17) 0.1251(10) 0.0484(8) 0.086(5) Uani 0.459(12) d P 2 H8AA H 0.2911(17) 0.1088(10) 0.0356(8) 0.128 Uiso 0.459(12) calc PR 2 H8AB H 0.1789(17) 0.1824(10) 0.0246(8) 0.128 Uiso 0.459(12) calc PR 2 H8AC H 0.1379(17) 0.0812(10) 0.0260(8) 0.128 Uiso 0.459(12) calc PR 2 C7A C 0.2292(14) 0.0279(8) 0.1687(10) 0.074(4) Uani 0.459(12) d P 2 H7AA H 0.3198(14) 0.0189(8) 0.1479(10) 0.111 Uiso 0.459(12) calc PR 2 H7AB H 0.1683(14) -0.0138(8) 0.1427(10) 0.111 Uiso 0.459(12) calc PR 2 H7AC H 0.2284(14) 0.0186(8) 0.2274(10) 0.111 Uiso 0.459(12) calc PR 2 C6A C 0.0602(11) 0.1513(11) 0.1724(10) 0.078(5) Uani 0.459(12) d P 2 H6AA H 0.0579(11) 0.1526(11) 0.2318(10) 0.116 Uiso 0.459(12) calc PR 2 H6AB H -0.0041(11) 0.1080(11) 0.1525(10) 0.116 Uiso 0.459(12) calc PR 2 H6AC H 0.0369(11) 0.2092(11) 0.1511(10) 0.116 Uiso 0.459(12) calc PR 2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Zr1 0.0648(3) 0.0490(2) 0.0406(2) 0.0130(2) 0.0286(2) 0.0256(2) P1 0.0362(5) 0.0419(5) 0.0242(4) -0.0016(4) 0.0024(4) 0.0029(4) P2 0.0377(5) 0.0330(5) 0.0293(4) -0.0002(4) -0.0011(4) 0.0044(4) Cl1 0.153(2) 0.0554(8) 0.0603(8) -0.0112(6) 0.0448(10) 0.0027(9) Cl2 0.0840(10) 0.122(2) 0.1187(14) 0.0502(12) 0.0654(10) 0.0583(11) N1 0.0295(14) 0.039(2) 0.0270(13) 0.0002(14) 0.0021(13) 0.0041(12) N2 0.087(3) 0.058(2) 0.047(2) 0.019(2) -0.035(2) -0.035(2) N3 0.036(2) 0.041(2) 0.042(2) 0.0041(14) -0.0026(15) 0.0084(15) N4 0.040(2) 0.043(2) 0.0250(14) 0.0008(14) 0.0055(13) 0.0004(14) C1 0.030(2) 0.054(2) 0.041(2) -0.001(2) 0.003(2) 0.001(2) C2 0.042(2) 0.057(3) 0.058(3) 0.003(2) 0.007(2) -0.009(2) C3 0.041(2) 0.077(3) 0.060(3) 0.002(3) -0.017(2) -0.007(2) C4 0.039(2) 0.067(3) 0.069(3) -0.002(3) 0.016(2) 0.012(2) C5 0.093(4) 0.059(3) 0.063(3) 0.014(3) -0.037(3) -0.041(3) C6 0.051(5) 0.096(9) 0.074(7) -0.008(6) -0.012(5) -0.014(6) C7 0.083(8) 0.076(8) 0.097(9) -0.016(8) 0.009(8) -0.045(7) C8 0.083(8) 0.063(7) 0.105(12) -0.040(8) -0.008(8) -0.011(6) C9 0.061(3) 0.060(3) 0.060(3) 0.000(2) -0.016(3) 0.023(3) C10 0.068(4) 0.124(6) 0.141(7) -0.001(6) -0.050(5) 0.038(4) C11 0.129(6) 0.049(3) 0.074(4) 0.003(3) -0.009(4) 0.028(4) C12 0.095(4) 0.072(3) 0.050(3) 0.018(3) -0.020(3) 0.011(3) C13 0.067(3) 0.063(3) 0.032(2) 0.016(2) 0.013(2) 0.005(2) C14 0.133(6) 0.087(4) 0.041(3) 0.027(3) 0.005(3) 0.035(4) C15 0.114(6) 0.146(8) 0.094(5) 0.048(5) 0.036(5) -0.042(6) C16 0.160(7) 0.082(4) 0.031(2) 0.005(3) 0.020(3) 0.013(5) C8A 0.120(12) 0.085(10) 0.052(7) -0.014(7) -0.034(8) -0.038(9) C7A 0.075(8) 0.045(6) 0.102(11) 0.000(7) -0.040(8) -0.011(6) C6A 0.038(6) 0.097(11) 0.098(12) -0.011(10) 0.003(6) -0.009(7) _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 N3 2.060(3) . ? Zr1 N4 2.067(3) . ? Zr1 Cl1 2.375(2) . ? Zr1 Cl2 2.397(2) . ? Zr1 N1 2.398(3) . ? Zr1 P1 2.8791(11) . ? Zr1 P2 2.8795(11) . ? P1 N3 1.682(3) . ? P1 N2 1.729(4) . ? P1 N1 1.790(3) . ? P2 N4 1.681(3) . ? P2 N2 1.743(4) . ? P2 N1 1.780(3) . ? N1 C1 1.495(4) . ? N2 C5 1.479(6) . ? N3 C9 1.499(6) . ? N4 C13 1.485(5) . ? C1 C2 1.515(6) . ? C1 C3 1.528(6) . ? C1 C4 1.534(6) . ? C5 C6A 1.292(14) . ? C5 C8 1.325(12) . ? C5 C6 1.625(13) . ? C5 C7 1.638(14) . ? C5 C8A 1.641(14) . ? C5 C7A 1.656(13) . ? C9 C11 1.522(7) . ? C9 C12 1.524(8) . ? C9 C10 1.535(9) . ? C13 C16 1.508(7) . ? C13 C14 1.517(8) . ? C13 C15 1.521(9) . ? 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 N3 Zr1 N4 124.62(13) . . ? N3 Zr1 Cl1 110.63(11) . . ? N4 Zr1 Cl1 110.43(10) . . ? N3 Zr1 Cl2 102.35(11) . . ? N4 Zr1 Cl2 101.58(10) . . ? Cl1 Zr1 Cl2 104.51(8) . . ? N3 Zr1 N1 68.68(12) . . ? N4 Zr1 N1 68.46(11) . . ? Cl1 Zr1 N1 100.82(9) . . ? Cl2 Zr1 N1 154.66(10) . . ? N3 Zr1 P1 35.10(9) . . ? N4 Zr1 P1 90.71(9) . . ? Cl1 Zr1 P1 122.99(5) . . ? Cl2 Zr1 P1 122.76(6) . . ? N1 Zr1 P1 38.30(7) . . ? N3 Zr1 P2 90.73(9) . . ? N4 Zr1 P2 35.10(8) . . ? Cl1 Zr1 P2 122.76(6) . . ? Cl2 Zr1 P2 122.38(6) . . ? N1 Zr1 P2 38.05(7) . . ? P1 Zr1 P2 55.95(3) . . ? N3 P1 N2 101.6(2) . . ? N3 P1 N1 93.5(2) . . ? N2 P1 N1 78.9(2) . . ? N3 P1 Zr1 44.79(11) . . ? N2 P1 Zr1 71.5(2) . . ? N1 P1 Zr1 56.13(9) . . ? N4 P2 N2 101.6(2) . . ? N4 P2 N1 93.7(2) . . ? N2 P2 N1 78.8(2) . . ? N4 P2 Zr1 45.01(11) . . ? N2 P2 Zr1 71.3(2) . . ? N1 P2 Zr1 56.14(9) . . ? C1 N1 P2 121.8(3) . . ? C1 N1 P1 121.3(3) . . ? P2 N1 P1 98.37(15) . . ? C1 N1 Zr1 133.4(2) . . ? P2 N1 Zr1 85.81(11) . . ? P1 N1 Zr1 85.57(11) . . ? C5 N2 P1 126.4(3) . . ? C5 N2 P2 126.2(3) . . ? P1 N2 P2 102.2(2) . . ? C9 N3 P1 124.1(3) . . ? C9 N3 Zr1 135.8(3) . . ? P1 N3 Zr1 100.1(2) . . ? C13 N4 P2 124.8(3) . . ? C13 N4 Zr1 135.3(3) . . ? P2 N4 Zr1 99.89(15) . . ? N1 C1 C2 108.1(3) . . ? N1 C1 C3 108.3(3) . . ? C2 C1 C3 111.3(4) . . ? N1 C1 C4 109.1(3) . . ? C2 C1 C4 109.8(4) . . ? C3 C1 C4 110.1(4) . . ? C6A C5 N2 110.5(9) . . ? C8 C5 N2 113.3(8) . . ? C8 C5 C6 114.4(9) . . ? N2 C5 C6 107.2(6) . . ? C8 C5 C7 114.2(9) . . ? N2 C5 C7 107.7(6) . . ? C6 C5 C7 99.0(9) . . ? C6A C5 C8A 115.0(10) . . ? N2 C5 C8A 107.9(6) . . ? C6A C5 C7A 116.2(10) . . ? N2 C5 C7A 109.2(6) . . ? C8A C5 C7A 97.2(10) . . ? N3 C9 C11 106.4(4) . . ? N3 C9 C12 111.2(4) . . ? C11 C9 C12 110.4(5) . . ? N3 C9 C10 110.0(5) . . ? C11 C9 C10 109.8(5) . . ? C12 C9 C10 109.1(5) . . ? N4 C13 C16 107.6(4) . . ? N4 C13 C14 111.1(4) . . ? C16 C13 C14 110.0(5) . . ? N4 C13 C15 108.9(4) . . ? C16 C13 C15 109.5(6) . . ? C14 C13 C15 109.7(6) . . ? 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 N3 Zr1 P1 N3 0.0 . . . . ? N4 Zr1 P1 N3 166.0(2) . . . . ? Cl1 Zr1 P1 N3 -78.9(2) . . . . ? Cl2 Zr1 P1 N3 61.8(2) . . . . ? N1 Zr1 P1 N3 -141.4(2) . . . . ? P2 Zr1 P1 N3 171.3(2) . . . . ? N3 Zr1 P1 N2 -129.7(2) . . . . ? N4 Zr1 P1 N2 36.3(2) . . . . ? Cl1 Zr1 P1 N2 151.4(2) . . . . ? Cl2 Zr1 P1 N2 -68.0(2) . . . . ? N1 Zr1 P1 N2 88.8(2) . . . . ? P2 Zr1 P1 N2 41.5(2) . . . . ? N3 Zr1 P1 N1 141.4(2) . . . . ? N4 Zr1 P1 N1 -52.55(15) . . . . ? Cl1 Zr1 P1 N1 62.55(13) . . . . ? Cl2 Zr1 P1 N1 -156.83(13) . . . . ? N1 Zr1 P1 N1 0.0 . . . . ? P2 Zr1 P1 N1 -47.33(12) . . . . ? N3 Zr1 P2 N4 -165.9(2) . . . . ? N4 Zr1 P2 N4 0.0 . . . . ? Cl1 Zr1 P2 N4 78.8(2) . . . . ? Cl2 Zr1 P2 N4 -60.7(2) . . . . ? N1 Zr1 P2 N4 141.4(2) . . . . ? P1 Zr1 P2 N4 -170.9(2) . . . . ? N3 Zr1 P2 N2 -36.2(2) . . . . ? N4 Zr1 P2 N2 129.7(2) . . . . ? Cl1 Zr1 P2 N2 -151.5(2) . . . . ? Cl2 Zr1 P2 N2 69.0(2) . . . . ? N1 Zr1 P2 N2 -88.8(2) . . . . ? P1 Zr1 P2 N2 -41.2(2) . . . . ? N3 Zr1 P2 N1 52.7(2) . . . . ? N4 Zr1 P2 N1 -141.4(2) . . . . ? Cl1 Zr1 P2 N1 -62.61(13) . . . . ? Cl2 Zr1 P2 N1 157.84(13) . . . . ? N1 Zr1 P2 N1 0.0 . . . . ? P1 Zr1 P2 N1 47.67(12) . . . . ? N4 P2 N1 C1 113.7(3) . . . . ? N2 P2 N1 C1 -145.2(3) . . . . ? Zr1 P2 N1 C1 139.9(3) . . . . ? N4 P2 N1 P1 -111.1(2) . . . . ? N2 P2 N1 P1 -10.0(2) . . . . ? Zr1 P2 N1 P1 -84.89(12) . . . . ? N4 P2 N1 Zr1 -26.22(13) . . . . ? N2 P2 N1 Zr1 74.9(2) . . . . ? Zr1 P2 N1 Zr1 0.0 . . . . ? N3 P1 N1 C1 -113.3(3) . . . . ? N2 P1 N1 C1 145.5(3) . . . . ? Zr1 P1 N1 C1 -139.4(3) . . . . ? N3 P1 N1 P2 111.2(2) . . . . ? N2 P1 N1 P2 10.1(2) . . . . ? Zr1 P1 N1 P2 85.09(12) . . . . ? N3 P1 N1 Zr1 26.12(14) . . . . ? N2 P1 N1 Zr1 -75.0(2) . . . . ? Zr1 P1 N1 Zr1 0.0 . . . . ? N3 Zr1 N1 C1 107.5(4) . . . . ? N4 Zr1 N1 C1 -108.5(4) . . . . ? Cl1 Zr1 N1 C1 -0.6(3) . . . . ? Cl2 Zr1 N1 C1 -179.2(3) . . . . ? P1 Zr1 N1 C1 130.1(4) . . . . ? P2 Zr1 N1 C1 -131.1(4) . . . . ? N3 Zr1 N1 P2 -121.4(2) . . . . ? N4 Zr1 N1 P2 22.67(12) . . . . ? Cl1 Zr1 N1 P2 130.52(10) . . . . ? Cl2 Zr1 N1 P2 -48.1(2) . . . . ? P1 Zr1 N1 P2 -98.75(14) . . . . ? P2 Zr1 N1 P2 0.0 . . . . ? N3 Zr1 N1 P1 -22.64(13) . . . . ? N4 Zr1 N1 P1 121.42(15) . . . . ? Cl1 Zr1 N1 P1 -130.73(10) . . . . ? Cl2 Zr1 N1 P1 50.6(2) . . . . ? P1 Zr1 N1 P1 0.0 . . . . ? P2 Zr1 N1 P1 98.75(14) . . . . ? N3 P1 N2 C5 102.9(6) . . . . ? N1 P1 N2 C5 -165.7(6) . . . . ? Zr1 P1 N2 C5 136.5(6) . . . . ? N3 P1 N2 P2 -101.8(2) . . . . ? N1 P1 N2 P2 -10.4(2) . . . . ? Zr1 P1 N2 P2 -68.2(2) . . . . ? N4 P2 N2 C5 -102.6(6) . . . . ? N1 P2 N2 C5 165.9(6) . . . . ? Zr1 P2 N2 C5 -136.3(6) . . . . ? N4 P2 N2 P1 102.0(3) . . . . ? N1 P2 N2 P1 10.5(2) . . . . ? Zr1 P2 N2 P1 68.3(2) . . . . ? N2 P1 N3 C9 -133.5(4) . . . . ? N1 P1 N3 C9 147.2(4) . . . . ? Zr1 P1 N3 C9 178.4(5) . . . . ? N2 P1 N3 Zr1 48.1(2) . . . . ? N1 P1 N3 Zr1 -31.3(2) . . . . ? Zr1 P1 N3 Zr1 0.0 . . . . ? N4 Zr1 N3 C9 164.8(4) . . . . ? Cl1 Zr1 N3 C9 -59.7(5) . . . . ? Cl2 Zr1 N3 C9 51.2(5) . . . . ? N1 Zr1 N3 C9 -153.6(5) . . . . ? P1 Zr1 N3 C9 -178.1(6) . . . . ? P2 Zr1 N3 C9 174.6(4) . . . . ? N4 Zr1 N3 P1 -17.1(2) . . . . ? Cl1 Zr1 N3 P1 118.43(14) . . . . ? Cl2 Zr1 N3 P1 -130.68(14) . . . . ? N1 Zr1 N3 P1 24.51(14) . . . . ? P1 Zr1 N3 P1 0.0 . . . . ? P2 Zr1 N3 P1 -7.24(15) . . . . ? N2 P2 N4 C13 134.0(4) . . . . ? N1 P2 N4 C13 -146.7(3) . . . . ? Zr1 P2 N4 C13 -177.9(4) . . . . ? N2 P2 N4 Zr1 -48.1(2) . . . . ? N1 P2 N4 Zr1 31.3(2) . . . . ? Zr1 P2 N4 Zr1 0.0 . . . . ? N3 Zr1 N4 C13 -165.2(4) . . . . ? Cl1 Zr1 N4 C13 59.3(4) . . . . ? Cl2 Zr1 N4 C13 -51.2(4) . . . . ? N1 Zr1 N4 C13 153.2(4) . . . . ? P1 Zr1 N4 C13 -174.9(4) . . . . ? P2 Zr1 N4 C13 177.6(5) . . . . ? N3 Zr1 N4 P2 17.2(2) . . . . ? Cl1 Zr1 N4 P2 -118.32(13) . . . . ? Cl2 Zr1 N4 P2 131.24(14) . . . . ? N1 Zr1 N4 P2 -24.40(13) . . . . ? P1 Zr1 N4 P2 7.53(14) . . . . ? P2 Zr1 N4 P2 0.0 . . . . ? P2 N1 C1 C2 -178.1(3) . . . . ? P1 N1 C1 C2 56.6(4) . . . . ? Zr1 N1 C1 C2 -60.2(4) . . . . ? P2 N1 C1 C3 -57.4(4) . . . . ? P1 N1 C1 C3 177.3(3) . . . . ? Zr1 N1 C1 C3 60.5(5) . . . . ? P2 N1 C1 C4 62.5(4) . . . . ? P1 N1 C1 C4 -62.8(4) . . . . ? Zr1 N1 C1 C4 -179.7(3) . . . . ? P1 N2 C5 C6A -103.5(10) . . . . ? P2 N2 C5 C6A 106.8(10) . . . . ? P1 N2 C5 C8 77.7(10) . . . . ? P2 N2 C5 C8 -72.0(10) . . . . ? P1 N2 C5 C6 -49.4(9) . . . . ? P2 N2 C5 C6 161.0(6) . . . . ? P1 N2 C5 C7 -155.1(7) . . . . ? P2 N2 C5 C7 55.3(9) . . . . ? P1 N2 C5 C8A 22.9(10) . . . . ? P2 N2 C5 C8A -126.7(8) . . . . ? P1 N2 C5 C7A 127.5(8) . . . . ? P2 N2 C5 C7A -22.1(10) . . . . ? P1 N3 C9 C11 -148.3(4) . . . . ? Zr1 N3 C9 C11 29.5(7) . . . . ? P1 N3 C9 C12 -28.1(6) . . . . ? Zr1 N3 C9 C12 149.7(4) . . . . ? P1 N3 C9 C10 92.9(5) . . . . ? Zr1 N3 C9 C10 -89.4(6) . . . . ? P2 N4 C13 C16 151.8(4) . . . . ? Zr1 N4 C13 C16 -25.3(7) . . . . ? P2 N4 C13 C14 31.4(6) . . . . ? Zr1 N4 C13 C14 -145.8(4) . . . . ? P2 N4 C13 C15 -89.5(6) . . . . ? Zr1 N4 C13 C15 93.3(6) . . . . ? _refine_diff_density_max 0.373 _refine_diff_density_min -1.039 _refine_diff_density_rms 0.073 #===END=== data_2 _database_code_CSD 197169 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C16 H36 Cl2 Hf N4 P2' _chemical_formula_weight 595.82 _chemical_melting_point ? _chemical_compound_source ? 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' P P 0.1023 0.0942 '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 Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 9.937(3) _cell_length_b 15.132(4) _cell_length_c 16.414(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2468(1) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used 184 _cell_measurement_theta_min 4.20 _cell_measurement_theta_max 20.67 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.603 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1184 _exptl_absorpt_coefficient_mu 4.580 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.738433 _exptl_absorpt_correction_T_max 0.942282 _exptl_special_details ; Data was collected using a Siemens SMART CCD (charge coupled device) based diffractometer equipped with an LT-2 low-temperature apparatus operating at 213 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.3\% per frame for 10 seconds, such that a hemisphere was collected. A total of 1271 frames were collected with a final resolution of 0.90 \%A. The first 50 frames were recollected at the end of data collection to monitor for decay. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software which corrects for Lp and decay. Absorption corrections were applied using SADABS supplied by George Sheldrick. The structures are solved by the direct method using the SHELX-90 program and refined by least squares method on F2 SHELXL-93, incorporated in SHELXTL-PC V 5.03. Carbon-bound H atoms were placed in idealized positions. ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens CCD' _diffrn_measurement_method '\w, 0.3 deg' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1 _diffrn_reflns_number 6141 _diffrn_reflns_av_R_equivalents 0.0221 _diffrn_reflns_av_sigmaI/netI 0.0334 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.83 _diffrn_reflns_theta_max 22.50 _reflns_number_total 3078 _reflns_number_observed 2871 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'ASTRO (SIEMENS, V4.033, 1994)' _computing_cell_refinement 'SMART (SIEMENS, V4.033, 1994)' _computing_data_reduction 'SAINT (SIEMENS, V4.035, 1994)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'SHELXTL (SIEMENS, 1994, ver 5.04)' _computing_publication_material 'CIFTAB (Sheldrick, 1993)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0511P)^2^+20.7304P] 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 0.0016(2) _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 0.19(2) _refine_ls_number_reflns 3078 _refine_ls_number_parameters 254 _refine_ls_number_restraints 24 _refine_ls_R_factor_all 0.0511 _refine_ls_R_factor_obs 0.0472 _refine_ls_wR_factor_all 0.1184 _refine_ls_wR_factor_obs 0.1138 _refine_ls_goodness_of_fit_all 1.050 _refine_ls_goodness_of_fit_obs 1.048 _refine_ls_restrained_S_all 1.046 _refine_ls_restrained_S_obs 1.044 _refine_ls_shift/esd_max -0.008 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Hf1 Hf -0.22350(7) 1.15703(4) 0.71788(3) 0.0633(3) Uani 1 d . . Cl1 Cl -0.1113(7) 1.0408(3) 0.6508(3) 0.104(2) Uani 1 d . . Cl2 Cl -0.4531(5) 1.1370(4) 0.6804(3) 0.123(2) Uani 1 d . . P1 P -0.1412(3) 1.2222(2) 0.8734(2) 0.0422(7) Uani 1 d . . P2 P -0.1057(3) 1.3277(2) 0.7409(2) 0.0413(7) Uani 1 d . . N1 N -0.0387(9) 1.2285(5) 0.7843(6) 0.040(2) Uani 1 d . . N2 N -0.2209(14) 1.3054(7) 0.8191(7) 0.073(4) Uani 1 d . . N3 N -0.2257(10) 1.1357(6) 0.8431(6) 0.048(2) Uani 1 d . . N4 N -0.1766(10) 1.2750(6) 0.6630(5) 0.042(2) Uani 1 d . . C1 C 0.1085(10) 1.2090(8) 0.7873(8) 0.048(3) Uani 1 d . . C2 C 0.1762(14) 1.2799(10) 0.8411(10) 0.072(4) Uani 1 d . . H2A H 0.1614(14) 1.3373(10) 0.8177(10) 0.107 Uiso 1 calc R . H2B H 0.2711(14) 1.2686(10) 0.8441(10) 0.107 Uiso 1 calc R . H2C H 0.1382(14) 1.2781(10) 0.8948(10) 0.107 Uiso 1 calc R . C3 C 0.1616(13) 1.2143(10) 0.6990(9) 0.072(4) Uani 1 d . . H3A H 0.1448(13) 1.2723(10) 0.6775(9) 0.108 Uiso 1 calc R . H3B H 0.1163(13) 1.1712(10) 0.6660(9) 0.108 Uiso 1 calc R . H3C H 0.2566(13) 1.2028(10) 0.6985(9) 0.108 Uiso 1 calc R . C4 C 0.1319(14) 1.1199(9) 0.8239(9) 0.062(4) Uani 1 d . . H4A H 0.0900(14) 1.0756(9) 0.7906(9) 0.094 Uiso 1 calc R . H4B H 0.0940(14) 1.1182(9) 0.8777(9) 0.094 Uiso 1 calc R . H4C H 0.2269(14) 1.1087(9) 0.8270(9) 0.094 Uiso 1 calc R . C5 C -0.3170(21) 1.3701(11) 0.8529(11) 0.092(6) Uani 1 d . . C6 C -0.4386(35) 1.3126(21) 0.8989(22) 0.087(6) Uani 0.50 d PU 1 H6A H -0.4691(35) 1.2663(21) 0.8634(22) 0.130 Uiso 0.50 calc PR 1 H6B H -0.5124(35) 1.3512(21) 0.9115(22) 0.130 Uiso 0.50 calc PR 1 H6C H -0.4043(35) 1.2872(21) 0.9483(22) 0.130 Uiso 0.50 calc PR 1 C7 C -0.4175(34) 1.4022(21) 0.7735(22) 0.086(6) Uani 0.50 d PU 1 H7A H -0.4486(34) 1.3509(21) 0.7447(22) 0.129 Uiso 0.50 calc PR 1 H7B H -0.3670(34) 1.4391(21) 0.7371(22) 0.129 Uiso 0.50 calc PR 1 H7C H -0.4933(34) 1.4345(21) 0.7941(22) 0.129 Uiso 0.50 calc PR 1 C8 C -0.2681(40) 1.4355(23) 0.8971(25) 0.099(8) Uani 0.50 d PU 1 H8A H -0.1990(40) 1.4654(23) 0.8669(25) 0.148 Uiso 0.50 calc PR 1 H8B H -0.2308(40) 1.4122(23) 0.9466(25) 0.148 Uiso 0.50 calc PR 1 H8C H -0.3389(40) 1.4763(23) 0.9099(25) 0.148 Uiso 0.50 calc PR 1 C6A C -0.3005(39) 1.3757(22) 0.9515(22) 0.100(8) Uani 0.50 d PU 2 H6AA H -0.2090(39) 1.3901(22) 0.9648(22) 0.150 Uiso 0.50 calc PR 2 H6AB H -0.3235(39) 1.3197(22) 0.9753(22) 0.150 Uiso 0.50 calc PR 2 H6AC H -0.3592(39) 1.4206(22) 0.9726(22) 0.150 Uiso 0.50 calc PR 2 C7A C -0.4345(38) 1.3514(24) 0.8288(24) 0.088(6) Uani 0.50 d PU 2 H7AA H -0.4359(38) 1.3493(24) 0.7704(24) 0.132 Uiso 0.50 calc PR 2 H7AB H -0.4962(38) 1.3957(24) 0.8476(24) 0.132 Uiso 0.50 calc PR 2 H7AC H -0.4604(38) 1.2949(24) 0.8503(24) 0.132 Uiso 0.50 calc PR 2 C8A C -0.2559(38) 1.4702(21) 0.8356(24) 0.098(8) Uani 0.50 d PU 2 H8AA H -0.1664(38) 1.4742(21) 0.8573(24) 0.147 Uiso 0.50 calc PR 2 H8AB H -0.3123(38) 1.5134(21) 0.8614(24) 0.147 Uiso 0.50 calc PR 2 H8AC H -0.2537(38) 1.4810(21) 0.7780(24) 0.147 Uiso 0.50 calc PR 2 C9 C -0.2799(15) 1.0644(9) 0.8957(10) 0.069(4) Uani 1 d . . C10 C -0.4257(18) 1.0819(15) 0.9207(15) 0.118(8) Uani 1 d . . H10A H -0.4804(18) 1.0880(15) 0.8729(15) 0.177 Uiso 1 calc R . H10B H -0.4300(18) 1.1353(15) 0.9522(15) 0.177 Uiso 1 calc R . H10C H -0.4581(18) 1.0333(15) 0.9529(15) 0.177 Uiso 1 calc R . C11 C -0.1962(19) 1.0551(11) 0.9746(9) 0.085(5) Uani 1 d . . H11A H -0.1038(19) 1.0440(11) 0.9608(9) 0.128 Uiso 1 calc R . H11B H -0.2304(19) 1.0067(11) 1.0063(9) 0.128 Uiso 1 calc R . H11C H -0.2024(19) 1.1087(11) 1.0057(9) 0.128 Uiso 1 calc R . C12 C -0.2720(23) 0.9745(8) 0.8480(10) 0.091(6) Uani 1 d . . H12A H -0.1805(23) 0.9634(8) 0.8322(10) 0.137 Uiso 1 calc R . H12B H -0.3276(23) 0.9777(8) 0.8003(10) 0.137 Uiso 1 calc R . H12C H -0.3030(23) 0.9274(8) 0.8824(10) 0.137 Uiso 1 calc R . C13 C -0.1938(15) 1.3132(8) 0.5794(7) 0.056(4) Uani 1 d . . C14 C -0.1926(22) 1.2373(10) 0.5181(8) 0.092(6) Uani 1 d . . H14A H -0.2637(22) 1.1966(10) 0.5308(8) 0.137 Uiso 1 calc R . H14B H -0.1077(22) 1.2072(10) 0.5207(8) 0.137 Uiso 1 calc R . H14C H -0.2058(22) 1.2603(10) 0.4642(8) 0.137 Uiso 1 calc R . C15 C -0.3291(22) 1.3614(15) 0.5749(12) 0.120(8) Uani 1 d . . H15A H -0.4005(22) 1.3208(15) 0.5872(12) 0.180 Uiso 1 calc R . H15B H -0.3416(22) 1.3848(15) 0.5211(12) 0.180 Uiso 1 calc R . H15C H -0.3300(22) 1.4089(15) 0.6137(12) 0.180 Uiso 1 calc R . C16 C -0.0815(21) 1.3782(12) 0.5599(9) 0.093(6) Uani 1 d . . H16A H -0.0830(21) 1.4257(12) 0.5987(9) 0.139 Uiso 1 calc R . H16B H -0.0945(21) 1.4015(12) 0.5061(9) 0.139 Uiso 1 calc R . H16C H 0.0037(21) 1.3485(12) 0.5626(9) 0.139 Uiso 1 calc R . