Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is © The Royal Society of Chemistry 2005 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'R. S. Brown' 'Zhong-Lin Lu.' 'Alexei A. Neverov' _publ_contact_author_name 'R. S. Brown' _publ_contact_author_address ; Department of Chemistry Queens University Kingston Ontario K7l 3N6 CANADA ; _publ_contact_author_email RSBROWN@CHEM.QUEENSU.CA _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; An Ortho-palladated Dimethylbenzylamine Complex as a Highly Efficient Turnover Catalyst for the Decomposition of P=S Insecticides. Mechanistic Studies of the Methanolysis of Some P=S Containing Phosphorothioate Triesters. ; data_rs02 _database_code_depnum_ccdc_archive 'CCDC 278462' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C15 H17 F3 N2 O3 Pd S' _chemical_formula_weight 468.77 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Pd Pd -0.9988 1.0072 '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 9.1402(17) _cell_length_b 12.351(2) _cell_length_c 15.852(3) _cell_angle_alpha 90.00 _cell_angle_beta 97.942(3) _cell_angle_gamma 90.00 _cell_volume 1772.3(6) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.757 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 936 _exptl_absorpt_coefficient_mu 1.211 _exptl_absorpt_correction_type 'Empirical (Bruker SADABS)' _exptl_absorpt_correction_T_min 0.7016 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11759 _diffrn_reflns_av_R_equivalents 0.0290 _diffrn_reflns_av_sigmaI/netI 0.0361 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.10 _diffrn_reflns_theta_max 28.31 _reflns_number_total 4005 _reflns_number_gt 3183 _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^)+(0.0249P)^2^+1.5007P] 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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4005 _refine_ls_number_parameters 294 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0460 _refine_ls_R_factor_gt 0.0300 _refine_ls_wR_factor_ref 0.0649 _refine_ls_wR_factor_gt 0.0601 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.041 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Pd1 Pd 0.24597(2) 0.018714(17) 0.127092(14) 0.02290(7) Uani 1 1 d . . . S1 S 0.34574(8) 0.03478(6) 0.33274(5) 0.02778(16) Uani 1 1 d . . . O1 O 0.2252(2) 0.04632(17) 0.26279(12) 0.0296(5) Uani 1 1 d . . . O2 O 0.3681(3) 0.12943(19) 0.38474(16) 0.0516(7) Uani 1 1 d . . . O3 O 0.4753(2) -0.01499(19) 0.30944(15) 0.0422(6) Uani 1 1 d . . . F1 F 0.2353(3) -0.1543(2) 0.35742(18) 0.0839(9) Uani 1 1 d . . . F2 F 0.3726(3) -0.0921(2) 0.46491(15) 0.0684(7) Uani 1 1 d . . . F3 F 0.1569(3) -0.0282(2) 0.43178(17) 0.0865(9) Uani 1 1 d . . . N1 N 0.3154(3) 0.17465(19) 0.10415(15) 0.0274(5) Uani 