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Hf1 0.0859(4) 0.0533(3) 0.0506(3) 0.0154(3) -0.0321(3) -0.0298(3) Cl1 0.189(6) 0.056(2) 0.067(2) -0.006(2) -0.050(3) -0.016(3) Cl2 0.107(3) 0.127(4) 0.135(4) 0.059(4) -0.072(3) -0.063(3) P1 0.052(2) 0.041(2) 0.034(2) -0.0062(13) -0.0039(14) -0.0060(15) P2 0.048(2) 0.036(2) 0.040(2) -0.0002(13) -0.0003(12) -0.0041(13) N1 0.053(5) 0.035(5) 0.032(5) 0.000(4) -0.011(5) -0.006(4) N2 0.101(9) 0.060(7) 0.059(6) 0.018(5) 0.042(7) 0.040(7) N3 0.030(5) 0.050(6) 0.064(6) -0.002(5) 0.019(5) -0.018(5) N4 0.051(6) 0.043(5) 0.033(5) -0.003(4) -0.010(4) -0.003(5) C1 0.027(5) 0.058(7) 0.057(7) 0.002(7) -0.003(6) -0.008(5) C2 0.051(8) 0.071(9) 0.093(11) 0.000(8) -0.012(7) -0.008(7) C3 0.052(7) 0.087(10) 0.076(10) 0.016(8) 0.032(7) 0.014(7) C4 0.053(8) 0.058(8) 0.077(9) 0.004(7) -0.001(7) 0.007(6) C5 0.112(15) 0.077(12) 0.085(11) 0.029(9) 0.044(11) 0.056(11) C6 0.091(13) 0.074(15) 0.095(16) -0.014(11) -0.004(14) 0.047(13) C7 0.092(13) 0.070(15) 0.095(16) -0.011(11) -0.006(14) 0.049(13) C8 0.103(15) 0.072(14) 0.121(19) -0.040(12) 0.065(16) -0.004(12) C6A 0.104(15) 0.074(14) 0.122(19) -0.039(12) 0.064(16) -0.003(12) C7A 0.093(13) 0.074(14) 0.097(15) -0.012(11) -0.005(14) 0.046(13) C8A 0.101(15) 0.071(14) 0.122(19) -0.041(13) 0.066(16) -0.002(12) C9 0.056(8) 0.059(8) 0.091(11) -0.012(7) 0.012(8) -0.021(7) C10 0.063(11) 0.130(18) 0.162(21) -0.007(16) 0.035(13) -0.027(12) C11 0.117(14) 0.084(11) 0.056(9) 0.020(8) 0.018(9) -0.024(11) C12 0.152(17) 0.036(7) 0.087(10) 0.001(7) 0.010(13) -0.024(10) C13 0.079(10) 0.051(7) 0.039(6) 0.005(5) -0.011(6) 0.004(7) C14 0.168(19) 0.073(10) 0.034(7) 0.010(7) -0.016(10) -0.003(12) C15 0.123(17) 0.126(18) 0.112(15) 0.050(14) -0.037(13) 0.034(15) C16 0.137(16) 0.090(12) 0.051(9) 0.034(8) 0.002(10) -0.033(11) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Hf1 N4 2.053(9) . ? Hf1 N3 2.081(10) . ? Hf1 Cl1 2.355(5) . ? Hf1 Cl2 2.382(4) . ? Hf1 N1 2.394(9) . ? Hf1 P1 2.857(3) . ? Hf1 P2 2.861(3) . ? P1 N3 1.632(9) . ? P1 N2 1.734(11) . ? P1 N1 1.785(10) . ? P2 N4 1.665(9) . ? P2 N2 1.752(11) . ? P2 N1 1.790(9) . ? N1 C1 1.493(13) . ? N2 C5 1.48(2) . ? N3 C9 1.48(2) . ? N4 C13 1.497(15) . ? C1 C4 1.49(2) . ? C1 C2 1.54(2) . ? C1 C3 1.54(2) . ? C5 C7A 1.26(4) . ? C5 C8 1.32(4) . ? C5 C6A 1.63(4) . ? C5 C8A 1.66(4) . ? C5 C6 1.67(4) . ? C5 C7 1.71(4) . ? C9 C10 1.53(2) . ? C9 C11 1.55(2) . ? C9 C12 1.57(2) . ? C13 C16 1.52(2) . ? C13 C14 1.53(2) . ? C13 C15 1.53(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 N4 Hf1 N3 124.8(4) . . ? N4 Hf1 Cl1 109.7(3) . . ? N3 Hf1 Cl1 110.5(3) . . ? N4 Hf1 Cl2 102.4(3) . . ? N3 Hf1 Cl2 103.0(3) . . ? Cl1 Hf1 Cl2 103.7(2) . . ? N4 Hf1 N1 68.5(3) . . ? N3 Hf1 N1 68.2(3) . . ? Cl1 Hf1 N1 100.8(2) . . ? Cl2 Hf1 N1 155.5(3) . . ? N4 Hf1 P1 91.6(3) . . ? N3 Hf1 P1 34.3(2) . . ? Cl1 Hf1 P1 122.68(13) . . ? Cl2 Hf1 P1 123.3(2) . . ? N1 Hf1 P1 38.5(2) . . ? N4 Hf1 P2 34.9(3) . . ? N3 Hf1 P2 90.8(3) . . ? Cl1 Hf1 P2 122.8(2) . . ? Cl2 Hf1 P2 122.7(2) . . ? N1 Hf1 P2 38.6(2) . . ? P1 Hf1 P2 56.83(9) . . ? N3 P1 N2 101.0(6) . . ? N3 P1 N1 95.0(5) . . ? N2 P1 N1 78.5(5) . . ? N3 P1 Hf1 45.9(4) . . ? N2 P1 Hf1 70.1(4) . . ? N1 P1 Hf1 56.6(3) . . ? N4 P2 N2 101.2(6) . . ? N4 P2 N1 93.5(5) . . ? N2 P2 N1 77.9(5) . . ? N4 P2 Hf1 45.0(3) . . ? N2 P2 Hf1 69.8(4) . . ? N1 P2 Hf1 56.5(3) . . ? C1 N1 P1 121.5(8) . . ? C1 N1 P2 122.9(7) . . ? P1 N1 P2 99.1(4) . . ? C1 N1 Hf1 132.6(7) . . ? P1 N1 Hf1 84.9(3) . . ? P2 N1 Hf1 85.0(3) . . ? C5 N2 P1 125.7(9) . . ? C5 N2 P2 124.7(9) . . ? P1 N2 P2 102.6(6) . . ? C9 N3 P1 126.4(9) . . ? C9 N3 Hf1 133.7(8) . . ? P1 N3 Hf1 99.9(4) . . ? C13 N4 P2 124.6(8) . . ? C13 N4 Hf1 135.3(8) . . ? P2 N4 Hf1 100.1(4) . . ? N1 C1 C4 110.1(10) . . ? N1 C1 C2 108.0(10) . . ? C4 C1 C2 109.2(11) . . ? N1 C1 C3 107.1(10) . . ? C4 C1 C3 111.8(11) . . ? C2 C1 C3 110.6(11) . . ? C7A C5 N2 109.3(23) . . ? C8 C5 N2 117.8(25) . . ? C7A C5 C6A 114.5(25) . . ? N2 C5 C6A 110.0(17) . . ? C7A C5 C8A 119.3(26) . . ? N2 C5 C8A 107.8(16) . . ? C6A C5 C8A 94.9(23) . . ? C8 C5 C6 114.1(23) . . ? N2 C5 C6 107.0(15) . . ? C8 C5 C7 114.9(25) . . ? N2 C5 C7 106.2(15) . . ? C6 C5 C7 94.0(22) . . ? N3 C9 C10 112.0(14) . . ? N3 C9 C11 111.0(11) . . ? C10 C9 C11 107.5(15) . . ? N3 C9 C12 108.8(11) . . ? C10 C9 C12 109.3(15) . . ? C11 C9 C12 108.1(14) . . ? N4 C13 C16 111.0(11) . . ? N4 C13 C14 108.2(10) . . ? C16 C13 C14 110.0(13) . . ? N4 C13 C15 109.2(12) . . ? C16 C13 C15 109.0(14) . . ? C14 C13 C15 109.5(15) . . ? _refine_diff_density_max 0.774 _refine_diff_density_min -1.795 _refine_diff_density_rms 0.127 #===END=== data_4a _database_code_CSD 197170 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H30 N4 P2' _chemical_formula_weight 388.42 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' P P 0.1023 0.0942 '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 16.7769(5) _cell_length_b 5.8729(2) _cell_length_c 22.4726(6) _cell_angle_alpha 90.00 _cell_angle_beta 102.090(1) _cell_angle_gamma 90.00 _cell_volume 2165.1(1) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used 155 _cell_measurement_theta_min 3.69 _cell_measurement_theta_max 20.09 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.192 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 832 _exptl_absorpt_coefficient_mu 0.212 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.8246 _exptl_absorpt_correction_T_max 0.9100 _exptl_special_details ; Data was collected using a Siemens SMART CCD (charge coupled device) based diffractometer equipped with an LT-2 low-temperature apparatus operating at 213 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.3\% per frame for 10 s , such that a hemisphere was collected. A total of 1271 frames were collected with a final resolution of 0.75 \%A. The first 50 frames were recollected at the end of data collection to monitor for decay. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software which corrects for Lp and decay. Absorption corrections were applied using SADABS based on Blessing, (1995). The structures are solved by the direct method using the SHELX-90 program and refined by least squares method on F2 SHELXL-93, incorporated in SHELXTL-PC V 5.03. Carbon-bound H atoms were placed in idealized positions and refined as a riding model. ; _diffrn_ambient_temperature 213(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type CCD _diffrn_measurement_method '\w, 0.3 deg' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1 _diffrn_reflns_number 5239 _diffrn_reflns_av_R_equivalents 0.0415 _diffrn_reflns_av_sigmaI/netI 0.0406 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -5 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 1.85 _diffrn_reflns_theta_max 24.74 _reflns_number_total 1848 _reflns_number_gt 1441 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'ASTRO (SIEMENS, V4.033, 1994)' _computing_cell_refinement 'SMART (SIEMENS, V4.033, 1994)' _computing_data_reduction 'SAINT (SIEMENS, V4.035, 1994)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (SIEMENS, 1994, ver 5.04)' _computing_publication_material 'CIFTAB (Sheldrick, 1993)' _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 w=1/[\s^2^(Fo^2^)+(0.1000P)^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 1848 _refine_ls_number_parameters 118 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0664 _refine_ls_R_factor_gt 0.0449 _refine_ls_wR_factor_ref 0.1607 _refine_ls_wR_factor_gt 0.1357 _refine_ls_goodness_of_fit_ref 1.137 _refine_ls_restrained_S_all 1.137 _refine_ls_shift/su_max 0.008 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group P1 P 0.96477(4) 0.07172(12) 0.29588(3) 0.0334(3) Uani 1 d . . . N2 N 1.06122(13) 0.1120(4) 0.28170(9) 0.0326(6) Uani 1 d . . . C7 C 1.13766(16) 0.0294(5) 0.32174(13) 0.0375(7) Uani 1 d . . . N1 N 0.94155(14) 0.3212(4) 0.32557(10) 0.0397(6) Uani 1 d . . . H1A H 0.9473 0.4449 0.3056 0.048 Uiso 1 calc R . . C10 C 1.1398(2) 0.1181(6) 0.38581(14) 0.0572(9) Uani 1 d . . . H10A H 1.1371 0.2831 0.3851 0.086 Uiso 1 calc R . . H10B H 1.1900 0.0699 0.4127 0.086 Uiso 1 calc R . . H10C H 1.0936 0.0577 0.4004 0.086 Uiso 1 calc R . . C4 C 0.8602(2) 0.3980(6) 0.48863(14) 0.0578(10) Uani 1 d . . . H4A H 0.8428 0.4158 0.5255 0.069 Uiso 1 calc R . . C1 C 0.91347(15) 0.3444(5) 0.38023(11) 0.0351(7) Uani 1 d . . . C9 C 1.20925(18) 0.1260(6) 0.29749(16) 0.0531(9) Uani 1 d . . . H9A H 1.2063 0.2910 0.2970 0.080 Uiso 1 calc R . . H9B H 1.2068 0.0704 0.2565 0.080 Uiso 1 calc R . . H9C H 1.2601 0.0779 0.3236 0.080 Uiso 1 calc R . . C6 C 0.92740(19) 0.5461(5) 0.41306(14) 0.0456(8) Uani 1 d . . . H6A H 0.9553 0.6660 0.3987 0.055 Uiso 1 calc R . . C2 C 0.87098(18) 0.1703(5) 0.40214(13) 0.0440(7) Uani 1 d . . . H2B H 0.8596 0.0341 0.3800 0.053 Uiso 1 calc R . . C8 C 1.1414(2) -0.2304(5) 0.32247(15) 0.0574(9) Uani 1 d . . . H8A H 1.1402 -0.2860 0.2816 0.086 Uiso 1 calc R . . H8B H 1.0950 -0.2906 0.3368 0.086 Uiso 1 calc R . . H8C H 1.1914 -0.2797 0.3494 0.086 Uiso 1 calc R . . C5 C 0.9004(2) 0.5717(6) 0.46686(14) 0.0574(9) Uani 1 d . . . H5A H 0.9098 0.7093 0.4886 0.069 Uiso 1 calc R . . C3 C 0.84540(19) 0.1981(6) 0.45673(14) 0.0544(9) Uani 1 d . . . H3A H 0.8178 0.0791 0.4718 0.065 Uiso 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 P1 0.0366(5) 0.0361(5) 0.0300(4) 0.0022(3) 0.0129(3) 0.0005(3) N2 0.0320(12) 0.0387(13) 0.0280(11) 0.0007(9) 0.0083(9) 0.0032(10) C7 0.0326(15) 0.0350(16) 0.0429(16) 0.0047(13) 0.0034(12) 0.0044(12) N1 0.0501(15) 0.0388(14) 0.0357(12) 0.0054(10) 0.0213(11) 0.0030(11) C10 0.060(2) 0.067(2) 0.0385(17) 0.0020(16) -0.0040(15) 0.0085(17) C4 0.068(2) 0.076(3) 0.0351(17) 0.0023(16) 0.0253(16) 0.0174(19) C1 0.0300(14) 0.0444(16) 0.0320(14) 0.0019(13) 0.0095(11) 0.0077(12) C9 0.0325(17) 0.053(2) 0.071(2) 0.0057(17) 0.0045(16) 0.0010(14) C6 0.0497(18) 0.0465(19) 0.0422(16) -0.0016(14) 0.0133(14) 0.0059(14) C2 0.0436(17) 0.0507(18) 0.0403(15) -0.0008(14) 0.0149(13) 0.0006(15) C8 0.052(2) 0.0418(18) 0.072(2) 0.0060(17) -0.0009(17) 0.0077(15) C5 0.073(2) 0.060(2) 0.0414(17) -0.0076(16) 0.0164(17) 0.0136(18) C3 0.055(2) 0.068(2) 0.0467(18) 0.0117(17) 0.0254(16) 0.0056(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 P1 N1 1.689(2) . ? P1 N2 1.723(2) 2_755 ? P1 N2 1.730(2) . ? P1 P1 2.5829(13) 2_755 ? N2 C7 1.485(3) . ? N2 P1 1.723(2) 2_755 ? C7 C10 1.524(4) . ? C7 C9 1.528(4) . ? C7 C8 1.527(4) . ? N1 C1 1.411(3) . ? C4 C5 1.368(5) . ? C4 C3 1.371(5) . ? C1 C6 1.389(4) . ? C1 C2 1.394(4) . ? C6 C5 1.385(4) . ? C2 C3 1.391(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 P1 N2 104.49(11) . 2_755 ? N1 P1 N2 104.84(11) . . ? N2 P1 N2 80.96(11) 2_755 . ? N1 P1 P1 119.83(7) . 2_755 ? N2 P1 P1 41.68(7) 2_755 2_755 ? N2 P1 P1 41.46(7) . 2_755 ? C7 N2 P1 124.87(18) . 2_755 ? C7 N2 P1 124.47(18) . . ? P1 N2 P1 96.86(11) 2_755 . ? N2 C7 C10 107.9(2) . . ? N2 C7 C9 107.8(2) . . ? C10 C7 C9 110.2(3) . . ? N2 C7 C8 111.2(2) . . ? C10 C7 C8 109.8(2) . . ? C9 C7 C8 109.9(2) . . ? C1 N1 P1 125.06(19) . . ? C5 C4 C3 120.0(3) . . ? C6 C1 C2 118.6(2) . . ? C6 C1 N1 119.7(3) . . ? C2 C1 N1 121.7(3) . . ? C5 C6 C1 120.4(3) . . ? C3 C2 C1 120.0(3) . . ? C4 C5 C6 120.5(3) . . ? C4 C3 C2 120.4(3) . . ? _diffrn_measured_fraction_theta_max 0.451 _diffrn_reflns_theta_full 24.74 _diffrn_measured_fraction_theta_full 0.451 _refine_diff_density_max 0.213 _refine_diff_density_min -0.252 _refine_diff_density_rms 0.047 #===END=== data_5a _database_code_CSD 197171 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H44 Li2 N4 O2 P2' _chemical_formula_weight 544.49 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' Li Li -0.0003 0.0001 '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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 17.701(5) _cell_length_b 11.549(2) _cell_length_c 17.547(4) _cell_angle_alpha 90.00 _cell_angle_beta 118.772(8) _cell_angle_gamma 90.00 _cell_volume 3144(1) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used 175 _cell_measurement_theta_min 2.89 _cell_measurement_theta_max 20.26 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.150 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1168 _exptl_absorpt_coefficient_mu 0.168 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9192 _exptl_absorpt_correction_T_max 0.9701 _exptl_special_details ; Data was collected using a Siemens SMART CCD (charge coupled device) based diffractometer equipped with an LT-2 low-temperature apparatus operating at 213 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.3\% per frame for 30 seconds, such that a hemisphere was collected. A total of 1271 frames were collected with a final resolution of 0.85 \%A. The first 50 frames were recollected at the end of data collection to monitor for decay. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software which corrects for Lp and decay. Absorption corrections were applied using SADABS supplied by George Sheldrick. The structures are solved by the direct method using the SHELX-90 program and refined by least squares method on F2 SHELXL-93, incorporated in SHELXTL-PC V 5.03. Carbon-bound H atoms were placed in idealized positions [C -H = 0.96\%A U(H)=0.08\%A^3^ (fixed)]. ; _diffrn_ambient_temperature 213(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type CCD _diffrn_measurement_method '\w, 0.3 deg' _diffrn_detector_area_resol_mean 836.6 _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1 _diffrn_reflns_number 12959 _diffrn_reflns_av_R_equivalents 0.0361 _diffrn_reflns_av_sigmaI/netI 0.0409 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.31 _diffrn_reflns_theta_max 25.00 _reflns_number_total 5416 _reflns_number_gt 4017 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'ASTRO (SIEMENS, V4.033, 1994)' _computing_cell_refinement 'SMART (SIEMENS, V4.033, 1994)' _computing_data_reduction 'SAINT (SIEMENS, V4.035, 1994)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (SIEMENS, 1994, ver 5.04)' _computing_publication_material 'CIFTAB (Sheldrick, 1993)' _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 w=1/[\s^2^(Fo^2^)+(0.0620P)^2^+4.6515P] 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 5416 _refine_ls_number_parameters 351 _refine_ls_number_restraints 174 _refine_ls_R_factor_all 0.0893 _refine_ls_R_factor_gt 0.0609 _refine_ls_wR_factor_ref 0.1702 _refine_ls_wR_factor_gt 0.1436 _refine_ls_goodness_of_fit_ref 1.031 _refine_ls_restrained_S_all 1.019 _refine_ls_shift/su_max 0.039 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group P1 P 1.28556(5) 0.16215(7) 1.26988(5) 0.0390(2) Uani 1 d . . . P2 P 1.35635(5) -0.03041(7) 1.35566(5) 0.0349(2) Uani 1 d . . . Li1 Li 1.2549(4) -0.0398(5) 1.1779(3) 0.0426(13) Uani 1 d . . . Li2 Li 1.1791(4) -0.0152(5) 1.2678(4) 0.0503(14) Uani 1 d . . . O1 O 1.23169(17) -0.1074(2) 1.07233(15) 0.0594(7) Uani 1 d . . . O2 O 1.07787(19) -0.0617(3) 1.2686(3) 0.0966(12) Uani 1 d . . . N1 N 1.28655(17) 0.0786(2) 1.35483(16) 0.0394(6) Uani 1 d . . . N2 N 1.35838(15) 0.0562(2) 1.27356(16) 0.0361(6) Uani 1 d . . . N3 N 1.19412(16) 0.1082(2) 1.18854(16) 0.0381(6) Uani 1 d . . . N4 N 1.27984(16) -0.1245(2) 1.29199(16) 0.0372(6) Uani 1 d . . . C1 C 1.3003(2) 0.1337(3) 1.4373(2) 0.0530(9) Uani 1 d U . . C2 C 1.2300(3) 0.2248(4) 1.4138(3) 0.0735(13) Uani 1 d U . . H2A H 1.1739 0.1880 1.3837 0.110 Uiso 1 calc R . . H2B H 1.2347 0.2827 1.3763 0.110 Uiso 1 calc R . . H2C H 1.2367 0.2615 1.4664 0.110 Uiso 1 calc R . . C3 C 1.3890(3) 0.1906(4) 1.4853(3) 0.0750(13) Uani 1 d U . . H3A H 1.3936 0.2505 1.4490 0.112 Uiso 1 calc R . . H3B H 1.4333 0.1327 1.4984 0.112 Uiso 1 calc R . . H3C H 1.3964 0.2247 1.5390 0.112 Uiso 1 calc R . . C4 C 1.2915(3) 0.0396(4) 1.4935(3) 0.0693(12) Uani 1 d U . . H4A H 1.2349 0.0045 1.4624 0.104 Uiso 1 calc R . . H4B H 1.2987 0.0736 1.5472 0.104 Uiso 1 calc R . . H4C H 1.3353 -0.0190 1.5068 0.104 Uiso 1 calc R . . C5 C 1.4380(2) 0.0812(3) 1.2685(2) 0.0484(9) Uani 1 d U . . C6 C 1.5015(2) 0.1522(4) 1.3467(3) 0.0731(13) Uani 1 d U . . H6A H 1.5177 0.1088 1.3997 0.110 Uiso 1 calc R . . H6B H 1.4745 0.2245 1.3488 0.110 Uiso 1 calc R . . H6C H 1.5525 0.1686 1.3414 0.110 Uiso 1 calc R . . C7 C 1.4784(3) -0.0342(4) 1.2660(3) 0.0642(11) Uani 1 d U . . H7A H 1.4378 -0.0784 1.2160 0.096 Uiso 1 calc R . . H7B H 1.4929 -0.0772 1.3187 0.096 Uiso 1 calc R . . H7C H 1.5302 -0.0203 1.2616 0.096 Uiso 1 calc R . . C8 C 1.4120(3) 0.1482(4) 1.1846(3) 0.0690(12) Uani 1 d U . . H8A H 1.3722 0.1021 1.1353 0.103 Uiso 1 calc R . . H8B H 1.4630 0.1650 1.1792 0.103 Uiso 1 calc R . . H8C H 1.3844 0.2202 1.1859 0.103 Uiso 1 calc R . . C9 C 1.13788(19) 0.1772(3) 1.1194(2) 0.0354(7) Uani 1 d U . . C10 C 1.1562(2) 0.2885(3) 1.1006(2) 0.0462(8) Uani 1 d U . . H10A H 1.2110 0.3206 1.1358 0.055 Uiso 1 calc R . . C11 C 1.0956(3) 0.3517(3) 1.0317(3) 0.0598(10) Uani 1 d U . . H11A H 1.1098 0.4263 1.0213 0.072 Uiso 1 calc R . . C12 C 1.0147(3) 0.3084(3) 0.9779(3) 0.0624(11) Uani 1 d U . . H12A H 0.9736 0.3529 0.9317 0.075 Uiso 1 calc R . . C13 C 0.9955(2) 0.1981(3) 0.9933(3) 0.0581(10) Uani 1 d U . . H13A H 0.9411 0.1659 0.9564 0.070 Uiso 1 calc R . . C14 C 1.0557(2) 0.1344(3) 1.0626(2) 0.0487(9) Uani 1 d U . . H14A H 1.0409 0.0596 1.0720 0.058 Uiso 1 calc R . . C15 C 1.2966(2) -0.2425(3) 1.2948(2) 0.0383(7) Uani 1 d U . . C16 C 1.3738(2) -0.2963(3) 1.3511(3) 0.0574(10) Uani 1 d U . . H16A H 1.4197 -0.2514 1.3921 0.069 Uiso 1 calc R . . C17 C 1.3847(3) -0.4155(4) 1.3482(3) 0.0757(13) Uani 1 d U . . H17A H 1.4375 -0.4495 1.3876 0.091 Uiso 1 calc R . . C18 C 1.3199(3) -0.4840(3) 1.2889(3) 0.0747(13) Uani 1 d U . . H18A H 1.3275 -0.5643 1.2872 0.090 Uiso 1 calc R . . C19 C 1.2446(3) -0.4326(3) 1.2327(3) 0.0657(11) Uani 1 d U . . H19A H 1.1996 -0.4784 1.1913 0.079 Uiso 1 calc R . . C20 C 1.2321(2) -0.3152(3) 1.2347(2) 0.0507(9) Uani 1 d U . . H20A H 1.1788 -0.2830 1.1946 0.061 Uiso 1 calc R . . C21 C 1.2630(3) -0.2151(4) 1.0584(3) 0.0776(14) Uani 1 d U . . H21A H 1.2167 -0.2728 1.0346 0.093 Uiso 1 calc R A 1 H21B H 1.3099 -0.2448 1.1132 0.093 Uiso 1 calc R A 1 C22 C 1.2942(5) -0.1907(6) 0.9968(4) 0.086(2) Uani 0.810(6) d PU B 1 H22A H 1.2786 -0.2535 0.9543 0.104 Uiso 0.810(6) calc PR B 1 H22B H 1.3570 -0.1816 1.0271 0.104 Uiso 0.810(6) calc PR B 1 C23 C 1.2506(5) -0.0793(6) 0.9526(4) 0.090(2) Uani 0.810(6) d PU B 1 H23A H 1.2936 -0.0200 0.9612 0.108 Uiso 0.810(6) calc PR B 1 H23B H 1.2139 -0.0917 0.8901 0.108 Uiso 0.810(6) calc PR B 1 C24 C 1.1996(3) -0.0443(4) 0.9923(3) 0.0759(13) Uani 1 d U . . H24A H 1.2052 0.0392 1.0035 0.091 Uiso 1 calc R C 1 H24B H 1.1387 -0.0624 0.9540 0.091 Uiso 1 calc R C 1 C25 C 1.0611(6) -0.1713(7) 1.2862(8) 0.214(5) Uani 1 d U . . H25A H 1.0545 -0.2237 1.2394 0.256 Uiso 1 calc R . . H25B H 1.1098 -0.1987 1.3405 0.256 Uiso 1 calc R . . C26 C 0.9887(6) -0.1733(8) 1.2934(7) 0.182(4) Uani 1 d U . . H26A H 1.0026 -0.1879 1.3538 0.219 Uiso 1 calc R . . H26B H 0.9498 -0.2342 1.2566 0.219 Uiso 1 calc R . . C27 C 0.9508(5) -0.0660(8) 1.2668(9) 0.209(5) Uani 1 d U . . H27A H 0.8952 -0.0732 1.2137 0.251 Uiso 1 calc R . . H27B H 0.9411 -0.0306 1.3121 0.251 Uiso 1 calc R . . C28 C 1.0056(5) -0.0011(7) 1.2519(9) 0.230(5) Uani 1 d U . . H28A H 1.0217 0.0680 1.2888 0.276 Uiso 1 calc R . . H28B H 0.9767 0.0243 1.1911 0.276 Uiso 1 calc R . . C22B C 1.222(2) -0.237(3) 0.9693(18) 0.086(2) Uani 0.190(6) d PU B 2 H22C H 1.1791 -0.2977 0.9545 0.104 Uiso 0.190(6) calc PR B 2 H22D H 1.2649 -0.2631 0.9523 0.104 Uiso 0.190(6) calc PR B 2 C23B C 1.181(2) -0.129(3) 0.9222(18) 0.090(2) Uani 0.190(6) d PU B 2 H23C H 1.2052 -0.1033 0.8854 0.108 Uiso 0.190(6) calc PR B 2 H23D H 1.1184 -0.1393 0.8859 0.108 Uiso 0.190(6) calc PR B 2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 P1 0.0399(5) 0.0280(4) 0.0364(5) -0.0002(3) 0.0083(4) -0.0023(4) P2 0.0366(4) 0.0293(4) 0.0313(4) 0.0001(3) 0.0103(4) -0.0017(3) Li1 0.048(3) 0.040(3) 0.033(3) -0.002(2) 0.014(2) -0.001(2) Li2 0.038(3) 0.049(3) 0.062(4) 0.004(3) 0.022(3) -0.004(3) O1 0.0776(18) 0.0561(15) 0.0372(13) 0.0004(12) 0.0219(13) 0.0180(14) O2 0.0583(19) 0.085(2) 0.158(3) 0.042(2) 0.062(2) 0.0047(17) N1 0.0469(16) 0.0325(14) 0.0331(14) -0.0035(11) 0.0149(12) 0.0021(12) N2 0.0328(13) 0.0324(13) 0.0377(14) 0.0041(11) 0.0128(12) -0.0033(11) N3 0.0356(14) 0.0287(13) 0.0373(15) 0.0010(11) 0.0074(12) 0.0004(11) N4 0.0381(14) 0.0286(13) 0.0391(15) -0.0015(11) 0.0140(12) -0.0031(11) C1 0.063(2) 0.051(2) 0.042(2) -0.0090(17) 0.0230(18) 0.0091(18) C2 0.091(3) 0.065(3) 0.067(3) -0.005(2) 0.040(3) 0.025(2) C3 0.084(3) 0.073(3) 0.049(2) -0.030(2) 0.017(2) -0.007(2) C4 0.090(3) 0.077(3) 0.049(2) 0.005(2) 0.040(2) 0.020(2) C5 0.0363(18) 0.049(2) 0.055(2) 0.0135(17) 0.0175(16) -0.0038(16) C6 0.042(2) 0.076(3) 0.080(3) 0.004(2) 0.012(2) -0.020(2) C7 0.053(2) 0.070(3) 0.079(3) 0.018(2) 0.039(2) 0.011(2) C8 0.058(2) 0.080(3) 0.074(3) 0.032(2) 0.036(2) 0.002(2) C9 0.0345(16) 0.0318(16) 0.0366(17) -0.0016(13) 0.0145(14) 0.0026(13) C10 0.0432(19) 0.0396(18) 0.045(2) 0.0045(15) 0.0122(16) -0.0038(15) C11 0.062(2) 0.045(2) 0.059(2) 0.0168(18) 0.019(2) -0.0005(18) C12 0.051(2) 0.057(2) 0.056(2) 0.0138(19) 0.0079(19) 0.0104(19) C13 0.040(2) 0.059(2) 0.052(2) 0.0019(18) 0.0036(17) -0.0010(17) C14 0.0398(19) 0.0401(19) 0.050(2) 0.0049(16) 0.0092(16) -0.0017(15) C15 0.0456(18) 0.0311(16) 0.0431(18) -0.0003(14) 0.0252(16) -0.0039(14) C16 0.050(2) 0.0368(19) 0.075(3) -0.0009(18) 0.021(2) -0.0030(17) C17 0.067(3) 0.043(2) 0.112(4) 0.008(2) 0.040(3) 0.011(2) C18 0.096(4) 0.0294(19) 0.117(4) -0.004(2) 0.066(3) -0.001(2) C19 0.090(3) 0.038(2) 0.080(3) -0.018(2) 0.050(3) -0.018(2) C20 0.061(2) 0.0375(19) 0.051(2) -0.0067(16) 0.0251(19) -0.0111(17) C21 0.112(4) 0.063(3) 0.064(3) 0.004(2) 0.047(3) 0.031(3) C22 0.115(5) 0.088(4) 0.085(4) 0.022(3) 0.071(4) 0.039(4) C23 0.127(6) 0.092(5) 0.078(4) 0.022(3) 0.072(4) 0.029(4) C24 0.099(3) 0.079(3) 0.047(2) 0.010(2) 0.032(2) 0.025(3) C25 0.179(8) 0.112(6) 0.445(16) 0.072(8) 0.227(10) 0.007(5) C26 0.163(7) 0.158(7) 0.295(11) 0.067(8) 0.165(8) -0.007(6) C27 0.119(6) 0.149(7) 0.415(14) 0.066(9) 0.172(8) 0.028(6) C28 0.114(6) 0.155(7) 0.472(16) 0.146(9) 0.180(8) 0.061(5) C22B 0.115(5) 0.088(4) 0.085(4) 0.022(3) 0.071(4) 0.039(4) C23B 0.127(6) 0.092(5) 0.078(4) 0.022(3) 0.072(4) 0.029(4) _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 P1 N3 1.680(3) . ? P1 N2 1.756(3) . ? P1 N1 1.769(3) . ? P1 P2 2.6393(12) . ? P1 Li1 2.738(5) . ? P1 Li2 2.772(6) . ? P2 N4 1.675(3) . ? P2 N1 1.759(3) . ? P2 N2 1.769(3) . ? P2 Li1 2.752(5) . ? P2 Li2 2.756(6) . ? Li1 O1 1.864(6) . ? Li1 N3 2.075(6) . ? Li1 N4 2.076(6) . ? Li1 N2 2.108(6) . ? Li1 Li2 2.532(8) . ? Li2 O2 1.877(6) . ? Li2 N4 2.055(6) . ? Li2 N1 2.080(6) . ? Li2 N3 2.096(6) . ? O1 C21 1.430(4) . ? O1 C24 1.435(4) . ? O2 C28 1.361(7) . ? O2 C25 1.370(7) . ? N1 C1 1.489(4) . ? N2 C5 1.482(4) . ? N3 C9 1.391(4) . ? N4 C15 1.391(4) . ? C1 C4 1.525(5) . ? C1 C3 1.527(6) . ? C1 C2 1.527(5) . ? C5 C7 1.523(5) . ? C5 C8 1.526(5) . ? C5 C6 1.528(5) . ? C9 C14 1.399(4) . ? C9 C10 1.402(4) . ? C10 C11 1.378(5) . ? C11 C12 1.374(5) . ? C12 C13 1.379(5) . ? C13 C14 1.381(5) . ? C15 C16 1.390(5) . ? C15 C20 1.400(5) . ? C16 C17 1.394(5) . ? C17 C18 1.369(6) . ? C18 C19 1.356(6) . ? C19 C20 1.377(5) . ? C21 C22B 1.39(3) . ? C21 C22 1.458(7) . ? C22 C23 1.508(8) . ? C23 C24 1.438(7) . ? C24 C23B 1.48(3) . ? C25 C26 1.347(9) . ? C26 C27 1.378(10) . ? C27 C28 1.348(9) . ? C22B C23B 1.48(3) . ? 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 N3 P1 N2 99.37(13) . . ? N3 P1 N1 97.37(13) . . ? N2 P1 N1 83.09(12) . . ? N3 P1 P2 99.83(9) . . ? N2 P1 P2 41.69(8) . . ? N1 P1 P2 41.44(9) . . ? N3 P1 Li1 49.19(15) . . ? N2 P1 Li1 50.34(14) . . ? N1 P1 Li1 87.20(14) . . ? P2 P1 Li1 61.55(11) . . ? N3 P1 Li2 48.99(16) . . ? N2 P1 Li2 88.17(15) . . ? N1 P1 Li2 48.60(15) . . ? P2 P1 Li2 61.17(12) . . ? Li1 P1 Li2 54.71(18) . . ? N4 P2 N1 96.87(13) . . ? N4 P2 N2 98.66(13) . . ? N1 P2 N2 82.99(12) . . ? N4 P2 P1 99.02(9) . . ? N1 P2 P1 41.70(9) . . ? N2 P2 P1 41.32(9) . . ? N4 P2 Li1 48.83(15) . . ? N1 P2 Li1 86.92(14) . . ? N2 P2 Li1 49.98(14) . . ? P1 P2 Li1 60.99(11) . . ? N4 P2 Li2 48.02(16) . . ? N1 P2 Li2 48.99(15) . . ? N2 P2 Li2 88.42(15) . . ? P1 P2 Li2 61.78(12) . . ? Li1 P2 Li2 54.73(18) . . ? O1 Li1 N3 124.0(3) . . ? O1 Li1 N4 127.1(3) . . ? N3 Li1 N4 100.4(3) . . ? O1 Li1 N2 134.7(3) . . ? N3 Li1 N2 77.6(2) . . ? N4 Li1 N2 77.3(2) . . ? O1 Li1 Li2 137.4(3) . . ? N3 Li1 Li2 53.0(2) . . ? N4 Li1 Li2 51.8(2) . . ? N2 Li1 Li2 87.8(2) . . ? O1 Li1 P1 146.0(3) . . ? N3 Li1 P1 37.78(11) . . ? N4 Li1 P1 86.73(19) . . ? N2 Li1 P1 39.89(12) . . ? Li2 Li1 P1 63.32(19) . . ? O1 Li1 P2 148.6(3) . . ? N3 Li1 P2 87.09(19) . . ? N4 Li1 P2 37.40(11) . . ? N2 Li1 P2 39.98(11) . . ? Li2 Li1 P2 62.70(18) . . ? P1 Li1 P2 57.47(11) . . ? O2 Li2 N4 124.0(3) . . ? O2 Li2 N1 133.0(4) . . ? N4 Li2 N1 76.9(2) . . ? O2 Li2 N3 128.7(3) . . ? N4 Li2 N3 100.4(3) . . ? N1 Li2 N3 76.7(2) . . ? O2 Li2 Li1 140.1(4) . . ? N4 Li2 Li1 52.6(2) . . ? N1 Li2 Li1 86.8(2) . . ? N3 Li2 Li1 52.3(2) . . ? O2 Li2 P2 144.3(3) . . ? N4 Li2 P2 37.30(12) . . ? N1 Li2 P2 39.66(12) . . ? N3 Li2 P2 86.6(2) . . ? Li1 Li2 P2 62.57(18) . . ? O2 Li2 P1 148.9(3) . . ? N4 Li2 P1 86.2(2) . . ? N1 Li2 P1 39.63(12) . . ? N3 Li2 P1 37.21(12) . . ? Li1 Li2 P1 61.96(18) . . ? P2 Li2 P1 57.05(11) . . ? C21 O1 C24 106.2(3) . . ? C21 O1 Li1 128.0(3) . . ? C24 O1 Li1 123.6(3) . . ? C28 O2 C25 103.9(5) . . ? C28 O2 Li2 130.8(4) . . ? C25 O2 Li2 125.2(4) . . ? C1 N1 P2 120.8(2) . . ? C1 N1 P1 121.1(2) . . ? P2 N1 P1 96.86(14) . . ? C1 N1 Li2 126.9(3) . . ? P2 N1 Li2 91.3(2) . . ? P1 N1 Li2 91.8(2) . . ? C5 N2 P1 124.4(2) . . ? C5 N2 P2 123.5(2) . . ? P1 N2 P2 96.99(13) . . ? C5 N2 Li1 122.8(3) . . ? P1 N2 Li1 89.77(18) . . ? P2 N2 Li1 90.04(18) . . ? C9 N3 P1 121.4(2) . . ? C9 N3 Li1 125.3(2) . . ? P1 N3 Li1 93.02(19) . . ? C9 N3 Li2 134.6(3) . . ? P1 N3 Li2 93.8(2) . . ? Li1 N3 Li2 74.7(2) . . ? C15 N4 P2 121.5(2) . . ? C15 N4 Li2 139.3(3) . . ? P2 N4 Li2 94.7(2) . . ? C15 N4 Li1 116.0(3) . . ? P2 N4 Li1 93.77(19) . . ? Li2 N4 Li1 75.6(2) . . ? N1 C1 C4 107.7(3) . . ? N1 C1 C3 111.3(3) . . ? C4 C1 C3 110.3(3) . . ? N1 C1 C2 107.5(3) . . ? C4 C1 C2 110.0(3) . . ? C3 C1 C2 109.9(3) . . ? N2 C5 C7 107.8(3) . . ? N2 C5 C8 107.6(3) . . ? C7 C5 C8 110.1(3) . . ? N2 C5 C6 111.1(3) . . ? C7 C5 C6 110.1(3) . . ? C8 C5 C6 110.1(3) . . ? N3 C9 C14 118.7(3) . . ? N3 C9 C10 125.5(3) . . ? C14 C9 C10 115.8(3) . . ? C11 C10 C9 121.4(3) . . ? C12 C11 C10 121.6(4) . . ? C11 C12 C13 118.3(3) . . ? C12 C13 C14 120.4(3) . . ? C13 C14 C9 122.4(3) . . ? C16 C15 N4 125.7(3) . . ? C16 C15 C20 115.7(3) . . ? N4 C15 C20 118.6(3) . . ? C15 C16 C17 121.4(4) . . ? C18 C17 C16 121.2(4) . . ? C19 C18 C17 118.1(4) . . ? C18 C19 C20 121.7(4) . . ? C19 C20 C15 121.8(4) . . ? C22B C21 O1 108.3(11) . . ? C22B C21 C22 51.5(13) . . ? O1 C21 C22 105.9(4) . . ? C21 C22 C23 105.3(4) . . ? C24 C23 C22 106.1(5) . . ? O1 C24 C23 106.6(4) . . ? O1 C24 C23B 107.7(11) . . ? C23 C24 C23B 49.8(13) . . ? C26 C25 O2 110.8(7) . . ? C25 C26 C27 106.5(7) . . ? C28 C27 C26 106.7(6) . . ? C27 C28 O2 111.2(6) . . ? C21 C22B C23B 109(2) . . ? C24 C23B C22B 104(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 N3 P1 P2 N4 0.20(14) . . . . ? N2 P1 P2 N4 -92.89(16) . . . . ? N1 P1 P2 N4 90.23(16) . . . . ? Li1 P1 P2 N4 -31.77(17) . . . . ? Li2 P1 P2 N4 31.37(18) . . . . ? N3 P1 P2 N1 -90.03(16) . . . . ? N2 P1 P2 N1 176.88(18) . . . . ? Li1 P1 P2 N1 -122.00(19) . . . . ? Li2 P1 P2 N1 -58.9(2) . . . . ? N3 P1 P2 N2 93.09(16) . . . . ? N1 P1 P2 N2 -176.88(18) . . . . ? Li1 P1 P2 N2 61.12(18) . . . . ? Li2 P1 P2 N2 124.3(2) . . . . ? N3 P1 P2 Li1 31.97(17) . . . . ? N2 P1 P2 Li1 -61.12(18) . . . . ? N1 P1 P2 Li1 122.00(19) . . . . ? Li2 P1 P2 Li1 63.1(2) . . . . ? N3 P1 P2 Li2 -31.17(18) . . . . ? N2 P1 P2 Li2 -124.3(2) . . . . ? N1 P1 P2 Li2 58.9(2) . . . . ? Li1 P1 P2 Li2 -63.1(2) . . . . ? N3 P1 Li1 O1 73.6(5) . . . . ? N2 P1 Li1 O1 -100.8(5) . . . . ? N1 P1 Li1 O1 175.9(5) . . . . ? P2 P1 Li1 O1 -149.9(6) . . . . ? Li2 P1 Li1 O1 136.8(6) . . . . ? N2 P1 Li1 N3 -174.4(3) . . . . ? N1 P1 Li1 N3 102.24(18) . . . . ? P2 P1 Li1 N3 136.4(2) . . . . ? Li2 P1 Li1 N3 63.2(2) . . . . ? N3 P1 Li1 N4 -111.6(3) . . . . ? N2 P1 Li1 N4 74.0(2) . . . . ? N1 P1 Li1 N4 -9.34(18) . . . . ? P2 P1 Li1 N4 24.85(12) . . . . ? Li2 P1 Li1 N4 -48.4(2) . . . . ? N3 P1 Li1 N2 174.4(3) . . . . ? N1 P1 Li1 N2 -83.34(17) . . . . ? P2 P1 Li1 N2 -49.16(13) . . . . ? Li2 P1 Li1 N2 -122.4(2) . . . . ? N3 P1 Li1 Li2 -63.2(2) . . . . ? N2 P1 Li1 Li2 122.4(2) . . . . ? N1 P1 Li1 Li2 39.05(19) . . . . ? P2 P1 Li1 Li2 73.24(18) . . . . ? N3 P1 Li1 P2 -136.4(2) . . . . ? N2 P1 Li1 P2 49.16(13) . . . . ? N1 P1 Li1 P2 -34.19(11) . . . . ? Li2 P1 Li1 P2 -73.24(18) . . . . ? N4 P2 Li1 O1 -76.3(5) . . . . ? N1 P2 Li1 O1 -178.2(6) . . . . ? N2 P2 Li1 O1 98.4(6) . . . . ? P1 P2 Li1 O1 147.4(6) . . . . ? Li2 P2 Li1 O1 -138.2(6) . . . . ? N4 P2 Li1 N3 111.3(3) . . . . ? N1 P2 Li1 N3 9.39(18) . . . . ? N2 P2 Li1 N3 -74.0(2) . . . . ? P1 P2 Li1 N3 -25.02(12) . . . . ? Li2 P2 Li1 N3 49.3(2) . . . . ? N1 P2 Li1 N4 -101.90(18) . . . . ? N2 P2 Li1 N4 174.7(3) . . . . ? P1 P2 Li1 N4 -136.3(2) . . . . ? Li2 P2 Li1 N4 -62.0(2) . . . . ? N4 P2 Li1 N2 -174.7(3) . . . . ? N1 P2 Li1 N2 83.43(17) . . . . ? P1 P2 Li1 N2 49.02(13) . . . . ? Li2 P2 Li1 N2 123.4(2) . . . . ? N4 P2 Li1 Li2 62.0(2) . . . . ? N1 P2 Li1 Li2 -39.93(19) . . . . ? N2 P2 Li1 Li2 -123.4(2) . . . . ? P1 P2 Li1 Li2 -74.33(18) . . . . ? N4 P2 Li1 P1 136.3(2) . . . . ? N1 P2 Li1 P1 34.40(11) . . . . ? N2 P2 Li1 P1 -49.02(13) . . . . ? Li2 P2 Li1 P1 74.33(18) . . . . ? O1 Li1 Li2 O2 5.6(8) . . . . ? N3 Li1 Li2 O2 107.9(5) . . . . ? N4 Li1 Li2 O2 -100.6(5) . . . . ? N2 Li1 Li2 O2 -176.1(5) . . . . ? P1 Li1 Li2 O2 151.1(5) . . . . ? P2 Li1 Li2 O2 -143.6(5) . . . . ? O1 Li1 Li2 N4 106.2(5) . . . . ? N3 Li1 Li2 N4 -151.5(3) . . . . ? N2 Li1 Li2 N4 -75.5(2) . . . . ? P1 Li1 Li2 N4 -108.3(2) . . . . ? P2 Li1 Li2 N4 -42.99(13) . . . . ? O1 Li1 Li2 N1 -178.0(4) . . . . ? N3 Li1 Li2 N1 -75.6(2) . . . . ? N4 Li1 Li2 