1 1 d . . . N2 N 0.1811(2) -0.13744(19) 0.13956(15) 0.0234(5) Uani 1 1 d . . . C1 C 0.3315(3) 0.0835(2) -0.03019(18) 0.0251(6) Uani 1 1 d . . . C2 C 0.3439(3) 0.0836(3) -0.11636(19) 0.0300(7) Uani 1 1 d . . . H2 H 0.395(3) 0.139(2) -0.1414(19) 0.025(8) Uiso 1 1 d . . . C3 C 0.2799(3) 0.0011(3) -0.1686(2) 0.0319(7) Uani 1 1 d . . . H3 H 0.291(4) 0.000(3) -0.226(3) 0.056(11) Uiso 1 1 d . . . C4 C 0.2005(3) -0.0789(3) -0.1350(2) 0.0327(7) Uani 1 1 d . . . H4 H 0.154(3) -0.138(2) -0.1708(19) 0.028(8) Uiso 1 1 d . . . C5 C 0.1858(3) -0.0792(2) -0.04871(19) 0.0278(6) Uani 1 1 d . . . H5 H 0.135(3) -0.133(2) -0.0252(18) 0.024(8) Uiso 1 1 d . . . C6 C 0.2527(3) 0.0017(2) 0.00489(17) 0.0238(6) Uani 1 1 d . . . C7 C 0.4025(3) 0.1658(3) 0.0309(2) 0.0297(7) Uani 1 1 d . . . H7A H 0.503(3) 0.143(2) 0.0561(18) 0.024(8) Uiso 1 1 d . . . H7B H 0.406(3) 0.235(3) 0.0039(19) 0.029(8) Uiso 1 1 d . . . C8 C 0.1847(4) 0.2445(3) 0.0791(3) 0.0405(9) Uani 1 1 d . . . H8A H 0.130(4) 0.216(3) 0.034(2) 0.051(12) Uiso 1 1 d . . . H8B H 0.213(4) 0.316(3) 0.073(2) 0.043(10) Uiso 1 1 d . . . H8C H 0.121(4) 0.245(3) 0.125(2) 0.051(11) Uiso 1 1 d . . . C9 C 0.4091(4) 0.2245(3) 0.1770(2) 0.0391(8) Uani 1 1 d . . . H9A H 0.358(3) 0.235(2) 0.219(2) 0.026(8) Uiso 1 1 d . . . H9B H 0.442(3) 0.295(3) 0.1605(19) 0.032(9) Uiso 1 1 d . . . H9C H 0.491(4) 0.176(3) 0.197(2) 0.045(10) Uiso 1 1 d . . . C10 C 0.2718(3) -0.2212(3) 0.1329(2) 0.0331(7) Uani 1 1 d . . . H10 H 0.363(3) -0.210(2) 0.1205(18) 0.024(8) Uiso 1 1 d . . . C11 C 0.2290(4) -0.3268(3) 0.1386(2) 0.0357(7) Uani 1 1 d . . . H11 H 0.295(4) -0.379(3) 0.134(2) 0.047(11) Uiso 1 1 d . . . C12 C 0.0861(4) -0.3485(3) 0.1518(2) 0.0379(8) Uani 1 1 d . . . H12 H 0.054(4) -0.416(3) 0.155(2) 0.042(10) Uiso 1 1 d . . . C13 C -0.0077(4) -0.2633(3) 0.1588(2) 0.0404(8) Uani 1 1 d . . . H13 H -0.106(4) -0.278(3) 0.168(2) 0.052(11) Uiso 1 1 d . . . C14 C 0.0428(3) -0.1595(3) 0.1529(2) 0.0307(7) Uani 1 1 d . . . H14 H -0.016(3) -0.096(2) 0.1569(19) 0.028(8) Uiso 1 1 d . . . C15 C 0.2738(4) -0.0658(3) 0.4005(2) 0.0453(9) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Pd1 0.02615(11) 0.02187(11) 0.02080(11) 0.00076(10) 0.00369(8) -0.00468(9) S1 0.0330(4) 0.0246(4) 0.0255(4) 0.0003(3) 0.0033(3) 0.0047(3) O1 0.0324(10) 0.0342(12) 0.0217(11) -0.0007(8) 0.0022(8) 0.0027(9) O2 0.0741(18) 0.0369(14) 0.0382(14) -0.0123(11) -0.0119(13) 0.0091(12) O3 0.0347(11) 0.0455(14) 0.0487(14) 0.0091(11) 0.0145(10) 0.0109(10) F1 0.109(2) 0.0519(16) 0.089(2) 0.0208(14) 0.0048(17) -0.0321(15) F2 0.0638(14) 0.0910(19) 0.0504(14) 0.0416(13) 0.0082(12) 0.0224(13) F3 0.0624(15) 0.130(2) 0.0772(18) 0.0580(17) 0.0443(14) 0.0424(15) N1 0.0313(13) 0.0246(13) 0.0259(14) -0.0007(10) 