N1 75.9(2) . . . . ? N2 Li1 Li2 N1 0.4(2) . . . . ? P1 Li1 Li2 N1 -32.41(14) . . . . ? P2 Li1 Li2 N1 32.89(14) . . . . ? O1 Li1 Li2 N3 -102.3(5) . . . . ? N4 Li1 Li2 N3 151.5(3) . . . . ? N2 Li1 Li2 N3 76.0(2) . . . . ? P1 Li1 Li2 N3 43.21(13) . . . . ? P2 Li1 Li2 N3 108.5(2) . . . . ? O1 Li1 Li2 P2 149.2(5) . . . . ? N3 Li1 Li2 P2 -108.5(2) . . . . ? N4 Li1 Li2 P2 42.99(13) . . . . ? N2 Li1 Li2 P2 -32.48(13) . . . . ? P1 Li1 Li2 P2 -65.29(10) . . . . ? O1 Li1 Li2 P1 -145.6(5) . . . . ? N3 Li1 Li2 P1 -43.21(13) . . . . ? N4 Li1 Li2 P1 108.3(2) . . . . ? N2 Li1 Li2 P1 32.81(13) . . . . ? P2 Li1 Li2 P1 65.29(11) . . . . ? N4 P2 Li2 O2 75.9(5) . . . . ? N1 P2 Li2 O2 -98.9(6) . . . . ? N2 P2 Li2 O2 179.0(6) . . . . ? P1 P2 Li2 O2 -147.9(6) . . . . ? Li1 P2 Li2 O2 139.3(6) . . . . ? N1 P2 Li2 N4 -174.8(3) . . . . ? N2 P2 Li2 N4 103.15(19) . . . . ? P1 P2 Li2 N4 136.2(2) . . . . ? Li1 P2 Li2 N4 63.4(2) . . . . ? N4 P2 Li2 N1 174.8(3) . . . . ? N2 P2 Li2 N1 -82.07(18) . . . . ? P1 P2 Li2 N1 -48.99(14) . . . . ? Li1 P2 Li2 N1 -121.9(2) . . . . ? N4 P2 Li2 N3 -112.1(3) . . . . ? N1 P2 Li2 N3 73.2(2) . . . . ? N2 P2 Li2 N3 -8.9(2) . . . . ? P1 P2 Li2 N3 24.17(13) . . . . ? Li1 P2 Li2 N3 -48.7(2) . . . . ? N4 P2 Li2 Li1 -63.4(2) . . . . ? N1 P2 Li2 Li1 121.9(2) . . . . ? N2 P2 Li2 Li1 39.78(18) . . . . ? P1 P2 Li2 Li1 72.86(17) . . . . ? N4 P2 Li2 P1 -136.2(2) . . . . ? N1 P2 Li2 P1 48.99(14) . . . . ? N2 P2 Li2 P1 -33.08(11) . . . . ? Li1 P2 Li2 P1 -72.86(17) . . . . ? N3 P1 Li2 O2 -79.5(6) . . . . ? N2 P1 Li2 O2 176.4(6) . . . . ? N1 P1 Li2 O2 94.0(7) . . . . ? P2 P1 Li2 O2 143.0(7) . . . . ? Li1 P1 Li2 O2 -143.1(7) . . . . ? N3 P1 Li2 N4 112.6(3) . . . . ? N2 P1 Li2 N4 8.5(2) . . . . ? N1 P1 Li2 N4 -73.9(2) . . . . ? P2 P1 Li2 N4 -24.84(13) . . . . ? Li1 P1 Li2 N4 49.1(2) . . . . ? N3 P1 Li2 N1 -173.5(3) . . . . ? N2 P1 Li2 N1 82.40(18) . . . . ? P2 P1 Li2 N1 49.04(14) . . . . ? Li1 P1 Li2 N1 123.0(2) . . . . ? N2 P1 Li2 N3 -104.11(19) . . . . ? N1 P1 Li2 N3 173.5(3) . . . . ? P2 P1 Li2 N3 -137.5(2) . . . . ? Li1 P1 Li2 N3 -63.5(2) . . . . ? N3 P1 Li2 Li1 63.5(2) . . . . ? N2 P1 Li2 Li1 -40.57(18) . . . . ? N1 P1 Li2 Li1 -123.0(2) . . . . ? P2 P1 Li2 Li1 -73.93(17) . . . . ? N3 P1 Li2 P2 137.5(2) . . . . ? N2 P1 Li2 P2 33.36(11) . . . . ? N1 P1 Li2 P2 -49.04(14) . . . . ? Li1 P1 Li2 P2 73.93(17) . . . . ? N3 Li1 O1 C21 -172.7(4) . . . . ? N4 Li1 O1 C21 -31.3(6) . . . . ? N2 Li1 O1 C21 79.8(6) . . . . ? Li2 Li1 O1 C21 -102.5(5) . . . . ? P1 Li1 O1 C21 142.2(5) . . . . ? P2 Li1 O1 C21 16.4(8) . . . . ? N3 Li1 O1 C24 26.6(6) . . . . ? N4 Li1 O1 C24 168.0(4) . . . . ? N2 Li1 O1 C24 -80.9(5) . . . . ? Li2 Li1 O1 C24 96.8(5) . . . . ? P1 Li1 O1 C24 -18.5(7) . . . . ? P2 Li1 O1 C24 -144.2(5) . . . . ? N4 Li2 O2 C28 -178.1(9) . . . . ? N1 Li2 O2 C28 77.2(10) . . . . ? N3 Li2 O2 C28 -33.0(11) . . . . ? Li1 Li2 O2 C28 -107.7(10) . . . . ? P2 Li2 O2 C28 136.8(9) . . . . ? P1 Li2 O2 C28 16.6(12) . . . . ? N4 Li2 O2 C25 0.9(9) . . . . ? N1 Li2 O2 C25 -103.9(8) . . . . ? N3 Li2 O2 C25 145.9(8) . . . . ? Li1 Li2 O2 C25 71.3(9) . . . . ? P2 Li2 O2 C25 -44.3(10) . . . . ? P1 Li2 O2 C25 -164.4(8) . . . . ? N4 P2 N1 C1 131.5(3) . . . . ? N2 P2 N1 C1 -130.6(3) . . . . ? P1 P2 N1 C1 -132.6(3) . . . . ? Li1 P2 N1 C1 179.4(3) . . . . ? Li2 P2 N1 C1 135.4(3) . . . . ? N4 P2 N1 P1 -95.86(14) . . . . ? N2 P2 N1 P1 2.08(12) . . . . ? Li1 P2 N1 P1 -47.96(15) . . . . ? Li2 P2 N1 P1 -91.9(2) . . . . ? N4 P2 N1 Li2 -3.9(2) . . . . ? N2 P2 N1 Li2 94.0(2) . . . . ? P1 P2 N1 Li2 91.9(2) . . . . ? Li1 P2 N1 Li2 44.0(2) . . . . ? N3 P1 N1 C1 -131.1(3) . . . . ? N2 P1 N1 C1 130.3(3) . . . . ? P2 P1 N1 C1 132.4(3) . . . . ? Li1 P1 N1 C1 -179.3(3) . . . . ? Li2 P1 N1 C1 -136.0(3) . . . . ? N3 P1 N1 P2 96.52(14) . . . . ? N2 P1 N1 P2 -2.09(12) . . . . ? Li1 P1 N1 P2 48.29(15) . . . . ? Li2 P1 N1 P2 91.6(2) . . . . ? N3 P1 N1 Li2 4.9(2) . . . . ? N2 P1 N1 Li2 -93.7(2) . . . . ? P2 P1 N1 Li2 -91.6(2) . . . . ? Li1 P1 N1 Li2 -43.3(2) . . . . ? O2 Li2 N1 C1 -3.2(6) . . . . ? N4 Li2 N1 C1 -127.8(3) . . . . ? N3 Li2 N1 C1 128.0(3) . . . . ? Li1 Li2 N1 C1 179.9(3) . . . . ? P2 Li2 N1 C1 -131.1(3) . . . . ? P1 Li2 N1 C1 132.0(3) . . . . ? O2 Li2 N1 P2 127.9(4) . . . . ? N4 Li2 N1 P2 3.25(17) . . . . ? N3 Li2 N1 P2 -100.95(18) . . . . ? Li1 Li2 N1 P2 -49.0(2) . . . . ? P1 Li2 N1 P2 -96.91(14) . . . . ? O2 Li2 N1 P1 -135.2(4) . . . . ? N4 Li2 N1 P1 100.15(18) . . . . ? N3 Li2 N1 P1 -4.04(17) . . . . ? Li1 Li2 N1 P1 47.9(2) . . . . ? P2 Li2 N1 P1 96.91(14) . . . . ? N3 P1 N2 C5 126.5(3) . . . . ? N1 P1 N2 C5 -137.1(3) . . . . ? P2 P1 N2 C5 -139.2(3) . . . . ? Li1 P1 N2 C5 130.8(3) . . . . ? Li2 P1 N2 C5 174.4(3) . . . . ? N3 P1 N2 P2 -94.29(14) . . . . ? N1 P1 N2 P2 2.08(12) . . . . ? Li1 P1 N2 P2 -90.02(19) . . . . ? Li2 P1 N2 P2 -46.42(16) . . . . ? N3 P1 N2 Li1 -4.28(19) . . . . ? N1 P1 N2 Li1 92.10(18) . . . . ? P2 P1 N2 Li1 90.02(19) . . . . ? Li2 P1 N2 Li1 43.6(2) . . . . ? N4 P2 N2 C5 -126.4(3) . . . . ? N1 P2 N2 C5 137.6(3) . . . . ? P1 P2 N2 C5 139.7(3) . . . . ? Li1 P2 N2 C5 -130.5(3) . . . . ? Li2 P2 N2 C5 -173.5(3) . . . . ? N4 P2 N2 P1 93.83(13) . . . . ? N1 P2 N2 P1 -2.09(12) . . . . ? Li1 P2 N2 P1 89.78(19) . . . . ? Li2 P2 N2 P1 46.76(16) . . . . ? N4 P2 N2 Li1 4.1(2) . . . . ? N1 P2 N2 Li1 -91.87(19) . . . . ? P1 P2 N2 Li1 -89.78(19) . . . . ? Li2 P2 N2 Li1 -43.0(2) . . . . ? O1 Li1 N2 C5 -2.6(6) . . . . ? N3 Li1 N2 C5 -128.5(3) . . . . ? N4 Li1 N2 C5 127.7(3) . . . . ? Li2 Li1 N2 C5 179.0(3) . . . . ? P1 Li1 N2 C5 -132.0(3) . . . . ? P2 Li1 N2 C5 131.0(3) . . . . ? O1 Li1 N2 P1 129.4(4) . . . . ? N3 Li1 N2 P1 3.50(16) . . . . ? N4 Li1 N2 P1 -100.30(17) . . . . ? Li2 Li1 N2 P1 -49.0(2) . . . . ? P2 Li1 N2 P1 -96.99(13) . . . . ? O1 Li1 N2 P2 -133.6(4) . . . . ? N3 Li1 N2 P2 100.49(17) . . . . ? N4 Li1 N2 P2 -3.31(16) . . . . ? Li2 Li1 N2 P2 48.0(2) . . . . ? P1 Li1 N2 P2 96.99(13) . . . . ? N2 P1 N3 C9 -130.9(2) . . . . ? N1 P1 N3 C9 145.0(2) . . . . ? P2 P1 N3 C9 -173.2(2) . . . . ? Li1 P1 N3 C9 -135.2(3) . . . . ? Li2 P1 N3 C9 149.9(3) . . . . ? N2 P1 N3 Li1 4.4(2) . . . . ? N1 P1 N3 Li1 -79.82(19) . . . . ? P2 P1 N3 Li1 -37.96(18) . . . . ? Li2 P1 N3 Li1 -74.9(2) . . . . ? N2 P1 N3 Li2 79.2(2) . . . . ? N1 P1 N3 Li2 -4.9(2) . . . . ? P2 P1 N3 Li2 36.94(19) . . . . ? Li1 P1 N3 Li2 74.9(2) . . . . ? O1 Li1 N3 C9 -7.1(5) . . . . ? N4 Li1 N3 C9 -156.8(3) . . . . ? N2 Li1 N3 C9 128.9(3) . . . . ? Li2 Li1 N3 C9 -134.3(3) . . . . ? P1 Li1 N3 C9 132.5(3) . . . . ? P2 Li1 N3 C9 168.1(2) . . . . ? O1 Li1 N3 P1 -139.7(3) . . . . ? N4 Li1 N3 P1 70.7(2) . . . . ? N2 Li1 N3 P1 -3.66(17) . . . . ? Li2 Li1 N3 P1 93.1(2) . . . . ? P2 Li1 N3 P1 35.58(15) . . . . ? O1 Li1 N3 Li2 127.2(4) . . . . ? N4 Li1 N3 Li2 -22.4(2) . . . . ? N2 Li1 N3 Li2 -96.8(2) . . . . ? P1 Li1 N3 Li2 -93.1(2) . . . . ? P2 Li1 N3 Li2 -57.5(2) . . . . ? O2 Li2 N3 C9 -3.6(7) . . . . ? N4 Li2 N3 C9 147.6(3) . . . . ? N1 Li2 N3 C9 -138.7(3) . . . . ? Li1 Li2 N3 C9 124.9(4) . . . . ? P2 Li2 N3 C9 -177.6(3) . . . . ? P1 Li2 N3 C9 -143.0(4) . . . . ? O2 Li2 N3 P1 139.4(4) . . . . ? N4 Li2 N3 P1 -69.4(2) . . . . ? N1 Li2 N3 P1 4.26(18) . . . . ? Li1 Li2 N3 P1 -92.10(19) . . . . ? P2 Li2 N3 P1 -34.62(16) . . . . ? O2 Li2 N3 Li1 -128.5(5) . . . . ? N4 Li2 N3 Li1 22.7(2) . . . . ? N1 Li2 N3 Li1 96.4(2) . . . . ? P2 Li2 N3 Li1 57.48(19) . . . . ? P1 Li2 N3 Li1 92.1(2) . . . . ? N1 P2 N4 C15 -156.5(2) . . . . ? N2 P2 N4 C15 119.6(2) . . . . ? P1 P2 N4 C15 161.5(2) . . . . ? Li1 P2 N4 C15 123.8(3) . . . . ? Li2 P2 N4 C15 -160.4(3) . . . . ? N1 P2 N4 Li2 4.0(2) . . . . ? N2 P2 N4 Li2 -79.9(2) . . . . ? P1 P2 N4 Li2 -38.1(2) . . . . ? Li1 P2 N4 Li2 -75.8(3) . . . . ? N1 P2 N4 Li1 79.8(2) . . . . ? N2 P2 N4 Li1 -4.1(2) . . . . ? P1 P2 N4 Li1 37.71(18) . . . . ? Li2 P2 N4 Li1 75.8(3) . . . . ? O2 Li2 N4 C15 17.1(7) . . . . ? N1 Li2 N4 C15 150.6(4) . . . . ? N3 Li2 N4 C15 -135.8(4) . . . . ? Li1 Li2 N4 C15 -113.3(4) . . . . ? P2 Li2 N4 C15 154.0(5) . . . . ? P1 Li2 N4 C15 -170.4(3) . . . . ? O2 Li2 N4 P2 -136.9(4) . . . . ? N1 Li2 N4 P2 -3.42(18) . . . . ? N3 Li2 N4 P2 70.1(2) . . . . ? Li1 Li2 N4 P2 92.7(2) . . . . ? P1 Li2 N4 P2 35.57(16) . . . . ? O2 Li2 N4 Li1 130.4(4) . . . . ? N1 Li2 N4 Li1 -96.1(2) . . . . ? N3 Li2 N4 Li1 -22.6(2) . . . . ? P2 Li2 N4 Li1 -92.7(2) . . . . ? P1 Li2 N4 Li1 -57.13(19) . . . . ? O1 Li1 N4 C15 12.7(5) . . . . ? N3 Li1 N4 C15 161.0(2) . . . . ? N2 Li1 N4 C15 -124.4(3) . . . . ? Li2 Li1 N4 C15 138.2(3) . . . . ? P1 Li1 N4 C15 -163.6(2) . . . . ? P2 Li1 N4 C15 -127.9(3) . . . . ? O1 Li1 N4 P2 140.7(4) . . . . ? N3 Li1 N4 P2 -71.1(2) . . . . ? N2 Li1 N4 P2 3.51(17) . . . . ? Li2 Li1 N4 P2 -93.9(2) . . . . ? P1 Li1 N4 P2 -35.69(15) . . . . ? O1 Li1 N4 Li2 -125.5(4) . . . . ? N3 Li1 N4 Li2 22.8(2) . . . . ? N2 Li1 N4 Li2 97.4(2) . . . . ? P1 Li1 N4 Li2 58.2(2) . . . . ? P2 Li1 N4 Li2 93.9(2) . . . . ? P2 N1 C1 C4 -62.3(4) . . . . ? P1 N1 C1 C4 176.3(3) . . . . ? Li2 N1 C1 C4 56.5(4) . . . . ? P2 N1 C1 C3 58.9(4) . . . . ? P1 N1 C1 C3 -62.6(4) . . . . ? Li2 N1 C1 C3 177.6(3) . . . . ? P2 N1 C1 C2 179.3(3) . . . . ? P1 N1 C1 C2 57.8(4) . . . . ? Li2 N1 C1 C2 -62.0(4) . . . . ? P1 N2 C5 C7 -175.1(2) . . . . ? P2 N2 C5 C7 55.9(4) . . . . ? Li1 N2 C5 C7 -59.3(4) . . . . ? P1 N2 C5 C8 -56.4(4) . . . . ? P2 N2 C5 C8 174.6(3) . . . . ? Li1 N2 C5 C8 59.4(4) . . . . ? P1 N2 C5 C6 64.2(4) . . . . ? P2 N2 C5 C6 -64.8(4) . . . . ? Li1 N2 C5 C6 180.0(3) . . . . ? P1 N3 C9 C14 -168.0(3) . . . . ? Li1 N3 C9 C14 71.5(4) . . . . ? Li2 N3 C9 C14 -32.7(5) . . . . ? P1 N3 C9 C10 12.1(4) . . . . ? Li1 N3 C9 C10 -108.4(4) . . . . ? Li2 N3 C9 C10 147.4(4) . . . . ? N3 C9 C10 C11 -178.4(3) . . . . ? C14 C9 C10 C11 1.7(5) . . . . ? C9 C10 C11 C12 -0.5(6) . . . . ? C10 C11 C12 C13 -1.1(7) . . . . ? C11 C12 C13 C14 1.6(7) . . . . ? C12 C13 C14 C9 -0.4(6) . . . . ? N3 C9 C14 C13 178.9(3) . . . . ? C10 C9 C14 C13 -1.2(5) . . . . ? P2 N4 C15 C16 3.5(5) . . . . ? Li2 N4 C15 C16 -145.7(4) . . . . ? Li1 N4 C15 C16 116.1(4) . . . . ? P2 N4 C15 C20 -174.6(2) . . . . ? Li2 N4 C15 C20 36.2(6) . . . . ? Li1 N4 C15 C20 -62.0(4) . . . . ? N4 C15 C16 C17 -179.2(4) . . . . ? C20 C15 C16 C17 -1.1(6) . . . . ? C15 C16 C17 C18 0.7(7) . . . . ? C16 C17 C18 C19 0.1(7) . . . . ? C17 C18 C19 C20 -0.5(7) . . . . ? C18 C19 C20 C15 0.1(6) . . . . ? C16 C15 C20 C19 0.7(5) . . . . ? N4 C15 C20 C19 178.9(3) . . . . ? C24 O1 C21 C22B -22.5(16) . . . . ? Li1 O1 C21 C22B 174.2(15) . . . . ? C24 O1 C21 C22 31.5(6) . . . . ? Li1 O1 C21 C22 -131.8(5) . . . . ? C22B C21 C22 C23 80.9(14) . . . . ? O1 C21 C22 C23 -20.1(7) . . . . ? C21 C22 C23 C24 1.6(8) . . . . ? C21 O1 C24 C23 -30.6(6) . . . . ? Li1 O1 C24 C23 133.7(5) . . . . ? C21 O1 C24 C23B 21.7(16) . . . . ? Li1 O1 C24 C23B -174.1(15) . . . . ? C22 C23 C24 O1 17.4(7) . . . . ? C22 C23 C24 C23B -82.1(15) . . . . ? C28 O2 C25 C26 -9.3(13) . . . . ? Li2 O2 C25 C26 171.5(8) . . . . ? O2 C25 C26 C27 9.1(15) . . . . ? C25 C26 C27 C28 -5.1(16) . . . . ? C26 C27 C28 O2 -0.7(16) . . . . ? C25 O2 C28 C27 6.0(14) . . . . ? Li2 O2 C28 C27 -174.9(8) . . . . ? O1 C21 C22B C23B 15(3) . . . . ? C22 C21 C22B C23B -81(2) . . . . ? O1 C24 C23B C22B -13(3) . . . . ? C23 C24 C23B C22B 84(2) . . . . ? C21 C22B C23B C24 -1(3) . . . . ? _diffrn_measured_fraction_theta_max 0.929 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.929 _refine_diff_density_max 0.406 _refine_diff_density_min -0.575 _refine_diff_density_rms 0.052 #===END=== data_6 _database_code_CSD 197172 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C40 H56 N8 P4 Zr' _chemical_formula_weight 864.03 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pbcn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 21.7990(5) _cell_length_b 9.7180(2) _cell_length_c 20.4069(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4323.05(16) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used 159 _cell_measurement_theta_min 2.45 _cell_measurement_theta_max 20.63 _exptl_crystal_description chunk _exptl_crystal_colour light_yellow _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.328 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1808 _exptl_absorpt_coefficient_mu 0.441 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.7960 _exptl_absorpt_correction_T_max 0.8975 _exptl_special_details ; Data was collected using a Siemens SMART CCD (charge coupled device) based diffractometer equipped with an LT-2 low-temperature apparatus operating at 213 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.3\% per frame for 30 seconds, such that a hemisphere was collected. A total of 1271 frames were collected with a final resolution of 0.75 \%A. The first 50 frames were recollected at the end of data collection to monitor for decay. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software which corrects for Lp and decay. Absorption corrections were applied using SADABS supplied by George Sheldrick. The structures are solved by the direct method using the SHELX-90 program and refined by least squares method on F2 SHELXL-97, incorporated in SHELXTL-PC V 5.03. ; _diffrn_ambient_temperature 213(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type CCD _diffrn_measurement_method '\w, 0.3 deg' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1 _diffrn_reflns_number 18997 _diffrn_reflns_av_R_equivalents 0.0407 _diffrn_reflns_av_sigmaI/netI 0.0288 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 1.87 _diffrn_reflns_theta_max 27.74 _reflns_number_total 4688 _reflns_number_gt 3910 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'ASTRO (SIEMENS, V4.033, 1994)' _computing_cell_refinement 'SMART (SIEMENS, V4.033, 1994)' _computing_data_reduction 'SAINT (SIEMENS, V4.035, 1994)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (SIEMENS, 1994, ver 5.04)' _computing_publication_material 'CIFTAB (Sheldrick, 1993)' _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^)+(0.0267P)^2^+4.0443P] 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 4688 _refine_ls_number_parameters 240 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0516 _refine_ls_R_factor_gt 0.0384 _refine_ls_wR_factor_ref 0.0880 _refine_ls_wR_factor_gt 0.0810 _refine_ls_goodness_of_fit_ref 1.153 _refine_ls_restrained_S_all 1.153 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.5000 0.39569(3) 0.7500 0.02203(9) Uani 1 2 d S . . P1 P 0.55462(3) 0.32760(7) 0.88362(3) 0.02822(14) Uani 1 1 d . . . P2 P 0.62483(3) 0.47939(7) 0.80697(3) 0.02964(14) Uani 1 1 d . . . N1 N 0.55069(8) 0.4912(2) 0.84355(9) 0.0263(4) Uani 1 1 d . . . N2 N 0.62501(9) 0.3240(2) 0.84739(10) 0.0341(5) Uani 1 1 d . . . N3 N 0.50509(8) 0.25276(19) 0.82957(9) 0.0266(4) Uani 1 1 d . . . N4 N 0.59441(9) 0.4559(2) 0.73127(9) 0.0281(4) Uani 1 1 d . . . C1 C 0.53863(11) 0.6184(2) 0.88462(12) 0.0315(5) Uani 1 1 d . . . C2 C 0.58897(13) 0.6349(3) 0.93671(14) 0.0465(7) Uani 1 1 d . . . H2A H 0.5812 0.7173 0.9623 0.070 Uiso 1 1 calc R . . H2B H 0.6286 0.6426 0.9154 0.070 Uiso 1 1 calc R . . H2C H 0.5889 0.5553 0.9654 0.070 Uiso 1 1 calc R . . C3 C 0.53807(15) 0.7415(3) 0.83864(14) 0.0486(7) Uani 1 1 d . . . H3A H 0.5044 0.7323 0.8078 0.073 Uiso 1 1 calc R . . H3B H 0.5766 0.7455 0.8149 0.073 Uiso 1 1 calc R . . H3C H 0.5329 0.8253 0.8639 0.073 Uiso 1 1 calc R . . C4 C 0.47680(12) 0.6010(3) 0.91810(12) 0.0369(6) Uani 1 1 d . . . H4A H 0.4448 0.5948 0.8852 0.055 Uiso 1 1 calc R . . H4B H 0.4690 0.6796 0.9462 0.055 Uiso 1 1 calc R . . H4C H 0.4771 0.5177 0.9442 0.055 Uiso 1 1 calc R . . C5 C 0.67665(12) 0.2283(3) 0.85992(14) 0.0441(7) Uani 1 1 d . . . C6 C 0.71037(16) 0.2737(5) 0.92172(18) 0.0787(12) Uani 1 1 d . . . H6A H 0.6823 0.2723 0.9586 0.118 Uiso 1 1 calc R . . H6B H 0.7261 0.3662 0.9157 0.118 Uiso 1 1 calc R . . H6C H 0.7442 0.2113 0.9302 0.118 Uiso 1 1 calc R . . C7 C 0.71889(17) 0.2319(5) 0.80127(19) 0.0868(14) Uani 1 1 d . . . H7A H 0.7527 0.1685 0.8082 0.130 Uiso 1 1 calc R . . H7B H 0.7348 0.3243 0.7956 0.130 Uiso 1 1 calc R . . H7C H 0.6963 0.2051 0.7623 0.130 Uiso 1 1 calc R . . C8 C 0.65072(17) 0.0843(4) 0.87051(19) 0.0687(10) Uani 1 1 d . . . H8A H 0.6230 0.0852 0.9077 0.103 Uiso 1 1 calc R . . H8B H 0.6841 0.0206 0.8790 0.103 Uiso 1 1 calc R . . H8C H 0.6286 0.0554 0.8316 0.103 Uiso 1 1 calc R . . C9 C 0.46984(10) 0.1370(2) 0.84925(11) 0.0277(5) Uani 1 1 d . . . C10 C 0.46597(13) 0.0916(3) 0.91412(13) 0.0410(6) Uani 1 1 d . . . H10A H 0.4905 0.1330 0.9464 0.049 Uiso 1 1 calc R . . C11 C 0.42641(14) -0.0137(3) 0.93129(15) 0.0507(7) Uani 1 1 d . . . H11A H 0.4243 -0.0424 0.9752 0.061 Uiso 1 1 calc R . . C12 C 0.39011(14) -0.0771(3) 0.88535(16) 0.0486(7) Uani 1 1 d . . . H12A H 0.3627 -0.1472 0.8976 0.058 Uiso 1 1 calc R . . C13 C 0.39467(14) -0.0358(3) 0.82088(15) 0.0488(7) Uani 1 1 d . . . H13A H 0.3708 -0.0796 0.7887 0.059 Uiso 1 1 calc R . . C14 C 0.43415(12) 0.0697(3) 0.80289(13) 0.0395(6) Uani 1 1 d . . . H14A H 0.4368 0.0960 0.7587 0.047 Uiso 1 1 calc R . . C15 C 0.63786(10) 0.4717(2) 0.67926(11) 0.0276(5) Uani 1 1 d . . . C16 C 0.67563(13) 0.5875(3) 0.67692(14) 0.0419(6) Uani 1 1 d . . . H16A H 0.6719 0.6558 0.7093 0.050 Uiso 1 1 calc R . . C17 C 0.71857(14) 0.6027(4) 0.62731(16) 0.0567(8) Uani 1 1 d . . . H17A H 0.7446 0.6798 0.6271 0.068 Uiso 1 1 calc R . . C18 C 0.72351(13) 0.5055(4) 0.57815(14) 0.0523(8) Uani 1 1 d . . . H18A H 0.7525 0.5165 0.5444 0.063 Uiso 1 1 calc R . . C19 C 0.68558(12) 0.3929(3) 0.57927(12) 0.0416(6) Uani 1 1 d . . . H19A H 0.6879 0.3275 0.5454 0.050 Uiso 1 1 calc R . . C20 C 0.64366(11) 0.3743(3) 0.62999(12) 0.0356(6) Uani 1 1 d . . . H20A H 0.6190 0.2949 0.6308 0.043 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Zr1 0.02117(14) 0.02344(15) 0.02149(15) 0.000 0.00030(12) 0.000 P1 0.0288(3) 0.0323(3) 0.0235(3) 0.0009(2) -0.0014(2) 0.0001(3) P2 0.0245(3) 0.0371(3) 0.0273(3) -0.0015(3) -0.0005(2) -0.0043(3) N1 0.0276(9) 0.0286(10) 0.0229(9) -0.0034(8) 0.0011(7) -0.0022(8) N2 0.0265(10) 0.0419(12) 0.0339(11) 0.0041(9) -0.0017(9) 0.0047(9) N3 0.0292(10) 0.0250(9) 0.0255(9) 0.0014(7) -0.0018(8) -0.0004(8) N4 0.0262(10) 0.0318(11) 0.0262(10) 0.0000(8) 0.0024(8) -0.0014(8) C1 0.0353(12) 0.0287(12) 0.0305(12) -0.0074(10) 0.0019(10) -0.0030(10) C2 0.0414(15) 0.0574(18) 0.0407(15) -0.0187(14) -0.0018(12) -0.0102(13) C3 0.0682(19) 0.0300(14) 0.0476(17) -0.0026(12) 0.0127(15) 0.0007(14) C4 0.0378(13) 0.0408(15) 0.0321(13) -0.0099(11) 0.0017(11) -0.0002(11) C5 0.0328(13) 0.0567(18) 0.0427(15) 0.0056(13) -0.0045(12) 0.0151(13) C6 0.060(2) 0.105(3) 0.071(2) -0.001(2) -0.0354(19) 0.015(2) C7 0.065(2) 0.116(4) 0.079(3) 0.030(2) 0.030(2) 0.053(2) C8 0.068(2) 0.055(2) 0.083(3) 0.0120(19) -0.0079(19) 0.0235(18) C9 0.0283(11) 0.0233(11) 0.0316(12) 0.0016(9) 0.0034(10) 0.0031(9) C10 0.0533(17) 0.0373(15) 0.0325(13) 0.0059(11) 0.0017(12) -0.0035(13) C11 0.0659(19) 0.0428(17) 0.0434(16) 0.0140(13) 0.0121(15) -0.0032(15) C12 0.0479(16) 0.0316(14) 0.066(2) 0.0080(14) 0.0138(15) -0.0079(12) C13 0.0509(17) 0.0395(16) 0.0561(18) 0.0006(14) -0.0005(14) -0.0138(14) C14 0.0445(15) 0.0360(14) 0.0381(14) 0.0039(11) 0.0014(12) -0.0085(12) C15 0.0220(10) 0.0337(13) 0.0272(11) 0.0065(10) -0.0020(9) 0.0021(9) C16 0.0442(15) 0.0415(15) 0.0399(14) 0.0052(12) 0.0009(12) -0.0106(13) C17 0.0474(17) 0.066(2) 0.0566(19) 0.0195(17) 0.0074(14) -0.0220(16) C18 0.0376(15) 0.078(2) 0.0412(16) 0.0224(16) 0.0118(12) 0.0022(16) C19 0.0369(14) 0.0590(18) 0.0289(13) 0.0062(12) 0.0058(11) 0.0140(13) C20 0.0314(12) 0.0411(15) 0.0342(13) -0.0004(11) 0.0027(10) -0.0005(11) _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 N3 2.1397(18) 3_656 ? Zr1 N3 2.1397(18) . ? Zr1 N4 2.1736(19) 3_656 ? Zr1 N4 2.1736(19) . ? Zr1 N1 2.3931(18) . ? Zr1 N1 2.3931(18) 3_656 ? Zr1 P1 3.0481(6) 3_656 ? Zr1 P1 3.0481(6) . ? Zr1 P2 3.0688(6) . ? Zr1 P2 3.0688(6) 3_656 ? P1 N2 1.704(2) . ? P1 N3 1.7062(19) . ? P1 N1 1.790(2) . ? P1 P2 2.6391(9) . ? P2 N4 1.6964(19) . ? P2 N2 1.721(2) . ? P2 N1 1.7839(19) . ? N1 C1 1.516(3) . ? N2 C5 1.482(3) . ? N3 C9 1.420(3) . ? N4 C15 1.431(3) . ? C1 C4 1.520(3) . ? C1 C3 1.521(4) . ? C1 C2 1.536(3) . ? C5 C7 1.511(4) . ? C5 C6 1.525(4) . ? C5 C8 1.525(5) . ? C9 C14 1.388(3) . ? C9 C10 1.398(3) . ? C10 C11 1.383(4) . ? C11 C12 1.373(4) . ? C12 C13 1.379(4) . ? C13 C14 1.388(4) . ? C15 C20 1.386(3) . ? C15 C16 1.395(3) . ? C16 C17 1.387(4) . ? C17 C18 1.382(5) . ? C18 C19 1.372(4) . ? C19 C20 1.393(3) . ? 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 N3 Zr1 N3 99.05(10) 3_656 . ? N3 Zr1 N4 105.02(7) 3_656 3_656 ? N3 Zr1 N4 95.20(7) . 3_656 ? N3 Zr1 N4 95.20(7) 3_656 . ? N3 Zr1 N4 105.02(7) . . ? N4 Zr1 N4 148.75(11) 3_656 . ? N3 Zr1 N1 151.78(7) 3_656 . ? N3 Zr1 N1 67.81(7) . . ? N4 Zr1 N1 101.10(7) 3_656 . ? N4 Zr1 N1 66.33(7) . . ? N3 Zr1 N1 67.81(7) 3_656 3_656 ? N3 Zr1 N1 151.78(7) . 3_656 ? N4 Zr1 N1 66.33(7) 3_656 3_656 ? N4 Zr1 N1 101.10(7) . 3_656 ? N1 Zr1 N1 134.37(9) . 3_656 ? N3 Zr1 P1 32.85(5) 3_656 3_656 ? N3 Zr1 P1 123.93(5) . 3_656 ? N4 Zr1 P1 81.13(5) 3_656 3_656 ? N4 Zr1 P1 105.73(5) . 3_656 ? N1 Zr1 P1 168.02(5) . 3_656 ? N1 Zr1 P1 35.92(5) 3_656 3_656 ? N3 Zr1 P1 123.93(5) 3_656 . ? N3 Zr1 P1 32.85(5) . . ? N4 Zr1 P1 105.73(5) 3_656 . ? N4 Zr1 P1 81.13(5) . . ? N1 Zr1 P1 35.92(5) . . ? N1 Zr1 P1 168.02(5) 3_656 . ? P1 Zr1 P1 154.92(3) 3_656 . ? N3 Zr1 P2 120.37(5) 3_656 . ? N3 Zr1 P2 80.71(5) . . ? N4 Zr1 P2 134.55(5) 3_656 . ? N4 Zr1 P2 32.40(5) . . ? N1 Zr1 P2 35.47(4) . . ? N1 Zr1 P2 127.51(5) 3_656 . ? P1 Zr1 P2 137.972(16) 3_656 . ? P1 Zr1 P2 51.116(16) . . ? N3 Zr1 P2 80.71(5) 3_656 3_656 ? N3 Zr1 P2 120.37(5) . 3_656 ? N4 Zr1 P2 32.40(5) 3_656 3_656 ? N4 Zr1 P2 134.55(5) . 3_656 ? N1 Zr1 P2 127.51(5) . 3_656 ? N1 Zr1 P2 35.47(4) 3_656 3_656 ? P1 Zr1 P2 51.116(16) 3_656 3_656 ? P1 Zr1 P2 137.972(16) . 3_656 ? P2 Zr1 P2 149.26(3) . 3_656 ? N2 P1 N3 106.30(10) . . ? N2 P1 N1 82.13(10) . . ? N3 P1 N1 93.04(9) . . ? N2 P1 P2 39.82(7) . . ? N3 P1 P2 102.83(7) . . ? N1 P1 P2 42.31(6) . . ? N2 P1 Zr1 88.17(7) . . ? N3 P1 Zr1 42.86(6) . . ? N1 P1 Zr1 51.67(6) . . ? P2 P1 Zr1 64.847(19) . . ? N4 P2 N2 108.63(10) . . ? N4 P2 N1 92.04(9) . . ? N2 P2 N1 81.83(9) . . ? N4 P2 P1 103.77(7) . . ? N2 P2 P1 39.35(7) . . ? N1 P2 P1 42.48(7) . . ? N4 P2 Zr1 43.35(6) . . ? N2 P2 Zr1 87.19(7) . . ? N1 P2 Zr1 51.12(6) . . ? P1 P2 Zr1 64.036(18) . . ? C1 N1 P2 116.15(14) . . ? C1 N1 P1 118.67(15) . . ? P2 N1 P1 95.21(9) . . ? C1 N1 Zr1 132.60(14) . . ? P2 N1 Zr1 93.41(8) . . ? P1 N1 Zr1 92.42(8) . . ? C5 N2 P1 128.47(18) . . ? C5 N2 P2 129.42(18) . . ? P1 N2 P2 100.83(11) . . ? C9 N3 P1 119.81(15) . . ? C9 N3 Zr1 134.48(15) . . ? P1 N3 Zr1 104.28(9) . . ? C15 N4 P2 113.73(15) . . ? C15 N4 Zr1 141.81(15) . . ? P2 N4 Zr1 104.25(9) . . ? N1 C1 C4 108.17(19) . . ? N1 C1 C3 107.57(19) . . ? C4 C1 C3 110.9(2) . . ? N1 C1 C2 110.1(2) . . ? C4 C1 C2 109.5(2) . . ? C3 C1 C2 110.5(2) . . ? N2 C5 C7 108.2(2) . . ? N2 C5 C6 109.1(3) . . ? C7 C5 C6 110.8(3) . . ? N2 C5 C8 108.6(2) . . ? C7 C5 C8 111.0(3) . . ? C6 C5 C8 109.1(3) . . ? C14 C9 C10 117.6(2) . . ? C14 C9 N3 118.9(2) . . ? C10 C9 N3 123.4(2) . . ? C11 C10 C9 120.7(3) . . ? C12 C11 C10 121.2(3) . . ? C11 C12 C13 118.6(3) . . ? C12 C13 C14 120.8(3) . . ? C13 C14 C9 121.0(3) . . ? C20 C15 C16 118.2(2) . . ? C20 C15 N4 121.7(2) . . ? C16 C15 N4 120.1(2) . . ? C17 C16 C15 120.6(3) . . ? C18 C17 C16 120.7(3) . . ? C19 C18 C17 119.1(3) . . ? C18 C19 C20 120.8(3) . . ? C15 C20 C19 120.7(3) . . ? _diffrn_measured_fraction_theta_max 0.920 _diffrn_reflns_theta_full 27.74 _diffrn_measured_fraction_theta_full 0.920 _refine_diff_density_max 0.432 _refine_diff_density_min -0.361 _refine_diff_density_rms 0.060 #===END=== data_7C6H5CH3 _database_code_CSD 197173 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C47 H64 Hf N8 P4' _chemical_formula_weight 1043.43 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Hf Hf -0.5830 6.1852 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.994(3) _cell_length_b 13.134(4) _cell_length_c 16.365(5) _cell_angle_alpha 90.765(10) _cell_angle_beta 101.60(3) _cell_angle_gamma 99.39(2) _cell_volume 2488.7(13) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 6.73 _cell_measurement_theta_max 12.57 _exptl_crystal_description needle _exptl_crystal_colour colorless _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.60 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.392 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1068 _exptl_absorpt_coefficient_mu 2.264 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.2543 _exptl_absorpt_correction_T_max 0.5408 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker P4' _diffrn_measurement_method '2\q/\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10087 _diffrn_reflns_av_R_equivalents 0.0326 _diffrn_reflns_av_sigmaI/netI 0.0330 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 1 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.76 _diffrn_reflns_theta_max 25.00 _reflns_number_total 8716 _reflns_number_gt 8068 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _computing_data_reduction 'Bruker SHELXTL' _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^)+(0.0780P)^2^+1.0951P] 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 8716 _refine_ls_number_parameters 542 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0468 _refine_ls_R_factor_gt 0.0413 _refine_ls_wR_factor_ref 0.1110 _refine_ls_wR_factor_gt 0.1058 _refine_ls_goodness_of_fit_ref 1.102 _refine_ls_restrained_S_all 1.102 _refine_ls_shift/su_max 0.104 _refine_ls_shift/su_mean 0.004 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Hf1 Hf 0.617683(14) 0.713783(12) 0.739357(10) 0.03638(9) Uani 1 1 d . . . P1 P 0.76562(10) 0.90795(9) 0.69327(7) 0.0437(3) Uani 1 1 d . . . P2 P 0.54153(11) 0.88796(9) 0.63205(7) 0.0437(3) Uani 1 1 d . . . P3 P 0.54867(10) 0.57450(9) 0.87559(7) 0.0399(2) Uani 1 1 d . . . P4 P 0.61380(11) 0.48158(9) 0.75321(8) 0.0428(3) Uani 1 1 d . . . N1 N 0.6560(3) 0.8178(3) 0.6261(2) 0.0402(8) Uani 1 1 d . . . N2 N 0.6516(3) 0.9712(3) 0.6960(3) 0.0469(9) Uani 1 1 d . . . N3 N 0.7706(3) 0.8234(3) 0.7715(2) 0.0396(8) Uani 1 1 d . . . N4 N 0.4833(3) 0.7991(3) 0.6925(2) 0.0424(8) Uani 1 1 d . . . N5 N 0.5028(3) 0.5534(3) 0.7646(2) 0.0382(8) Uani 1 1 d . . . N6 N 0.6529(4) 0.5043(3) 0.8601(2) 0.0477(9) Uani 1 1 d . . . N7 N 0.6013(3) 0.7016(3) 0.8658(2) 0.0407(8) Uani 1 1 d . . . N8 N 0.6837(3) 0.5806(3) 0.7077(2) 0.0417(8) Uani 1 1 d . . . C10 C 0.6718(5) 0.7962(4) 0.5377(3) 0.0532(12) Uani 1 1 d . . . C11 C 0.5683(6) 0.7170(5) 0.4960(3) 0.0757(18) Uani 1 1 d . . . H11A H 0.5689 0.6537 0.5247 0.114 Uiso 1 1 calc R . . H11B H 0.5722 0.7043 0.4388 0.114 Uiso 1 1 calc R . . H11C H 0.4985 0.7428 0.4982 0.114 Uiso 1 1 calc R . . C12 C 0.7837(6) 0.7545(6) 0.5419(4) 0.079(2) Uani 1 1 d . . . H12A H 0.8481 0.8081 0.5632 0.118 Uiso 1 1 calc R . . H12B H 0.7884 0.7314 0.4869 0.118 Uiso 1 1 calc R . . H12C H 0.7853 0.6976 0.5781 0.118 Uiso 1 1 calc R . . C13 C 0.6783(6) 0.8970(5) 0.4895(3) 0.0694(16) Uani 1 1 d . . . H13A H 0.6079 0.9240 0.4862 0.104 Uiso 1 1 calc R . . H13B H 0.6889 0.8825 0.4342 0.104 Uiso 1 1 calc R . . H13C H 0.7421 0.9469 0.5183 0.104 Uiso 1 1 calc R . . C20 C 0.6520(5) 1.0813(4) 0.7172(4) 0.0561(13) Uani 1 1 d . . . C21 C 0.5376(6) 1.0896(5) 0.7407(5) 0.0803(19) Uani 1 1 d . . . H21A H 0.4756 1.0651 0.6944 0.121 Uiso 1 1 calc R . . H21B H 0.5360 1.1604 0.7550 0.121 Uiso 1 1 calc R . . H21C H 0.5289 1.0485 0.7878 0.121 Uiso 1 1 calc R . . C22 C 0.6686(7) 1.1463(5) 0.6415(5) 0.085(2) Uani 1 1 d . . . H22A H 0.7433 1.1433 0.6297 0.128 Uiso 1 1 calc R . . H22B H 0.6631 1.2167 0.6539 0.128 Uiso 1 1 calc R . . H22C H 0.6099 1.1194 0.5938 0.128 Uiso 1 1 calc R . . C23 C 0.7532(6) 1.1173(5) 0.7907(4) 0.0750(18) Uani 1 1 d . . . H23A H 0.7425 1.0778 0.8382 0.112 Uiso 1 1 calc R . . H23B H 0.7565 1.1892 0.8043 0.112 Uiso 1 1 calc R . . H23C H 0.8241 1.1075 0.7755 0.112 Uiso 1 1 calc R . . C30 C 0.8681(4) 0.8367(4) 0.8386(3) 0.0410(9) Uani 1 1 d . . . C31 C 0.9479(4) 0.9269(4) 0.8572(3) 0.0539(12) Uani 1 1 d . . . H31 H 0.9374 0.9839 0.8251 0.065 Uiso 1 1 calc R . . C32 C 1.0427(5) 0.9344(5) 0.9221(4) 0.0650(15) Uani 1 1 d . . . H32 H 1.0953 0.9957 0.9329 0.078 Uiso 1 1 calc R . . C33 C 1.0597(5) 0.8518(5) 0.9709(4) 0.0691(16) Uani 1 1 d . . . H33 H 1.1231 0.8570 1.0151 0.083 Uiso 1 1 calc R . . C34 C 0.9814(5) 0.7608(5) 0.9535(4) 0.0707(16) Uani 1 1 d . . . H34 H 0.9929 0.7040 0.9855 0.085 Uiso 1 1 calc R . . C35 C 0.8871(4) 0.7536(4) 0.8896(3) 0.0544(12) Uani 1 1 d . . . H35 H 0.8344 0.6922 0.8797 0.065 Uiso 1 1 calc R . . C40 C 0.3710(4) 0.8107(3) 0.7030(3) 0.0498(11) Uani 1 1 d . . . C41 C 0.3491(5) 0.8250(5) 0.7824(4) 0.0639(15) Uani 1 1 d . . . H41 H 0.4087 0.8294 0.8292 0.077 Uiso 1 1 calc R . . C42 C 0.2382(6) 0.8328(6) 0.7916(6) 0.085(2) Uani 1 1 d . . . H42 H 0.2238 0.8404 0.8449 0.102 Uiso 1 1 calc R . . C43 C 0.1515(6) 0.8296(6) 0.7254(7) 0.104(3) Uani 1 1 d . . . H43 H 0.0784 0.8368 0.7330 0.124 Uiso 1 1 calc R . . C44 C 0.1703(6) 0.8154(7) 0.6451(6) 0.096(3) Uani 1 1 d . . . H44 H 0.1097 0.8117 0.5991 0.115 Uiso 1 1 calc R . . C45 C 0.2809(5) 0.8067(5) 0.6343(4) 0.0691(15) Uani 1 1 d . . . H45 H 0.2943 0.7982 0.5808 0.083 Uiso 1 1 calc R . . C50 C 0.3798(4) 0.5021(4) 0.7282(3) 0.0487(11) Uani 1 1 d . . . C51 C 0.3625(5) 0.5095(5) 0.6348(4) 0.0694(16) Uani 1 1 d . . . H51A H 0.3711 0.5809 0.6212 0.104 Uiso 1 1 calc R . . H51B H 0.2865 0.4749 0.6090 0.104 Uiso 1 1 calc R . . H51C H 0.4190 0.4775 0.6147 0.104 Uiso 1 1 calc R . . C52 C 0.2974(4) 0.5581(4) 0.7624(4) 0.0612(14) Uani 1 1 d . . . H52A H 0.3133 0.5567 0.8222 0.092 Uiso 1 1 calc R . . H52B H 0.2195 0.5248 0.7405 0.092 Uiso 1 1 calc R . . H52C H 0.3071 0.6285 0.7463 0.092 Uiso 1 1 calc R . . C53 C 0.3609(5) 0.3889(4) 0.7523(4) 0.0680(15) Uani 1 1 d . . . H53A H 0.4067 0.3509 0.7258 0.102 Uiso 1 1 calc R . . H53B H 0.2808 0.3594 0.7345 0.102 Uiso 1 1 calc R . . H53C H 0.3833 0.3858 0.8118 0.102 Uiso 1 1 calc R . . C60 C 0.7294(5) 0.4516(4) 0.9191(3) 0.0530(12) Uani 1 1 d . . . C61 C 0.8382(6) 0.4454(6) 0.8855(4) 0.0775(18) Uani 1 1 d . . . H61A H 0.8180 0.4032 0.8346 0.116 Uiso 1 1 calc R . . H61B H 0.8915 0.4154 0.9260 0.116 Uiso 1 1 calc R . . H61C H 0.8734 0.5136 0.8748 0.116 Uiso 1 1 calc R . . C62 C 0.6691(7) 0.3436(5) 0.9328(5) 0.085(2) Uani 1 1 d . . . H62A H 0.6009 0.3486 0.9538 0.128 Uiso 1 1 calc R . . H62B H 0.7203 0.3105 0.9724 0.128 Uiso 1 1 calc R . . H62C H 0.6481 0.3038 0.8808 0.128 Uiso 1 1 calc R . . C63 C 0.7627(6) 0.5141(5) 1.0037(4) 0.0759(17) Uani 1 1 d . . . H63A H 0.8020 0.5821 0.9962 0.114 Uiso 1 1 calc R . . H63B H 0.8126 0.4797 1.0432 0.114 Uiso 1 1 calc R . . H63C H 0.6942 0.5195 1.0241 0.114 Uiso 1 1 calc R . . C70 C 0.6167(4) 0.7741(3) 0.9335(3) 0.0402(9) Uani 1 1 d . . . C71 C 0.6162(5) 0.7467(4) 1.0150(3) 0.0549(12) Uani 1 1 d . . . H71 H 0.6115 0.6776 1.0278 0.066 Uiso 1 1 calc R . . C72 C 0.6227(6) 0.8212(5) 1.0778(3) 0.0669(15) Uani 1 1 d . . . H72 H 0.6198 0.8012 1.1318 0.080 Uiso 1 1 calc R . . C73 C 0.6331(5) 0.9230(5) 1.0610(4) 0.0663(15) Uani 1 1 d . . . H73 H 0.6377 0.9724 1.1033 0.080 Uiso 1 1 calc R . . C74 C 0.6369(5) 0.9525(4) 0.9815(4) 0.0604(13) Uani 1 1 d . . . H74 H 0.6444 1.0222 0.9700 0.072 Uiso 1 1 calc R . . C75 C 0.6295(4) 0.8787(4) 0.9176(3) 0.0500(11) Uani 1 1 d . . . H75 H 0.6333 0.8997 0.8641 0.060 Uiso 1 1 calc R . . C80 C 0.7740(4) 0.5538(4) 0.6715(3) 0.0454(10) Uani 1 1 d . . . C81 C 0.7505(5) 0.4795(4) 0.6058(3) 0.0595(13) Uani 1 1 d . . . H81 H 0.6754 0.4453 0.5862 0.071 Uiso 1 1 calc R . . C82 C 0.8394(7) 0.4568(6) 0.5699(4) 0.0786(19) Uani 1 1 d . . . H82 H 0.8231 0.4083 0.5254 0.094 Uiso 1 1 calc R . . C83 C 0.9512(6) 0.5048(6) 0.5991(4) 0.081(2) Uani 1 1 d . . . H83 H 1.0102 0.4883 0.5750 0.097 Uiso 1 1 calc R . . C84 C 0.9750(6) 0.5762(6) 0.6634(5) 0.0732(17) Uani 1 1 d . . . H84 H 1.0507 0.6090 0.6832 0.088 Uiso 1 1 calc R . . C85 C 0.8875(5) 0.6010(4) 0.7002(4) 0.0569(13) Uani 1 1 d . . . H85 H 0.9053 0.6499 0.7446 0.068 Uiso 1 1 calc R . . C90 C 0.0560(8) 0.2848(8) 0.8080(7) 0.154(5) Uani 1 1 d G . . H90 H 0.0590 0.3286 0.8538 0.185 Uiso 1 1 calc R . . C91 C 0.0026(7) 0.3083(6) 0.7287(8) 0.294(15) Uani 1 1 d G . . H91 H -0.0302 0.3679 0.7214 0.353 Uiso 1 1 calc R . . C92 C -0.0018(7) 0.2428(8) 0.6603(6) 0.144(5) Uani 1 1 d G . . H92 H -0.0376 0.2585 0.6072 0.172 Uiso 1 1 calc R . . C93 C 0.0472(7) 0.1538(7) 0.6712(6) 0.317(19) Uani 1 1 d G . . C94 C 0.1006(7) 0.1303(7) 0.7505(7) 0.192(9) Uani 1 1 d G . . H94 H 0.1334 0.0707 0.7578 0.230 Uiso 1 1 calc R . . C95 C 0.1051(7) 0.1958(9) 0.8189(5) 0.252(13) Uani 1 1 d G . . H95 H 0.1408 0.1800 0.8720 0.302 Uiso 1 1 calc R . . C96 C 0.0446(15) 0.0936(12) 0.6134(13) 0.253(12) Uani 1 1 d . . . H96A H 0.1107 0.0597 0.6254 0.380 Uiso 1 1 calc R . . H96B H 0.0456 0.1307 0.5633 0.380 Uiso 1 1 calc R . . H96C H -0.0246 0.0431 0.6058 0.380 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Hf1 0.03669(13) 0.03645(12) 0.03673(12) 0.00328(7) 0.00680(8) 0.00917(8) P1 0.0402(6) 0.0463(6) 0.0438(6) 0.0117(5) 0.0073(5) 0.0060(5) P2 0.0431(6) 0.0433(6) 0.0432(6) 0.0060(5) 0.0014(5) 0.0120(5) P3 0.0426(6) 0.0389(6) 0.0398(6) 0.0035(4) 0.0111(5) 0.0080(5) P4 0.0488(7) 0.0364(6) 0.0461(6) 0.0007(5) 0.0134(5) 0.0110(5) N1 0.044(2) 0.044(2) 0.0336(18) 0.0056(15) 0.0071(15) 0.0115(16) N2 0.047(2) 0.0363(19) 0.053(2) 0.0045(16) 0.0016(18) 0.0056(16) N3 0.0396(19) 0.0400(19) 0.0380(18) 0.0082(15) 0.0045(15) 0.0072(15) N4 0.0354(19) 0.043(2) 0.049(2) 0.0041(16) 0.0044(16) 0.0124(16) N5 0.0361(19) 0.0353(18) 0.0419(19) 0.0002(14) 0.0076(15) 0.0035(15) N6 0.056(2) 0.047(2) 0.043(2) 0.0025(17) 0.0086(18) 0.0190(19) N7 0.048(2) 0.0368(19) 0.0379(18) -0.0020(15) 0.0098(16) 0.0095(16) N8 0.041(2) 0.043(2) 0.045(2) 0.0031(15) 0.0144(16) 0.0122(16) C10 0.071(3) 0.059(3) 0.034(2) 0.011(2) 0.013(2) 0.023(3) C11 0.110(5) 0.069(4) 0.044(3) -0.007(3) 0.009(3) 0.015(4) C12 0.094(5) 0.101(5) 0.067(4) 0.032(3) 0.045(4) 0.051(4) C13 0.089(4) 0.079(4) 0.046(3) 0.028(3) 0.019(3) 0.025(3) C20 0.062(3) 0.033(2) 0.070(3) 0.006(2) 0.002(3) 0.012(2) C21 0.075(4) 0.060(4) 0.106(5) -0.012(3) 0.014(4) 0.018(3) C22 0.098(5) 0.052(3) 0.099(5) 0.031(3) 0.002(4) 0.013(3) C23 0.081(4) 0.050(3) 0.083(4) -0.012(3) -0.010(3) 0.011(3) C30 0.037(2) 0.050(2) 0.037(2) 0.0027(18) 0.0072(17) 0.0133(19) C31 0.044(3) 0.052(3) 0.064(3) 0.003(2) 0.004(2) 0.010(2) C32 0.046(3) 0.067(3) 0.072(4) -0.010(3) -0.003(3) 0.002(3) C33 0.052(3) 0.091(4) 0.057(3) 0.001(3) -0.009(3) 0.017(3) C34 0.061(4) 0.083(4) 0.063(3) 0.023(3) -0.003(3) 0.016(3) C35 0.049(3) 0.059(3) 0.050(3) 0.016(2) -0.003(2) 0.008(2) C40 0.046(3) 0.034(2) 0.070(3) 0.000(2) 0.011(2) 0.0090(19) C41 0.053(3) 0.057(3) 0.086(4) -0.012(3) 0.024(3) 0.011(3) C42 0.072(4) 0.071(4) 0.121(6) -0.021(4) 0.041(4) 0.011(3) C43 0.050(4) 0.091(5) 0.178(10) 0.002(6) 0.034(5) 0.019(4) C44 0.044(3) 0.102(6) 0.138(7) 0.018(5) 0.000(4) 0.024(4) C45 0.049(3) 0.074(4) 0.082(4) 0.016(3) 0.004(3) 0.015(3) C50 0.044(3) 0.040(2) 0.057(3) 0.001(2) 0.004(2) 0.0021(19) C51 0.062(3) 0.075(4) 0.057(3) -0.007(3) -0.009(3) -0.003(3) C52 0.039(3) 0.057(3) 0.086(4) 0.007(3) 0.011(3) 0.004(2) C53 0.054(3) 0.046(3) 0.098(4) 0.009(3) 0.010(3) -0.003(2) C60 0.056(3) 0.048(3) 0.057(3) 0.016(2) 0.011(2) 0.018(2) C61 0.066(4) 0.099(5) 0.081(4) 0.034(4) 0.022(3) 0.043(4) C62 0.096(5) 0.054(3) 0.104(5) 0.034(3) 0.015(4) 0.011(3) C63 0.091(5) 0.082(4) 0.053(3) 0.011(3) -0.002(3) 0.031(4) C70 0.038(2) 0.044(2) 0.039(2) -0.0017(18) 0.0054(18) 0.0094(18) C71 0.067(3) 0.050(3) 0.047(3) 0.003(2) 0.011(2) 0.010(2) C72 0.085(4) 0.071(4) 0.044(3) -0.009(2) 0.014(3) 0.013(3) C73 0.075(4) 0.064(3) 0.060(3) -0.022(3) 0.016(3) 0.008(3) C74 0.066(3) 0.044(3) 0.069(3) -0.010(2) 0.014(3) 0.005(2) C75 0.055(3) 0.044(3) 0.051(3) -0.003(2) 0.012(2) 0.007(2) C80 0.050(3) 0.048(2) 0.046(2) 0.0120(19) 0.017(2) 0.020(2) C81 0.068(3) 0.067(3) 0.047(3) -0.004(2) 0.014(2) 0.021(3) C82 0.101(5) 0.093(5) 0.058(3) 0.000(3) 0.030(3) 0.049(4) C83 0.077(5) 0.108(5) 0.082(4) 0.026(4) 0.046(4) 0.051(4) C84 0.054(3) 0.087(4) 0.090(5) 0.026(4) 0.030(3) 0.029(3) C85 0.057(3) 0.060(3) 0.059(3) 0.011(2) 0.017(3) 0.019(3) C90 0.111(9) 0.174(13) 0.162(12) 0.023(10) 0.037(8) -0.036(8) C91 0.154(15) 0.46(4) 0.21(2) 0.12(2) 0.038(15) -0.11(2) C92 0.103(7) 0.111(8) 0.227(15) 0.083(9) 0.042(9) 0.035(7) C93 0.31(3) 0.166(16) 0.52(5) -0.13(2) 0.33(3) -0.123(17) C94 0.158(12) 0.27(2) 0.096(8) 0.038(10) 0.000(9) -0.081(12) C95 0.117(10) 0.25(2) 0.33(3) 0.21(2) -0.057(13) -0.037(12) C96 0.269(19) 0.170(13) 0.36(2) -0.117(15) 0.26(2) -0.082(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 Hf1 N3 2.109(4) . ? Hf1 N7 2.124(4) . ? Hf1 N8 2.133(4) . ? Hf1 N4 2.134(4) . ? Hf1 N1 2.391(4) . ? Hf1 N5 2.411(4) . ? Hf1 P2 3.0487(14) . ? Hf1 P4 3.0546(15) . ? Hf1 P1 3.0552(15) . ? Hf1 P3 3.0593(14) . ? P1 N3 1.704(4) . ? P1 N2 1.719(4) . ? P1 N1 1.793(4) . ? P1 P2 2.6414(19) . ? P2 N4 1.694(4) . ? P2 N2 1.725(4) . ? P2 N1 1.791(4) . ? P3 N7 1.707(4) . ? P3 N6 1.725(4) . ? P3 N5 1.793(4) . ? P3 P4 2.6430(17) . ? P4 N8 1.695(4) . ? P4 N6 1.727(4) . ? P4 N5 1.789(4) . ? N1 C10 1.525(6) . ? N2 C20 1.482(6) . ? N3 C30 1.420(6) . ? N4 C40 1.423(6) . ? N5 C50 1.516(6) . ? N6 C60 1.457(6) . ? N7 C70 1.414(5) . ? N8 C80 1.422(6) . ? C10 C11 1.519(8) . ? C10 C12 1.521(8) . ? C10 C13 1.548(7) . ? C20 C21 1.518(9) . ? C20 C23 1.535(8) . ? C20 C22 1.541(9) . ? C30 C31 1.383(7) . ? C30 C35 1.403(7) . ? C31 C32 1.381(7) . ? C32 C33 1.373(9) . ? C33 C34 1.382(9) . ? C34 C35 1.366(7) . ? C40 C45 1.388(8) . ? C40 C41 1.393(8) . ? C41 C42 1.389(9) . ? C42 C43 1.338(12) . ? C43 C44 1.392(13) . ? C44 C45 1.395(9) . ? C50 C51 1.507(8) . ? C50 C52 1.511(7) . ? C50 C53 1.535(7) . ? C60 C62 1.524(8) . ? C60 C61 1.528(8) . ? C60 C63 1.545(8) . ? C70 C71 1.386(7) . ? C70 C75 1.391(7) . ? C71 C72 1.393(7) . ? C72 C73 1.359(9) . ? C73 C74 1.370(9) . ? C74 C75 1.395(7) . ? C80 C85 1.385(8) . ? C80 C81 1.396(7) . ? C81 C82 1.386(8) . ? C82 C83 1.371(10) . ? C83 C84 1.355(10) . ? C84 C85 1.389(8) . ? C90 C91 1.3900 . ? C90 C95 1.3900 . ? C91 C92 1.3900 . ? C92 C93 1.3900 . ? C93 C96 1.217(14) . ? C93 C94 1.3900 . ? C94 C95 1.3900 . ? 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 N3 Hf1 N7 92.44(14) . . ? N3 Hf1 N8 101.17(14) . . ? N7 Hf1 N8 106.53(14) . . ? N3 Hf1 N4 106.03(14) . . ? N7 Hf1 N4 100.76(15) . . ? N8 Hf1 N4 140.25(14) . . ? N3 Hf1 N1 66.87(13) . . ? N7 Hf1 N1 149.94(13) . . ? N8 Hf1 N1 99.03(13) . . ? N4 Hf1 N1 66.96(14) . . ? N3 Hf1 N5 149.73(13) . . ? N7 Hf1 N5 66.91(13) . . ? N8 Hf1 N5 66.59(13) . . ? N4 Hf1 N5 99.67(14) . . ? N1 Hf1 N5 140.11(12) . . ? N3 Hf1 P2 81.17(10) . . ? N7 Hf1 P2 123.00(10) . . ? N8 Hf1 P2 130.36(11) . . ? N4 Hf1 P2 32.48(11) . . ? N1 Hf1 P2 35.94(9) . . ? N5 Hf1 P2 128.32(9) . . ? N3 Hf1 P4 122.88(10) . . ? N7 Hf1 P4 81.32(10) . . ? N8 Hf1 P4 32.35(10) . . ? N4 Hf1 P4 131.00(11) . . ? N1 Hf1 P4 127.90(9) . . ? N5 Hf1 P4 35.83(9) . . ? P2 Hf1 P4 147.13(3) . . ? N3 Hf1 P1 32.41(10) . . ? N7 Hf1 P1 117.84(10) . . ? N8 Hf1 P1 109.56(11) . . ? N4 Hf1 P1 81.28(11) . . ? N1 Hf1 P1 35.89(9) . . ? N5 Hf1 P1 174.99(8) . . ? P2 Hf1 P1 51.28(4) . . ? P4 Hf1 P1 141.03(4) . . ? N3 Hf1 P3 117.75(10) . . ? N7 Hf1 P3 32.54(10) . . ? N8 Hf1 P3 81.31(11) . . ? N4 Hf1 P3 109.80(11) . . ? N1 Hf1 P3 175.27(9) . . ? N5 Hf1 P3 35.84(9) . . ? P2 Hf1 P3 141.52(4) . . ? P4 Hf1 P3 51.23(3) . . ? P1 Hf1 P3 148.35(3) . . ? N3 P1 N2 107.1(2) . . ? N3 P1 N1 90.80(18) . . ? N2 P1 N1 82.52(18) . . ? N3 P1 P2 102.10(14) . . ? N2 P1 P2 40.02(13) . . ? N1 P1 P2 42.50(12) . . ? N3 P1 Hf1 41.56(12) . . ? N2 P1 Hf1 87.46(14) . . ? N1 P1 Hf1 51.43(12) . . ? P2 P1 Hf1 64.23(4) . . ? N4 P2 N2 107.9(2) . . ? N4 P2 N1 91.88(18) . . ? N2 P2 N1 82.40(19) . . ? N4 P2 P1 103.33(14) . . ? N2 P2 P1 39.85(14) . . ? N1 P2 P1 42.55(12) . . ? N4 P2 Hf1 42.56(13) . . ? N2 P2 Hf1 87.57(14) . . ? N1 P2 Hf1 51.60(12) . . ? P1 P2 Hf1 64.49(4) . . ? N7 P3 N6 107.4(2) . . ? N7 P3 N5 91.66(17) . . ? N6 P3 N5 82.45(18) . . ? N7 P3 P4 102.68(13) . . ? N6 P3 P4 40.05(14) . . ? N5 P3 P4 42.40(12) . . ? N7 P3 Hf1 42.00(12) . . ? N6 P3 Hf1 87.33(15) . . ? N5 P3 Hf1 51.95(12) . . ? P4 P3 Hf1 64.29(4) . . ? N8 P4 N6 108.2(2) . . ? N8 P4 N5 91.91(18) . . ? N6 P4 N5 82.50(18) . . ? N8 P4 P3 103.42(13) . . ? N6 P4 P3 40.00(14) . . ? N5 P4 P3 42.50(12) . . ? N8 P4 Hf1 42.34(12) . . ? N6 P4 Hf1 87.45(14) . . ? N5 P4 Hf1 52.07(12) . . ? P3 P4 Hf1 64.48(4) . . ? C10 N1 P2 114.6(3) . . ? C10 N1 P1 118.1(3) . . ? P2 N1 P1 94.95(18) . . ? C10 N1 Hf1 135.1(3) . . ? P2 N1 Hf1 92.45(15) . . ? P1 N1 Hf1 92.68(15) . . ? C20 N2 P1 129.6(3) . . ? C20 N2 P2 126.4(3) . . ? P1 N2 P2 100.1(2) . . ? C30 N3 P1 119.5(3) . . ? C30 N3 Hf1 134.4(3) . . ? P1 N3 Hf1 106.03(18) . . ? C40 N4 P2 114.1(3) . . ? C40 N4 Hf1 140.5(3) . . ? P2 N4 Hf1 104.97(18) . . ? C50 N5 P4 116.3(3) . . ? C50 N5 P3 119.3(3) . . ? P4 N5 P3 95.09(18) . . ? C50 N5 Hf1 133.0(3) . . ? P4 N5 Hf1 92.10(15) . . ? P3 N5 Hf1 92.21(14) . . ? C60 N6 P3 130.6(3) . . ? C60 N6 P4 127.2(3) . . ? P3 N6 P4 100.0(2) . . ? C70 N7 P3 120.5(3) . . ? C70 N7 Hf1 133.9(3) . . ? P3 N7 Hf1 105.46(17) . . ? C80 N8 P4 114.0(3) . . ? C80 N8 Hf1 140.1(3) . . ? P4 N8 Hf1 105.31(18) . . ? C11 C10 C12 111.0(5) . . ? C11 C10 N1 106.7(4) . . ? C12 C10 N1 109.3(4) . . ? C11 C10 C13 110.9(5) . . ? C12 C10 C13 108.6(5) . . ? N1 C10 C13 110.3(4) . . ? N2 C20 C21 108.0(4) . . ? N2 C20 C23 108.1(4) . . ? C21 C20 C23 111.0(5) . . ? N2 C20 C22 109.6(5) . . ? C21 C20 C22 110.8(5) . . ? C23 C20 C22 109.2(5) . . ? C31 C30 C35 116.9(4) . . ? C31 C30 N3 124.2(4) . . ? C35 C30 N3 118.9(4) . . ? C32 C31 C30 121.6(5) . . ? C33 C32 C31 120.5(5) . . ? C32 C33 C34 119.0(5) . . ? C35 C34 C33 120.6(6) . . ? C34 C35 C30 121.4(5) . . ? C45 C40 C41 118.7(5) . . ? C45 C40 N4 120.6(5) . . ? C41 C40 N4 120.7(5) . . ? C42 C41 C40 119.8(7) . . ? C43 C42 C41 121.4(8) . . ? C42 C43 C44 120.3(7) . . ? C43 C44 C45 119.4(7) . . ? C40 C45 C44 120.4(7) . . ? C51 C50 C52 110.7(5) . . ? C51 C50 N5 106.8(4) . . ? C52 C50 N5 109.2(4) . . ? C51 C50 C53 111.1(5) . . ? C52 C50 C53 108.8(5) . . ? N5 C50 C53 110.1(4) . . ? N6 C60 C62 110.7(5) . . ? N6 C60 C61 109.0(4) . . ? C62 C60 C61 110.3(5) . . ? N6 C60 C63 108.8(4) . . ? C62 C60 C63 108.5(5) . . ? C61 C60 C63 109.5(5) . . ? C71 C70 C75 117.7(4) . . ? C71 C70 N7 123.6(4) . . ? C75 C70 N7 118.6(4) . . ? C70 C71 C72 121.0(5) . . ? C73 C72 C71 120.5(5) . . ? C72 C73 C74 119.8(5) . . ? C73 C74 C75 120.4(5) . . ? C70 C75 C74 120.5(5) . . ? C85 C80 C81 118.2(5) . . ? C85 C80 N8 120.9(4) . . ? C81 C80 N8 120.9(5) . . ? C82 C81 C80 119.9(6) . . ? C83 C82 C81 121.0(6) . . ? C84 C83 C82 119.6(6) . . ? C83 C84 C85 120.6(6) . . ? C80 C85 C84 120.7(6) . . ? C91 C90 C95 120.0 . . ? C92 C91 C90 120.0 . . ? C91 C92 C93 120.0 . . ? C96 C93 C92 122.4(13) . . ? C96 C93 C94 117.6(13) . . ? C92 C93 C94 120.0 . . ? C95 C94 C93 120.0 . . ? C94 C95 C90 120.0 . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 1.485 _refine_diff_density_min -3.141 _refine_diff_density_rms 0.175 #===END=== data_8a _database_code_CSD 197174 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H28 Cl2 N4 P2 Ti' _chemical_formula_weight 505.20 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' P P 0.1023 0.0942 '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' 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 Cc 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' _cell_length_a 9.2541(3) _cell_length_b 15.4971(6) _cell_length_c 16.7405(6) _cell_angle_alpha 90.00 _cell_angle_beta 94.248(10) _cell_angle_gamma 90.00 _cell_volume 2394.2(2) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used 379 _cell_measurement_theta_min 2.10 _cell_measurement_theta_max 23.88 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.402 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1048 _exptl_absorpt_coefficient_mu 0.729 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.7940 _exptl_absorpt_correction_T_max 0.9229 _exptl_special_details ; Data was collected using a Siemens SMART CCD (charge coupled device) based diffractometer equipped with an LT-2 low-temperature apparatus operating at 213 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.3\% per frame for 30 seconds, such that a hemisphere was collected. A total of 1271 frames were collected with a final resolution of 0.75 \%A. The first 50 frames were recollected at the end of data collection to monitor for decay. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software which corrects for Lp and decay. Absorption corrections were applied using SADABS supplied by George Sheldrick. The structures are solved by the direct method using the SHELX-90 program and refined by least squares method on F2 SHELXL-97, incorporated in SHELXTL-PC V 5.03. ; _diffrn_ambient_temperature 213(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type CCD _diffrn_measurement_method '\w, 0.3 deg' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1 _diffrn_reflns_number 7805 _diffrn_reflns_av_R_equivalents 0.0238 _diffrn_reflns_av_sigmaI/netI 0.0247 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.44 _diffrn_reflns_theta_max 28.28 _reflns_number_total 3819 _reflns_number_gt 3767 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'ASTRO (SIEMENS, V4.033, 1994)' _computing_cell_refinement 'SMART (SIEMENS, V4.033, 1994)' _computing_data_reduction 'SAINT (SIEMENS, V4.035, 1994)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (SIEMENS, 1994, ver 5.04)' _computing_publication_material 'CIFTAB (Sheldrick, 1993)' _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 w=1/[\s^2^(Fo^2^)+(0.0422P)^2^+0.7963P] 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 -0.001(19) _refine_ls_number_reflns 3819 _refine_ls_number_parameters 262 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0246 _refine_ls_R_factor_gt 0.0240 _refine_ls_wR_factor_ref 0.0654 _refine_ls_wR_factor_gt 0.0645 _refine_ls_goodness_of_fit_ref 1.036 _refine_ls_restrained_S_all 1.035 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ti1 Ti 0.27198(3) 0.33843(2) 0.15477(2) 0.02555(8) Uani 1 d . . . Cl1 Cl 0.25802(7) 0.48212(3) 0.14073(4) 0.04270(14) Uani 1 d . . . Cl2 Cl 0.48500(6) 0.32583(4) 0.22782(4) 0.04389(14) Uani 1 d . . . P1 P 0.03104(5) 0.22139(3) 0.16801(3) 0.02471(10) Uani 1 d . . . P2 P 0.16852(5) 0.21214(3) 0.03595(3) 0.02645(11) Uani 1 d . . . N1 N 0.20865(18) 0.19767(10) 0.14028(10) 0.0246(3) Uani 1 d . . . N2 N -0.00213(18) 0.22929(11) 0.06651(10) 0.0264(3) Uani 1 d . . . N3 N 0.2627(2) 0.30837(11) 0.04246(10) 0.0285(3) Uani 1 d . . . N4 N 0.09446(19) 0.31936(11) 0.20509(11) 0.0275(3) Uani 1 d . . . C1 C 0.2803(2) 0.11553(13) 0.17132(13) 0.0319(5) Uani 1 d . . . C2 C 0.4281(3) 0.10932(17) 0.13763(18) 0.0442(6) Uani 1 d . . . H2A H 0.4160 0.1059 0.0797 0.066 Uiso 1 calc R . . H2B H 0.4778 0.0581 0.1586 0.066 Uiso 1 calc R . . H2C H 0.4849 0.1600 0.1532 0.066 Uiso 1 calc R . . C3 C 0.2945(3) 0.12047(17) 0.26263(15) 0.0429(6) Uani 1 d . . . H3A H 0.3551 0.1692 0.2793 0.064 Uiso 1 calc R . . H3B H 0.3382 0.0677 0.2842 0.064 Uiso 1 calc R . . H3C H 0.1993 0.1276 0.2824 0.064 Uiso 1 calc R . . C4 C 0.1851(3) 0.03826(14) 0.14388(17) 0.0420(5) Uani 1 d . . . H4A H 0.1775 0.0354 0.0858 0.063 Uiso 1 calc R . . H4B H 0.0893 0.0452 0.1629 0.063 Uiso 1 calc R . . H4C H 0.2285 -0.0145 0.1656 0.063 Uiso 1 calc R . . C5 C -0.1352(2) 0.25627(14) 0.01892(14) 0.0318(4) Uani 1 d . . . C6 C -0.1398(3) 0.2099(2) -0.06170(17) 0.0543(7) Uani 1 d . . . H6A H -0.1410 0.1481 -0.0531 0.081 Uiso 1 calc R . . H6B H -0.0549 0.2254 -0.0892 0.081 Uiso 1 calc R . . H6C H -0.2264 0.2269 -0.0940 0.081 Uiso 1 calc R . . C7 C -0.2656(3) 0.2292(2) 0.06306(19) 0.0518(7) Uani 1 d . . . H7A H -0.2634 0.2589 0.1142 0.078 Uiso 1 calc R . . H7B H -0.2627 0.1674 0.0720 0.078 Uiso 1 calc R . . H7C H -0.3538 0.2442 0.0312 0.078 Uiso 1 calc R . . C8 C -0.1337(3) 0.35325(17) 0.0065(2) 0.0549(8) Uani 1 d . . . H8A H -0.1315 0.3820 0.0580 0.082 Uiso 1 calc R . . H8B H -0.2202 0.3704 -0.0259 0.082 Uiso 1 calc R . . H8C H -0.0486 0.3693 -0.0206 0.082 Uiso 1 calc R . . C9 C 0.3110(2) 0.35016(13) -0.02574(13) 0.0310(4) Uani 1 d . . . C10 C 0.2434(3) 0.33796(15) -0.10194(15) 0.0395(5) Uani 1 d . . . H10A H 0.1625 0.3013 -0.1092 0.047 Uiso 1 calc R . . C11 C 0.2955(4) 0.38011(19) -0.16761(16) 0.0505(7) Uani 1 d . . . H11A H 0.2512 0.3703 -0.2192 0.061 Uiso 1 calc R . . C12 C 0.4104(3) 0.43562(19) -0.15768(17) 0.0501(7) Uani 1 d . . . H12A H 0.4432 0.4649 -0.2021 0.060 Uiso 1 calc R . . C13 C 0.4780(3) 0.44858(18) -0.08258(18) 0.0493(6) Uani 1 d . . . H13A H 0.5569 0.4867 -0.0759 0.059 Uiso 1 calc R . . C14 C 0.4299(3) 0.40544(16) -0.01621(16) 0.0406(5) Uani 1 d . . . H14A H 0.4777 0.4137 0.0348 0.049 Uiso 1 calc R . . C15 C 0.0251(2) 0.36216(12) 0.26685(12) 0.0245(4) Uani 1 d . . . C16 C -0.1215(3) 0.35034(14) 0.27794(14) 0.0328(4) Uani 1 d . . . H16A H -0.1794 0.3171 0.2411 0.039 Uiso 1 calc R . . C17 C -0.1825(3) 0.38745(15) 0.34309(15) 0.0373(5) Uani 1 d . . . H17A H -0.2811 0.3786 0.3504 0.045 Uiso 1 calc R . . C18 C -0.0993(3) 0.43710(14) 0.39707(13) 0.0368(5) Uani 1 d . . . H18A H -0.1405 0.4615 0.4415 0.044 Uiso 1 calc R . . C19 C 0.0450(3) 0.45077(15) 0.38546(14) 0.0374(5) Uani 1 d . . . H19A H 0.1014 0.4856 0.4216 0.045 Uiso 1 calc R . . C20 C 0.1074(3) 0.41368(13) 0.32121(14) 0.0325(4) Uani 1 d . . . H20A H 0.2059 0.4233 0.3142 0.039 Uiso 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 Ti1 0.02099(16) 0.02915(16) 0.02671(16) -0.00107(13) 0.00312(12) -0.00209(13) Cl1 0.0446(3) 0.0307(2) 0.0540(4) 0.0013(2) 0.0109(3) 0.0019(2) Cl2 0.0277(3) 0.0542(3) 0.0482(3) -0.0008(3) -0.0073(2) -0.0045(2) P1 0.0224(2) 0.0268(2) 0.0251(2) -0.00034(18) 0.00328(17) -0.00114(17) P2 0.0269(2) 0.0286(2) 0.0241(2) -0.00145(19) 0.00365(18) 0.00170(18) N1 0.0239(8) 0.0261(7) 0.0242(8) 0.0022(6) 0.0038(6) 0.0022(6) N2 0.0232(9) 0.0307(8) 0.0252(8) -0.0017(6) 0.0006(6) -0.0009(6) N3 0.0266(8) 0.0320(8) 0.0277(9) 0.0024(7) 0.0065(6) -0.0004(7) N4 0.0244(8) 0.0305(8) 0.0282(9) -0.0036(7) 0.0063(6) -0.0014(6) C1 0.0296(10) 0.0273(8) 0.0385(12) 0.0061(8) 0.0002(9) 0.0061(8) C2 0.0332(13) 0.0421(12) 0.0579(16) 0.0007(11) 0.0068(11) 0.0111(9) C3 0.0475(15) 0.0409(12) 0.0392(13) 0.0119(10) -0.0031(10) 0.0034(10) C4 0.0456(14) 0.0269(9) 0.0532(15) 0.0035(10) 0.0021(11) -0.0005(9) C5 0.0260(10) 0.0355(10) 0.0329(10) 0.0012(9) -0.0040(8) -0.0029(8) C6 0.0470(16) 0.0735(18) 0.0396(14) -0.0115(13) -0.0148(12) -0.0014(13) C7 0.0240(12) 0.0770(18) 0.0540(16) 0.0142(14) -0.0007(11) -0.0046(11) C8 0.0440(15) 0.0402(12) 0.078(2) 0.0129(13) -0.0097(14) 0.0069(10) C9 0.0301(11) 0.0312(9) 0.0327(11) 0.0055(8) 0.0097(8) 0.0064(8) C10 0.0461(14) 0.0412(11) 0.0319(11) 0.0034(9) 0.0080(10) 0.0015(10) C11 0.0656(19) 0.0565(15) 0.0308(12) 0.0100(11) 0.0132(11) 0.0171(13) C12 0.0536(16) 0.0545(14) 0.0453(14) 0.0230(12) 0.0253(12) 0.0150(12) C13 0.0394(14) 0.0522(14) 0.0586(17) 0.0197(13) 0.0183(12) -0.0016(11) C14 0.0325(12) 0.0519(13) 0.0381(12) 0.0089(10) 0.0077(9) -0.0039(10) C15 0.0250(9) 0.0260(8) 0.0228(8) 0.0010(7) 0.0043(7) 0.0027(7) C16 0.0286(10) 0.0351(10) 0.0351(11) -0.0053(8) 0.0060(8) -0.0014(8) C17 0.0336(12) 0.0383(11) 0.0415(12) -0.0031(10) 0.0137(9) 0.0002(9) C18 0.0515(14) 0.0330(10) 0.0276(10) -0.0017(9) 0.0134(9) 0.0064(9) C19 0.0466(14) 0.0367(11) 0.0282(10) -0.0062(9) -0.0017(9) 0.0006(9) C20 0.0273(11) 0.0356(10) 0.0342(11) -0.0057(9) 0.0004(8) -0.0012(8) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ti1 N4 1.9237(18) . ? Ti1 N3 1.9326(18) . ? Ti1 Cl1 2.2420(6) . ? Ti1 Cl2 2.2500(6) . ? Ti1 N1 2.2670(17) . ? Ti1 P1 2.8954(6) . ? Ti1 P2 2.9019(6) . ? P1 N2 1.7085(18) . ? P1 N4 1.7265(18) . ? P1 N1 1.7791(18) . ? P1 P2 2.6350(7) . ? P2 N2 1.7164(19) . ? P2 N3 1.7267(18) . ? P2 N1 1.7727(17) . ? N1 C1 1.509(2) . ? N2 C5 1.477(3) . ? N3 C9 1.414(3) . ? N4 C15 1.421(3) . ? C1 C2 1.521(4) . ? C1 C3 1.526(3) . ? C1 C4 1.536(3) . ? C5 C8 1.517(3) . ? C5 C7 1.519(4) . ? C5 C6 1.527(4) . ? C9 C10 1.392(3) . ? C9 C14 1.395(3) . ? C10 C11 1.395(4) . ? C11 C12 1.369(5) . ? C12 C13 1.377(4) . ? C13 C14 1.397(3) . ? C15 C20 1.394(3) . ? C15 C16 1.395(3) . ? C16 C17 1.389(3) . ? C17 C18 1.378(3) . ? C18 C19 1.379(4) . ? C19 C20 1.383(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N4 Ti1 N3 114.27(8) . . ? N4 Ti1 Cl1 98.86(6) . . ? N3 Ti1 Cl1 98.01(6) . . ? N4 Ti1 Cl2 119.40(6) . . ? N3 Ti1 Cl2 118.81(6) . . ? Cl1 Ti1 Cl2 100.63(3) . . ? N4 Ti1 N1 71.14(7) . . ? N3 Ti1 N1 70.82(7) . . ? Cl1 Ti1 N1 158.76(5) . . ? Cl2 Ti1 N1 100.59(5) . . ? N4 Ti1 P1 35.20(5) . . ? N3 Ti1 P1 86.82(5) . . ? Cl1 Ti1 P1 126.26(2) . . ? Cl2 Ti1 P1 123.55(2) . . ? N1 Ti1 P1 37.91(4) . . ? N4 Ti1 P2 86.99(5) . . ? N3 Ti1 P2 35.12(5) . . ? Cl1 Ti1 P2 125.77(2) . . ? Cl2 Ti1 P2 123.05(2) . . ? N1 Ti1 P2 37.65(4) . . ? P1 Ti1 P2 54.068(15) . . ? N2 P1 N4 109.02(8) . . ? N2 P1 N1 81.76(8) . . ? N4 P1 N1 88.82(8) . . ? N2 P1 P2 39.81(6) . . ? N4 P1 P2 100.20(6) . . ? N1 P1 P2 42.01(5) . . ? N2 P1 Ti1 87.80(6) . . ? N4 P1 Ti1 39.96(6) . . ? N1 P1 Ti1 51.53(6) . . ? P2 P1 Ti1 63.092(17) . . ? N2 P2 N3 108.58(8) . . ? N2 P2 N1 81.73(8) . . ? N3 P2 N1 88.80(8) . . ? N2 P2 P1 39.59(6) . . ? N3 P2 P1 99.95(6) . . ? N1 P2 P1 42.20(6) . . ? N2 P2 Ti1 87.44(6) . . ? N3 P2 Ti1 40.08(6) . . ? N1 P2 Ti1 51.36(5) . . ? P1 P2 Ti1 62.839(16) . . ? C1 N1 P2 120.02(13) . . ? C1 N1 P1 118.35(14) . . ? P2 N1 P1 95.78(8) . . ? C1 N1 Ti1 132.16(13) . . ? P2 N1 Ti1 91.00(7) . . ? P1 N1 Ti1 90.56(7) . . ? C5 N2 P1 129.64(15) . . ? C5 N2 P2 129.19(15) . . ? P1 N2 P2 100.60(9) . . ? C9 N3 P2 122.20(14) . . ? C9 N3 Ti1 132.95(14) . . ? P2 N3 Ti1 104.80(9) . . ? C15 N4 P1 120.81(14) . . ? C15 N4 Ti1 133.90(14) . . ? P1 N4 Ti1 104.84(9) . . ? N1 C1 C2 108.04(18) . . ? N1 C1 C3 107.80(17) . . ? C2 C1 C3 111.2(2) . . ? N1 C1 C4 109.10(17) . . ? C2 C1 C4 110.6(2) . . ? C3 C1 C4 110.1(2) . . ? N2 C5 C8 109.82(19) . . ? N2 C5 C7 108.66(19) . . ? C8 C5 C7 110.8(2) . . ? N2 C5 C6 108.14(19) . . ? C8 C5 C6 110.1(2) . . ? C7 C5 C6 109.2(2) . . ? C10 C9 C14 119.1(2) . . ? C10 C9 N3 122.0(2) . . ? C14 C9 N3 118.9(2) . . ? C9 C10 C11 120.0(3) . . ? C12 C11 C10 120.6(3) . . ? C11 C12 C13 119.9(2) . . ? C12 C13 C14 120.4(3) . . ? C9 C14 C13 119.9(2) . . ? C20 C15 C16 118.6(2) . . ? C20 C15 N4 119.20(19) . . ? C16 C15 N4 122.12(18) . . ? C17 C16 C15 120.4(2) . . ? C18 C17 C16 120.4(2) . . ? C17 C18 C19 119.5(2) . . ? C18 C19 C20 120.7(2) . . ? C19 C20 C15 120.4(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 N4 Ti1 P1 N2 123.61(11) . . . . ? N3 Ti1 P1 N2 -18.87(8) . . . . ? Cl1 Ti1 P1 N2 78.74(7) . . . . ? Cl2 Ti1 P1 N2 -141.70(6) . . . . ? N1 Ti1 P1 N2 -81.22(9) . . . . ? P2 Ti1 P1 N2 -32.59(6) . . . . ? N3 Ti1 P1 N4 -142.48(11) . . . . ? Cl1 Ti1 P1 N4 -44.88(10) . . . . ? Cl2 Ti1 P1 N4 94.68(10) . . . . ? N1 Ti1 P1 N4 155.17(11) . . . . ? P2 Ti1 P1 N4 -156.20(10) . . . . ? N4 Ti1 P1 N1 -155.17(11) . . . . ? N3 Ti1 P1 N1 62.35(8) . . . . ? Cl1 Ti1 P1 N1 159.95(7) . . . . ? Cl2 Ti1 P1 N1 -60.49(7) . . . . ? P2 Ti1 P1 N1 48.63(7) . . . . ? N4 Ti1 P1 P2 156.20(10) . . . . ? N3 Ti1 P1 P2 13.72(5) . . . . ? Cl1 Ti1 P1 P2 111.32(3) . . . . ? Cl2 Ti1 P1 P2 -109.12(3) . . . . ? N1 Ti1 P1 P2 -48.63(7) . . . . ? N4 P1 P2 N2 -107.53(11) . . . . ? N1 P1 P2 N2 175.82(12) . . . . ? Ti1 P1 P2 N2 -122.80(9) . . . . ? N2 P1 P2 N3 107.19(11) . . . . ? N4 P1 P2 N3 -0.34(9) . . . . ? N1 P1 P2 N3 -76.99(10) . . . . ? Ti1 P1 P2 N3 -15.61(6) . . . . ? N2 P1 P2 N1 -175.82(12) . . . . ? N4 P1 P2 N1 76.65(11) . . . . ? Ti1 P1 P2 N1 61.38(8) . . . . ? N2 P1 P2 Ti1 122.80(9) . . . . ? N4 P1 P2 Ti1 15.27(6) . . . . ? N1 P1 P2 Ti1 -61.38(8) . . . . ? N4 Ti1 P2 N2 18.96(8) . . . . ? N3 Ti1 P2 N2 -123.26(11) . . . . ? Cl1 Ti1 P2 N2 -79.79(6) . . . . ? Cl2 Ti1 P2 N2 142.48(6) . . . . ? N1 Ti1 P2 N2 81.45(9) . . . . ? P1 Ti1 P2 N2 32.43(6) . . . . ? N4 Ti1 P2 N3 142.22(11) . . . . ? Cl1 Ti1 P2 N3 43.46(10) . . . . ? Cl2 Ti1 P2 N3 -94.26(10) . . . . ? N1 Ti1 P2 N3 -155.29(12) . . . . ? P1 Ti1 P2 N3 155.69(10) . . . . ? N4 Ti1 P2 N1 -62.49(9) . . . . ? N3 Ti1 P2 N1 155.29(12) . . . . ? Cl1 Ti1 P2 N1 -161.24(8) . . . . ? Cl2 Ti1 P2 N1 61.03(8) . . . . ? P1 Ti1 P2 N1 -49.02(7) . . . . ? N4 Ti1 P2 P1 -13.47(6) . . . . ? N3 Ti1 P2 P1 -155.69(10) . . . . ? Cl1 Ti1 P2 P1 -112.22(3) . . . . ? Cl2 Ti1 P2 P1 110.05(3) . . . . ? N1 Ti1 P2 P1 49.02(7) . . . . ? N2 P2 N1 C1 124.89(16) . . . . ? N3 P2 N1 C1 -126.14(16) . . . . ? P1 P2 N1 C1 127.58(18) . . . . ? Ti1 P2 N1 C1 -141.76(18) . . . . ? N2 P2 N1 P1 -2.69(8) . . . . ? N3 P2 N1 P1 106.28(9) . . . . ? Ti1 P2 N1 P1 90.66(7) . . . . ? N2 P2 N1 Ti1 -93.35(7) . . . . ? N3 P2 N1 Ti1 15.62(7) . . . . ? P1 P2 N1 Ti1 -90.66(7) . . . . ? N2 P1 N1 C1 -126.06(15) . . . . ? N4 P1 N1 C1 124.53(15) . . . . ? P2 P1 N1 C1 -128.76(17) . . . . ? Ti1 P1 N1 C1 140.18(16) . . . . ? N2 P1 N1 P2 2.70(8) . . . . ? N4 P1 N1 P2 -106.71(9) . . . . ? Ti1 P1 N1 P2 -91.06(7) . . . . ? N2 P1 N1 Ti1 93.76(7) . . . . ? N4 P1 N1 Ti1 -15.65(7) . . . . ? P2 P1 N1 Ti1 91.06(7) . . . . ? N4 Ti1 N1 C1 -115.69(19) . . . . ? N3 Ti1 N1 C1 118.95(19) . . . . ? Cl1 Ti1 N1 C1 179.77(14) . . . . ? Cl2 Ti1 N1 C1 1.95(18) . . . . ? P1 Ti1 N1 C1 -130.5(2) . . . . ? P2 Ti1 N1 C1 133.7(2) . . . . ? N4 Ti1 N1 P2 110.61(9) . . . . ? N3 Ti1 N1 P2 -14.75(7) . . . . ? Cl1 Ti1 N1 P2 46.07(17) . . . . ? Cl2 Ti1 N1 P2 -131.75(6) . . . . ? P1 Ti1 N1 P2 95.79(8) . . . . ? N4 Ti1 N1 P1 14.82(7) . . . . ? N3 Ti1 N1 P1 -110.54(8) . . . . ? Cl1 Ti1 N1 P1 -49.73(16) . . . . ? Cl2 Ti1 N1 P1 132.45(5) . . . . ? P2 Ti1 N1 P1 -95.79(8) . . . . ? N4 P1 N2 C5 -88.80(19) . . . . ? N1 P1 N2 C5 -174.68(18) . . . . ? P2 P1 N2 C5 -171.9(2) . . . . ? Ti1 P1 N2 C5 -123.25(17) . . . . ? N4 P1 N2 P2 83.05(10) . . . . ? N1 P1 N2 P2 -2.82(8) . . . . ? Ti1 P1 N2 P2 48.60(7) . . . . ? N3 P2 N2 C5 88.82(18) . . . . ? N1 P2 N2 C5 174.74(18) . . . . ? P1 P2 N2 C5 171.9(2) . . . . ? Ti1 P2 N2 C5 123.43(17) . . . . ? N3 P2 N2 P1 -83.08(10) . . . . ? N1 P2 N2 P1 2.83(8) . . . . ? Ti1 P2 N2 P1 -48.47(7) . . . . ? N2 P2 N3 C9 -116.11(16) . . . . ? N1 P2 N3 C9 163.03(17) . . . . ? P1 P2 N3 C9 -156.08(15) . . . . ? Ti1 P2 N3 C9 -177.9(2) . . . . ? N2 P2 N3 Ti1 61.80(10) . . . . ? N1 P2 N3 Ti1 -19.06(9) . . . . ? P1 P2 N3 Ti1 21.83(8) . . . . ? N4 Ti1 N3 C9 135.43(18) . . . . ? Cl1 Ti1 N3 C9 31.89(19) . . . . ? Cl2 Ti1 N3 C9 -74.97(19) . . . . ? N1 Ti1 N3 C9 -166.7(2) . . . . ? P1 Ti1 N3 C9 158.08(19) . . . . ? P2 Ti1 N3 C9 177.6(2) . . . . ? N4 Ti1 N3 P2 -42.15(11) . . . . ? Cl1 Ti1 N3 P2 -145.69(7) . . . . ? Cl2 Ti1 N3 P2 107.45(8) . . . . ? N1 Ti1 N3 P2 15.68(7) . . . . ? P1 Ti1 N3 P2 -19.50(8) . . . . ? N2 P1 N4 C15 124.99(15) . . . . ? N1 P1 N4 C15 -154.14(16) . . . . ? P2 P1 N4 C15 165.22(14) . . . . ? Ti1 P1 N4 C15 -173.3(2) . . . . ? N2 P1 N4 Ti1 -61.67(11) . . . . ? N1 P1 N4 Ti1 19.20(9) . . . . ? P2 P1 N4 Ti1 -21.45(9) . . . . ? N3 Ti1 N4 C15 -146.11(17) . . . . ? Cl1 Ti1 N4 C15 -43.10(19) . . . . ? Cl2 Ti1 N4 C15 64.5(2) . . . . ? N1 Ti1 N4 C15 156.2(2) . . . . ? P1 Ti1 N4 C15 172.1(2) . . . . ? P2 Ti1 N4 C15 -168.85(19) . . . . ? N3 Ti1 N4 P1 41.84(12) . . . . ? Cl1 Ti1 N4 P1 144.84(7) . . . . ? Cl2 Ti1 N4 P1 -107.57(8) . . . . ? N1 Ti1 N4 P1 -15.82(7) . . . . ? P2 Ti1 N4 P1 19.10(8) . . . . ? P2 N1 C1 C2 62.2(2) . . . . ? P1 N1 C1 C2 178.59(15) . . . . ? Ti1 N1 C1 C2 -61.2(2) . . . . ? P2 N1 C1 C3 -177.56(15) . . . . ? P1 N1 C1 C3 -61.2(2) . . . . ? Ti1 N1 C1 C3 59.0(2) . . . . ? P2 N1 C1 C4 -58.0(2) . . . . ? P1 N1 C1 C4 58.3(2) . . . . ? Ti1 N1 C1 C4 178.59(16) . . . . ? P1 N2 C5 C8 89.1(3) . . . . ? P2 N2 C5 C8 -80.6(3) . . . . ? P1 N2 C5 C7 -32.3(3) . . . . ? P2 N2 C5 C7 158.09(18) . . . . ? P1 N2 C5 C6 -150.71(19) . . . . ? P2 N2 C5 C6 39.6(3) . . . . ? P2 N3 C9 C10 25.3(3) . . . . ? Ti1 N3 C9 C10 -151.96(18) . . . . ? P2 N3 C9 C14 -154.86(18) . . . . ? Ti1 N3 C9 C14 27.9(3) . . . . ? C14 C9 C10 C11 0.6(4) . . . . ? N3 C9 C10 C11 -179.5(2) . . . . ? C9 C10 C11 C12 -1.9(4) . . . . ? C10 C11 C12 C13 1.6(4) . . . . ? C11 C12 C13 C14 0.0(4) . . . . ? C10 C9 C14 C13 1.0(4) . . . . ? N3 C9 C14 C13 -178.9(2) . . . . ? C12 C13 C14 C9 -1.3(4) . . . . ? P1 N4 C15 C20 149.09(16) . . . . ? Ti1 N4 C15 C20 -22.0(3) . . . . ? P1 N4 C15 C16 -27.0(3) . . . . ? Ti1 N4 C15 C16 161.95(17) . . . . ? C20 C15 C16 C17 -1.7(3) . . . . ? N4 C15 C16 C17 174.4(2) . . . . ? C15 C16 C17 C18 0.7(3) . . . . ? C16 C17 C18 C19 0.9(4) . . . . ? C17 C18 C19 C20 -1.4(3) . . . . ? C18 C19 C20 C15 0.3(3) . . . . ? C16 C15 C20 C19 1.2(3) . . . . ? N4 C15 C20 C19 -175.06(19) . . . . ? _diffrn_measured_fraction_theta_max 0.488 _diffrn_reflns_theta_full 28.28 _diffrn_measured_fraction_theta_full 0.488 _refine_diff_density_max 0.299 _refine_diff_density_min -0.274 _refine_diff_density_rms 0.041 #===END=== data_9 _database_code_CSD 197175 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H36 Cl N4 O P2 V' _chemical_formula_weight 544.90 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' P P 0.1023 0.0942 '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' V V 0.3005 0.5294 '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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 10.4689(1) _cell_length_b 12.8799(2) _cell_length_c 20.9860(1) _cell_angle_alpha 90.00 _cell_angle_beta 102.520(1) _cell_angle_gamma 90.00 _cell_volume 2762.43(5) _cell_formula_units_Z 4 _cell_measurement_temperature 213(2) _cell_measurement_reflns_used 209 _cell_measurement_theta_min 2.55 _cell_measurement_theta_max 20.27 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.310 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1144 _exptl_absorpt_coefficient_mu 0.595 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9165 _exptl_absorpt_correction_T_max 0.9605 _exptl_absorpt_process_details ? _exptl_special_details ; Data was collected using a Bruker SMART CCD (charge coupled device) based diffractometer equipped with an LT-2 low-temperature apparatus operating at 213 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.3\% per frame for 30 seconds, such that a hemisphere was collected. A total of 1271 frames were collected with a final resolution of 0.75 \%A. The first 50 frames were recollected at the end of data collection to monitor for decay. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software which corrects for Lp and decay. Absorption corrections were applied using SADABS supplied by George Sheldrick. The structures are solved by the direct method using the SHELX-90 program and refined by least squares method on F2 SHELXL-97, incorporated in SHELXTL-PC V 5.10. ; _diffrn_ambient_temperature 213(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type CCD _diffrn_measurement_method '\w, 0.3 deg' _diffrn_detector_area_resol_mean 836.6 _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time ? _diffrn_standards_decay_% <1 _diffrn_reflns_number 17903 _diffrn_reflns_av_R_equivalents 0.0335 _diffrn_reflns_av_sigmaI/netI 0.0390 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 1.87 _diffrn_reflns_theta_max 27.58 _reflns_number_total 5822 _reflns_number_gt 4482 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'ASTRO (Bruker, V4.050, 1995)' _computing_cell_refinement 'SMART (Bruker, V4.050, 1995)' _computing_data_reduction 'SAINT (Bruker, V5.A06, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Bruker, 1998, ver 5.10)' _computing_publication_material 'CIFTAB (Sheldrick, 1993)' _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^)+(0.0481P)^2^+0.7521P] 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 5822 _refine_ls_number_parameters 298 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0554 _refine_ls_R_factor_gt 0.0355 _refine_ls_wR_factor_ref 0.0952 _refine_ls_wR_factor_gt 0.0877 _refine_ls_goodness_of_fit_ref 1.030 _refine_ls_restrained_S_all 1.030 _refine_ls_shift/su_max 0.005 _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 V1 V 0.30552(3) 0.21227(3) 0.043111(17) 0.02443(10) Uani 1 1 d . . . P1 P 0.15490(5) 0.37912(4) 0.07755(3) 0.02882(14) Uani 1 1 d . . . P2 P 0.08406(5) 0.18650(4) 0.10027(3) 0.02839(13) Uani 1 1 d . . . Cl1 Cl 0.32867(6) 0.15994(5) -0.05815(3) 0.04140(15) Uani 1 1 d . . . N1 N 0.10534(16) 0.26311(13) 0.03169(8) 0.0266(4) Uani 1 1 d . . . N2 N 0.11458(17) 0.30506(13) 0.13920(9) 0.0306(4) Uani 1 1 d . . . N3 N 0.31409(16) 0.35471(13) 0.07404(9) 0.0293(4) Uani 1 1 d . . . N4 N 0.22838(16) 0.12517(13) 0.10044(9) 0.0274(4) Uani 1 1 d . . . C1 C -0.0041(2) 0.26696(17) -0.02882(11) 0.0332(5) Uani 1 1 d . . . C2 C 0.0393(2) 0.33761(19) -0.07849(12) 0.0419(6) Uani 1 1 d . . . H2A H 0.1181 0.3098 -0.0893 0.063 Uiso 1 1 calc R . . H2B H 0.0569 0.4066 -0.0601 0.063 Uiso 1 1 calc R . . H2C H -0.0295 0.3414 -0.1177 0.063 Uiso 1 1 calc R . . C3 C -0.1293(2) 0.3099(2) -0.01166(13) 0.0459(6) Uani 1 1 d . . . H3A H -0.1564 0.2645 0.0198 0.069 Uiso 1 1 calc R . . H3B H -0.1981 0.3135 -0.0509 0.069 Uiso 1 1 calc R . . H3C H -0.1125 0.3788 0.0069 0.069 Uiso 1 1 calc R . . C4 C -0.0260(2) 0.15640(19) -0.05538(13) 0.0469(6) Uani 1 1 d . . . H4A H -0.0535 0.1125 -0.0232 0.070 Uiso 1 1 calc R . . H4B H 0.0548 0.1297 -0.0645 0.070 Uiso 1 1 calc R . . H4C H -0.0933 0.1568 -0.0952 0.070 Uiso 1 1 calc R . . C5 C 0.1276(2) 0.33060(18) 0.20902(11) 0.0356(5) Uani 1 1 d . . . C6 C 0.0349(3) 0.2608(2) 0.23745(13) 0.0522(7) Uani 1 1 d . . . H6A H -0.0543 0.2714 0.2134 0.078 Uiso 1 1 calc R . . H6B H 0.0412 0.2782 0.2830 0.078 Uiso 1 1 calc R . . H6C H 0.0591 0.1887 0.2339 0.078 Uiso 1 1 calc R . . C7 C 0.0868(3) 0.44451(19) 0.21453(13) 0.0489(6) Uani 1 1 d . . . H7A H 0.1453 0.4895 0.1971 0.073 Uiso 1 1 calc R . . H7B H 0.0915 0.4615 0.2600 0.073 Uiso 1 1 calc R . . H7C H -0.0021 0.4543 0.1899 0.073 Uiso 1 1 calc R . . C8 C 0.2691(3) 0.3137(2) 0.24657(12) 0.0513(7) Uani 1 1 d . . . H8A H 0.3272 0.3580 0.2285 0.077 Uiso 1 1 calc R . . H8B H 0.2933 0.2416 0.2427 0.077 Uiso 1 1 calc R . . H8C H 0.2761 0.3307 0.2922 0.077 Uiso 1 1 calc R . . C9 C 0.4167(2) 0.42769(16) 0.09352(10) 0.0298(5) Uani 1 1 d . . . C10 C 0.5290(2) 0.41919(18) 0.06747(12) 0.0393(5) Uani 1 1 d . . . H10A H 0.5350 0.3655 0.0379 0.047 Uiso 1 1 calc R . . C11 C 0.6311(2) 0.4893(2) 0.08502(13) 0.0470(6) Uani 1 1 d . . . H11A H 0.7063 0.4817 0.0678 0.056 Uiso 1 1 calc R . . C12 C 0.6241(3) 0.5700(2) 0.12746(13) 0.0487(7) Uani 1 1 d . . . H12A H 0.6933 0.6176 0.1389 0.058 Uiso 1 1 calc R . . C13 C 0.5137(3) 0.57942(19) 0.15270(14) 0.0497(7) Uani 1 1 d . . . H13A H 0.5077 0.6344 0.1814 0.060 Uiso 1 1 calc R . . C14 C 0.4111(2) 0.50920(17) 0.13652(12) 0.0405(6) Uani 1 1 d . . . H14A H 0.3371 0.5167 0.1548 0.049 Uiso 1 1 calc R . . C15 C 0.26915(19) 0.03208(15) 0.13463(10) 0.0264(4) Uani 1 1 d . . . C16 C 0.3469(2) -0.03735(16) 0.10831(11) 0.0316(5) Uani 1 1 d . . . H16A H 0.3714 -0.0207 0.0690 0.038 Uiso 1 1 calc R . . C17 C 0.3882(2) -0.12999(17) 0.13933(12) 0.0369(5) Uani 1 1 d . . . H17A H 0.4411 -0.1753 0.1212 0.044 Uiso 1 1 calc R . . C18 C 0.3522(2) -0.15636(18) 0.19693(12) 0.0420(6) Uani 1 1 d . . . H18A H 0.3794 -0.2197 0.2177 0.050 Uiso 1 1 calc R . . C19 C 0.2761(3) -0.08907(19) 0.22349(12) 0.0444(6) Uani 1 1 d . . . H19A H 0.2519 -0.1066 0.2627 0.053 Uiso 1 1 calc R . . C20 C 0.2345(2) 0.00479(17) 0.19299(11) 0.0367(5) Uani 1 1 d . . . H20A H 0.1827 0.0501 0.2118 0.044 Uiso 1 1 calc R . . O1 O 0.49972(14) 0.17234(11) 0.08636(7) 0.0315(3) Uani 1 1 d . . . C21 C 0.5462(2) 0.18598(19) 0.15668(11) 0.0376(5) Uani 1 1 d . . . H21A H 0.4803 0.1622 0.1802 0.045 Uiso 1 1 calc R . . H21B H 0.5662 0.2591 0.1674 0.045 Uiso 1 1 calc R . . C22 C 0.6664(3) 0.1213(3) 0.17368(16) 0.0743(10) Uani 1 1 d . . . H22A H 0.7290 0.1514 0.2106 0.089 Uiso 1 1 calc R . . H22B H 0.6452 0.0506 0.1851 0.089 Uiso 1 1 calc R . . C23 C 0.7207(3) 0.1212(3) 0.11448(15) 0.0704(10) Uani 1 1 d . . . H23A H 0.7703 0.0574 0.1119 0.084 Uiso 1 1 calc R . . H23B H 0.7786 0.1809 0.1144 0.084 Uiso 1 1 calc R . . C24 C 0.6039(2) 0.1277(2) 0.05851(12) 0.0426(6) Uani 1 1 d . . . H24A H 0.6226 0.1722 0.0238 0.051 Uiso 1 1 calc R . . H24B H 0.5791 0.0586 0.0405 0.051 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 V1 0.02588(19) 0.02450(18) 0.02341(19) -0.00009(14) 0.00644(14) -0.00173(13) P1 0.0292(3) 0.0273(3) 0.0294(3) -0.0004(2) 0.0050(2) 0.0018(2) P2 0.0244(3) 0.0314(3) 0.0298(3) 0.0020(2) 0.0066(2) -0.0009(2) Cl1 0.0465(3) 0.0519(3) 0.0271(3) -0.0024(3) 0.0109(3) 0.0069(3) N1 0.0249(9) 0.0274(9) 0.0262(9) 0.0006(7) 0.0025(7) -0.0008(7) N2 0.0308(9) 0.0336(10) 0.0285(10) 0.0000(8) 0.0091(8) 0.0030(7) N3 0.0294(9) 0.0265(9) 0.0323(10) -0.0014(8) 0.0076(8) -0.0026(7) N4 0.0255(9) 0.0275(9) 0.0295(10) 0.0031(8) 0.0065(7) 0.0003(7) C1 0.0278(11) 0.0388(12) 0.0287(12) 0.0013(10) -0.0032(9) -0.0006(9) C2 0.0430(14) 0.0484(14) 0.0318(13) 0.0068(11) 0.0029(11) 0.0048(11) C3 0.0285(12) 0.0574(16) 0.0484(15) 0.0064(13) 0.0008(11) 0.0037(10) C4 0.0439(14) 0.0462(14) 0.0425(15) -0.0035(12) -0.0081(12) -0.0085(11) C5 0.0388(13) 0.0408(13) 0.0292(12) -0.0028(10) 0.0118(10) 0.0046(10) C6 0.0614(17) 0.0581(16) 0.0450(16) -0.0010(13) 0.0289(14) 0.0003(13) C7 0.0584(17) 0.0469(15) 0.0441(15) -0.0118(12) 0.0168(13) 0.0083(12) C8 0.0537(16) 0.0639(17) 0.0324(14) 0.0013(13) 0.0012(12) 0.0051(13) C9 0.0321(11) 0.0256(10) 0.0302(12) 0.0039(9) 0.0034(9) -0.0030(8) C10 0.0442(14) 0.0353(12) 0.0410(14) -0.0024(11) 0.0151(11) -0.0095(10) C11 0.0399(14) 0.0484(15) 0.0555(16) 0.0025(13) 0.0167(12) -0.0127(11) C12 0.0466(15) 0.0410(14) 0.0547(17) 0.0022(13) 0.0030(13) -0.0194(11) C13 0.0531(16) 0.0335(13) 0.0582(17) -0.0130(12) 0.0027(13) -0.0085(11) C14 0.0384(13) 0.0336(12) 0.0498(15) -0.0080(11) 0.0106(11) -0.0017(9) C15 0.0260(10) 0.0259(10) 0.0261(11) 0.0005(9) 0.0026(8) -0.0040(8) C16 0.0338(12) 0.0318(11) 0.0317(12) 0.0020(9) 0.0125(10) -0.0022(9) C17 0.0351(12) 0.0339(12) 0.0430(14) 0.0032(11) 0.0111(11) 0.0054(9) C18 0.0486(14) 0.0357(12) 0.0406(14) 0.0125(11) 0.0074(12) 0.0077(10) C19 0.0619(17) 0.0431(14) 0.0312(13) 0.0095(11) 0.0166(12) 0.0028(12) C20 0.0464(14) 0.0343(12) 0.0332(12) 0.0018(10) 0.0166(11) 0.0043(10) O1 0.0270(8) 0.0405(8) 0.0271(8) -0.0038(7) 0.0062(6) 0.0020(6) C21 0.0355(12) 0.0479(14) 0.0270(12) -0.0047(10) 0.0013(10) -0.0004(10) C22 0.0549(19) 0.106(3) 0.0539(19) -0.0012(19) -0.0058(15) 0.0232(18) C23 0.0329(15) 0.120(3) 0.0565(19) -0.0146(19) 0.0054(13) 0.0150(16) C24 0.0309(12) 0.0571(15) 0.0424(14) -0.0076(12) 0.0134(11) 0.0030(11) _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 V1 N3 1.9416(17) . ? V1 N4 1.9441(17) . ? V1 O1 2.1028(14) . ? V1 N1 2.1588(17) . ? V1 Cl1 2.2918(7) . ? V1 P1 2.8498(6) . ? V1 P2 2.8513(6) . ? P1 N3 1.7133(18) . ? P1 N2 1.7316(18) . ? P1 N1 1.7921(17) . ? P1 P2 2.6618(8) . ? P2 N4 1.7042(17) . ? P2 N2 1.7287(18) . ? P2 N1 1.7983(18) . ? N1 C1 1.515(3) . ? N2 C5 1.479(3) . ? N3 C9 1.419(3) . ? N4 C15 1.415(2) . ? C1 C2 1.525(3) . ? C1 C4 1.528(3) . ? C1 C3 1.536(3) . ? C5 C8 1.535(3) . ? C5 C6 1.536(3) . ? C5 C7 1.539(3) . ? C9 C14 1.394(3) . ? C9 C10 1.404(3) . ? C10 C11 1.386(3) . ? C11 C12 1.381(4) . ? C12 C13 1.377(4) . ? C13 C14 1.389(3) . ? C15 C20 1.396(3) . ? C15 C16 1.401(3) . ? C16 C17 1.383(3) . ? C17 C18 1.385(3) . ? C18 C19 1.374(3) . ? C19 C20 1.393(3) . ? O1 C21 1.461(3) . ? O1 C24 1.462(3) . ? C21 C22 1.487(4) . ? C22 C23 1.474(4) . ? C23 C24 1.503(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N3 V1 N4 109.49(7) . . ? N3 V1 O1 96.69(7) . . ? N4 V1 O1 94.83(6) . . ? N3 V1 N1 73.97(7) . . ? N4 V1 N1 73.76(7) . . ? O1 V1 N1 161.19(6) . . ? N3 V1 Cl1 125.54(6) . . ? N4 V1 Cl1 123.08(6) . . ? O1 V1 Cl1 92.38(4) . . ? N1 V1 Cl1 106.35(5) . . ? N3 V1 P1 35.97(5) . . ? N4 V1 P1 87.21(5) . . ? O1 V1 P1 127.69(4) . . ? N1 V1 P1 38.94(5) . . ? Cl1 V1 P1 129.24(2) . . ? N3 V1 P2 87.26(5) . . ? N4 V1 P2 35.68(5) . . ? O1 V1 P2 126.03(4) . . ? N1 V1 P2 39.08(5) . . ? Cl1 V1 P2 127.95(2) . . ? P1 V1 P2 55.665(17) . . ? N3 P1 N2 109.15(9) . . ? N3 P1 N1 89.71(8) . . ? N2 P1 N1 81.55(8) . . ? N3 P1 P2 98.51(6) . . ? N2 P1 P2 39.67(6) . . ? N1 P1 P2 42.24(6) . . ? N3 P1 V1 41.74(6) . . ? N2 P1 V1 90.69(6) . . ? N1 P1 V1 49.21(5) . . ? P2 P1 V1 62.196(18) . . ? N4 P2 N2 109.61(9) . . ? N4 P2 N1 89.57(8) . . ? N2 P2 N1 81.45(8) . . ? N4 P2 P1 98.69(6) . . ? N2 P2 P1 39.76(6) . . ? N1 P2 P1 42.06(6) . . ? N4 P2 V1 41.71(6) . . ? N2 P2 V1 90.70(6) . . ? N1 P2 V1 49.18(5) . . ? P1 P2 V1 62.139(18) . . ? C1 N1 P1 120.07(13) . . ? C1 N1 P2 119.10(13) . . ? P1 N1 P2 95.69(9) . . ? C1 N1 V1 129.96(13) . . ? P1 N1 V1 91.85(7) . . ? P2 N1 V1 91.74(7) . . ? C5 N2 P2 129.25(15) . . ? C5 N2 P1 129.25(15) . . ? P2 N2 P1 100.57(9) . . ? C9 N3 P1 123.28(14) . . ? C9 N3 V1 134.37(14) . . ? P1 N3 V1 102.29(8) . . ? C15 N4 P2 124.32(14) . . ? C15 N4 V1 133.05(13) . . ? P2 N4 V1 102.61(8) . . ? N1 C1 C2 108.01(17) . . ? N1 C1 C4 107.56(17) . . ? C2 C1 C4 110.5(2) . . ? N1 C1 C3 110.12(18) . . ? C2 C1 C3 109.95(19) . . ? C4 C1 C3 110.64(19) . . ? N2 C5 C8 110.38(19) . . ? N2 C5 C6 108.94(19) . . ? C8 C5 C6 109.8(2) . . ? N2 C5 C7 108.60(19) . . ? C8 C5 C7 110.5(2) . . ? C6 C5 C7 108.6(2) . . ? C14 C9 C10 117.9(2) . . ? C14 C9 N3 123.3(2) . . ? C10 C9 N3 118.79(19) . . ? C11 C10 C9 120.5(2) . . ? C12 C11 C10 121.0(2) . . ? C13 C12 C11 118.8(2) . . ? C12 C13 C14 121.2(2) . . ? C13 C14 C9 120.6(2) . . ? C20 C15 C16 117.97(19) . . ? C20 C15 N4 123.45(19) . . ? C16 C15 N4 118.57(18) . . ? C17 C16 C15 120.9(2) . . ? C16 C17 C18 120.4(2) . . ? C19 C18 C17 119.4(2) . . ? C18 C19 C20 120.8(2) . . ? C19 C20 C15 120.5(2) . . ? C21 O1 C24 109.72(16) . . ? C21 O1 V1 119.05(12) . . ? C24 O1 V1 131.21(13) . . ? O1 C21 C22 104.7(2) . . ? C23 C22 C21 105.0(3) . . ? C22 C23 C24 105.2(2) . . ? O1 C24 C23 105.1(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 N4 V1 P1 N3 129.49(11) . . . . ? O1 V1 P1 N3 35.54(11) . . . . ? N1 V1 P1 N3 -163.17(12) . . . . ? Cl1 V1 P1 N3 -98.78(10) . . . . ? P2 V1 P1 N3 147.41(9) . . . . ? N3 V1 P1 N2 -118.64(11) . . . . ? N4 V1 P1 N2 10.85(8) . . . . ? O1 V1 P1 N2 -83.09(8) . . . . ? N1 V1 P1 N2 78.20(9) . . . . ? Cl1 V1 P1 N2 142.58(7) . . . . ? P2 V1 P1 N2 28.77(6) . . . . ? N3 V1 P1 N1 163.17(12) . . . . ? N4 V1 P1 N1 -67.34(9) . . . . ? O1 V1 P1 N1 -161.29(9) . . . . ? Cl1 V1 P1 N1 64.39(8) . . . . ? P2 V1 P1 N1 -49.43(7) . . . . ? N3 V1 P1 P2 -147.41(9) . . . . ? N4 V1 P1 P2 -17.92(5) . . . . ? O1 V1 P1 P2 -111.87(6) . . . . ? N1 V1 P1 P2 49.43(7) . . . . ? Cl1 V1 P1 P2 113.81(3) . . . . ? N3 P1 P2 N4 -0.49(9) . . . . ? N2 P1 P2 N4 -110.30(11) . . . . ? N1 P1 P2 N4 79.58(10) . . . . ? V1 P1 P2 N4 20.77(6) . . . . ? N3 P1 P2 N2 109.82(11) . . . . ? N1 P1 P2 N2 -170.11(12) . . . . ? V1 P1 P2 N2 131.08(9) . . . . ? N3 P1 P2 N1 -80.07(10) . . . . ? N2 P1 P2 N1 170.11(12) . . . . ? V1 P1 P2 N1 -58.81(8) . . . . ? N3 P1 P2 V1 -21.26(6) . . . . ? N2 P1 P2 V1 -131.08(9) . . . . ? N1 P1 P2 V1 58.81(8) . . . . ? N3 V1 P2 N4 -129.74(10) . . . . ? O1 V1 P2 N4 -33.46(10) . . . . ? N1 V1 P2 N4 162.56(12) . . . . ? Cl1 V1 P2 N4 95.77(9) . . . . ? P1 V1 P2 N4 -148.21(9) . . . . ? N3 V1 P2 N2 -10.36(8) . . . . ? N4 V1 P2 N2 119.38(11) . . . . ? O1 V1 P2 N2 85.92(8) . . . . ? N1 V1 P2 N2 -78.05(9) . . . . ? Cl1 V1 P2 N2 -144.85(6) . . . . ? P1 V1 P2 N2 -28.82(6) . . . . ? N3 V1 P2 N1 67.70(9) . . . . ? N4 V1 P2 N1 -162.56(12) . . . . ? O1 V1 P2 N1 163.98(9) . . . . ? Cl1 V1 P2 N1 -66.79(8) . . . . ? P1 V1 P2 N1 49.23(7) . . . . ? N3 V1 P2 P1 18.47(5) . . . . ? N4 V1 P2 P1 148.21(9) . . . . ? O1 V1 P2 P1 114.75(5) . . . . ? N1 V1 P2 P1 -49.23(7) . . . . ? Cl1 V1 P2 P1 -116.02(3) . . . . ? N3 P1 N1 C1 -128.45(16) . . . . ? N2 P1 N1 C1 122.13(16) . . . . ? P2 P1 N1 C1 128.50(18) . . . . ? V1 P1 N1 C1 -139.57(18) . . . . ? N3 P1 N1 P2 103.05(9) . . . . ? N2 P1 N1 P2 -6.36(8) . . . . ? V1 P1 N1 P2 91.93(8) . . . . ? N3 P1 N1 V1 11.12(8) . . . . ? N2 P1 N1 V1 -98.30(8) . . . . ? P2 P1 N1 V1 -91.93(8) . . . . ? N4 P2 N1 C1 127.29(16) . . . . ? N2 P2 N1 C1 -122.80(16) . . . . ? P1 P2 N1 C1 -129.18(18) . . . . ? V1 P2 N1 C1 138.79(17) . . . . ? N4 P2 N1 P1 -103.53(8) . . . . ? N2 P2 N1 P1 6.37(8) . . . . ? V1 P2 N1 P1 -92.03(8) . . . . ? N4 P2 N1 V1 -11.50(8) . . . . ? N2 P2 N1 V1 98.40(8) . . . . ? P1 P2 N1 V1 92.03(8) . . . . ? N3 V1 N1 C1 122.73(18) . . . . ? N4 V1 N1 C1 -120.83(18) . . . . ? O1 V1 N1 C1 -175.14(17) . . . . ? Cl1 V1 N1 C1 -0.37(17) . . . . ? P1 V1 N1 C1 132.9(2) . . . . ? P2 V1 N1 C1 -131.32(19) . . . . ? N3 V1 N1 P1 -10.20(7) . . . . ? N4 V1 N1 P1 106.25(8) . . . . ? O1 V1 N1 P1 51.9(2) . . . . ? Cl1 V1 N1 P1 -133.29(6) . . . . ? P2 V1 N1 P1 95.76(9) . . . . ? N3 V1 N1 P2 -105.95(8) . . . . ? N4 V1 N1 P2 10.49(7) . . . . ? O1 V1 N1 P2 -43.8(2) . . . . ? Cl1 V1 N1 P2 130.95(5) . . . . ? P1 V1 N1 P2 -95.76(9) . . . . ? N4 P2 N2 C5 -89.81(19) . . . . ? N1 P2 N2 C5 -176.27(19) . . . . ? P1 P2 N2 C5 -169.6(2) . . . . ? V1 P2 N2 C5 -127.79(18) . . . . ? N4 P2 N2 P1 79.79(10) . . . . ? N1 P2 N2 P1 -6.68(8) . . . . ? V1 P2 N2 P1 41.80(7) . . . . ? N3 P1 N2 C5 89.56(19) . . . . ? N1 P1 N2 C5 176.29(19) . . . . ? P2 P1 N2 C5 169.6(2) . . . . ? V1 P1 N2 C5 127.77(18) . . . . ? N3 P1 N2 P2 -80.03(10) . . . . ? N1 P1 N2 P2 6.70(8) . . . . ? V1 P1 N2 P2 -41.83(7) . . . . ? N2 P1 N3 C9 -109.33(17) . . . . ? N1 P1 N3 C9 169.72(17) . . . . ? P2 P1 N3 C9 -148.81(16) . . . . ? V1 P1 N3 C9 -177.6(2) . . . . ? N2 P1 N3 V1 68.28(10) . . . . ? N1 P1 N3 V1 -12.67(9) . . . . ? P2 P1 N3 V1 28.80(8) . . . . ? N4 V1 N3 C9 122.4(2) . . . . ? O1 V1 N3 C9 24.8(2) . . . . ? N1 V1 N3 C9 -171.9(2) . . . . ? Cl1 V1 N3 C9 -73.0(2) . . . . ? P1 V1 N3 C9 177.2(3) . . . . ? P2 V1 N3 C9 150.8(2) . . . . ? N4 V1 N3 P1 -54.85(10) . . . . ? O1 V1 N3 P1 -152.41(8) . . . . ? N1 V1 N3 P1 10.92(8) . . . . ? Cl1 V1 N3 P1 109.82(8) . . . . ? P2 V1 N3 P1 -26.44(7) . . . . ? N2 P2 N4 C15 113.90(16) . . . . ? N1 P2 N4 C15 -165.34(17) . . . . ? P1 P2 N4 C15 153.44(15) . . . . ? V1 P2 N4 C15 -178.4(2) . . . . ? N2 P2 N4 V1 -67.66(10) . . . . ? N1 P2 N4 V1 13.11(9) . . . . ? P1 P2 N4 V1 -28.11(8) . . . . ? N3 V1 N4 C15 -127.19(18) . . . . ? O1 V1 N4 C15 -28.34(19) . . . . ? N1 V1 N4 C15 166.9(2) . . . . ? Cl1 V1 N4 C15 67.68(19) . . . . ? P1 V1 N4 C15 -155.94(18) . . . . ? P2 V1 N4 C15 178.2(2) . . . . ? N3 V1 N4 P2 54.56(10) . . . . ? O1 V1 N4 P2 153.42(8) . . . . ? N1 V1 N4 P2 -11.35(8) . . . . ? Cl1 V1 N4 P2 -110.56(7) . . . . ? P1 V1 N4 P2 25.82(7) . . . . ? P1 N1 C1 C2 62.5(2) . . . . ? P2 N1 C1 C2 179.49(15) . . . . ? V1 N1 C1 C2 -59.7(2) . . . . ? P1 N1 C1 C4 -178.20(15) . . . . ? P2 N1 C1 C4 -61.2(2) . . . . ? V1 N1 C1 C4 59.6(2) . . . . ? P1 N1 C1 C3 -57.6(2) . . . . ? P2 N1 C1 C3 59.4(2) . . . . ? V1 N1 C1 C3 -179.81(14) . . . . ? P2 N2 C5 C8 86.5(2) . . . . ? P1 N2 C5 C8 -80.3(2) . . . . ? P2 N2 C5 C6 -34.1(3) . . . . ? P1 N2 C5 C6 159.15(17) . . . . ? P2 N2 C5 C7 -152.28(17) . . . . ? P1 N2 C5 C7 41.0(3) . . . . ? P1 N3 C9 C14 22.4(3) . . . . ? V1 N3 C9 C14 -154.35(18) . . . . ? P1 N3 C9 C10 -156.36(17) . . . . ? V1 N3 C9 C10 26.9(3) . . . . ? C14 C9 C10 C11 0.9(3) . . . . ? N3 C9 C10 C11 179.7(2) . . . . ? C9 C10 C11 C12 -1.2(4) . . . . ? C10 C11 C12 C13 0.5(4) . . . . ? C11 C12 C13 C14 0.4(4) . . . . ? C12 C13 C14 C9 -0.7(4) . . . . ? C10 C9 C14 C13 0.1(4) . . . . ? N3 C9 C14 C13 -178.7(2) . . . . ? P2 N4 C15 C20 -30.9(3) . . . . ? V1 N4 C15 C20 151.14(18) . . . . ? P2 N4 C15 C16 148.16(16) . . . . ? V1 N4 C15 C16 -29.8(3) . . . . ? C20 C15 C16 C17 -0.1(3) . . . . ? N4 C15 C16 C17 -179.25(19) . . . . ? C15 C16 C17 C18 0.7(3) . . . . ? C16 C17 C18 C19 -0.8(4) . . . . ? C17 C18 C19 C20 0.4(4) . . . . ? C18 C19 C20 C15 0.2(4) . . . . ? C16 C15 C20 C19 -0.3(3) . . . . ? N4 C15 C20 C19 178.8(2) . . . . ? N3 V1 O1 C21 55.72(16) . . . . ? N4 V1 O1 C21 -54.59(16) . . . . ? N1 V1 O1 C21 -3.1(3) . . . . ? Cl1 V1 O1 C21 -178.08(15) . . . . ? P1 V1 O1 C21 35.61(17) . . . . ? P2 V1 O1 C21 -35.76(16) . . . . ? N3 V1 O1 C24 -126.46(19) . . . . ? N4 V1 O1 C24 123.23(19) . . . . ? N1 V1 O1 C24 174.7(2) . . . . ? Cl1 V1 O1 C24 -0.25(18) . . . . ? P1 V1 O1 C24 -146.57(17) . . . . ? P2 V1 O1 C24 142.06(17) . . . . ? C24 O1 C21 C22 -15.8(3) . . . . ? V1 O1 C21 C22 162.48(19) . . . . ? O1 C21 C22 C23 29.5(3) . . . . ? C21 C22 C23 C24 -32.1(4) . . . . ? C21 O1 C24 C23 -3.9(3) . . . . ? V1 O1 C24 C23 178.17(19) . . . . ? C22 C23 C24 O1 22.2(3) . . . . ? _diffrn_measured_fraction_theta_max 0.910 _diffrn_reflns_theta_full 27.58 _diffrn_measured_fraction_theta_full 0.910 _refine_diff_density_max 0.919 _refine_diff_density_min -0.448 _refine_diff_density_rms 0.052