0.0025(11) -0.0059(10) N2 0.0253(11) 0.0246(13) 0.0206(13) 0.0020(9) 0.0041(10) -0.0026(9) C1 0.0201(12) 0.0285(16) 0.0259(16) 0.0051(12) 0.0008(11) -0.0002(11) C2 0.0245(14) 0.0394(19) 0.0263(16) 0.0092(14) 0.0045(12) -0.0039(13) C3 0.0310(15) 0.041(2) 0.0242(16) -0.0005(13) 0.0067(12) 0.0058(13) C4 0.0354(15) 0.0343(18) 0.0274(17) -0.0052(14) 0.0012(13) 0.0029(14) C5 0.0283(14) 0.0258(16) 0.0294(16) 0.0027(13) 0.0044(12) -0.0024(12) C6 0.0241(13) 0.0256(16) 0.0223(14) 0.0020(11) 0.0056(11) 0.0005(11) C7 0.0316(16) 0.0309(17) 0.0262(17) 0.0050(13) 0.0021(13) -0.0075(13) C8 0.043(2) 0.026(2) 0.052(3) 0.0003(16) 0.0061(19) 0.0012(15) C9 0.052(2) 0.0317(19) 0.033(2) -0.0033(16) 0.0034(17) -0.0148(17) C10 0.0273(16) 0.0360(18) 0.038(2) 0.0044(15) 0.0099(14) -0.0011(13) C11 0.0454(19) 0.0285(18) 0.0331(19) 0.0050(14) 0.0053(15) 0.0052(15) C12 0.0445(19) 0.0273(18) 0.039(2) 0.0075(15) -0.0047(15) -0.0133(15) C13 0.0305(17) 0.039(2) 0.051(2) 0.0125(16) 0.0026(15) -0.0108(14) C14 0.0249(14) 0.0318(17) 0.0358(18) 0.0049(14) 0.0051(13) 0.0009(13) C15 0.0434(19) 0.055(2) 0.040(2) 0.0202(18) 0.0130(17) 0.0105(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 Pd1 C6 1.958(3) . ? Pd1 N2 2.035(2) . ? Pd1 N1 2.075(2) . ? Pd1 O1 2.212(2) . ? S1 O3 1.427(2) . ? S1 O2 1.429(2) . ? S1 O1 1.458(2) . ? S1 C15 1.823(4) . ? F1 C15 1.311(5) . ? F2 C15 1.307(4) . ? F3 C15 1.323(4) . ? N1 C9 1.474(4) . ? N1 C8 1.482(4) . ? N1 C7 1.500(4) . ? N2 C14 1.338(3) . ? N2 C10 1.339(4) . ? C1 C2 1.386(4) . ? C1 C6 1.400(4) . ? C1 C7 1.490(4) . ? C2 C3 1.390(4) . ? C3 C4 1.376(4) . ? C4 C5 1.394(4) . ? C5 C6 1.396(4) . ? C10 C11 1.368(5) . ? C11 C12 1.377(5) . ? C12 C13 1.371(5) . ? C13 C14 1.370(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 C6 Pd1 N2 92.50(10) . . ? C6 Pd1 N1 82.78(10) . . ? N2 Pd1 N1 175.20(9) . . ? C6 Pd1 O1 175.89(9) . . ? N2 Pd1 O1 89.22(8) . . ? N1 Pd1 O1 95.55(9) . . ? O3 S1 O2 116.36(16) . . ? O3 S1 O1 114.34(13) . . ? O2 S1 O1 113.05(14) . . ? O3 S1 C15 103.79(15) . . ? O2 S1 C15 104.61(18) . . ? O1 S1 C15 102.62(15) . . ? S1 O1 Pd1 124.55(11) . . ? C9 N1 C8 109.1(3) . . ? C9 N1 C7 108.9(2) . . ? C8 N1 C7 109.2(3) . . ? C9 N1 Pd1 114.1(2) . . ? C8 N1 Pd1 109.44(19) . . ? C7 N1 Pd1 106.02(18) . . ? C14 N2 C10 117.6(3) . . ? C14 N2 Pd1 120.2(2) . . ? C10 N2 Pd1 122.19(19) . . ? C2 C1 C6 120.6(3) . . ? C2 C1 C7 123.5(3) . . ? C6 C1 C7 115.9(3) . . ? C1 C2 C3 120.1(3) . . ? C4 C3 C2 119.8(3) . . ? C3 C4 C5 120.6(3) . . ? C4 C5 C6 120.2(3) . . ? C5 C6 C1 118.7(3) . . ? C5 C6 Pd1 127.4(2) . . ? C1 C6 Pd1 113.8(2) . . ? C1 C7 N1 108.8(2) . . ? N2 C10 C11 123.0(3) . . ? C10 C11 C12 118.8(3) . . ? C13 C12 C11 118.6(3) . . ? C14 C13 C12 119.5(3) . . ? N2 C14 C13 122.4(3) . . ? F2 C15 F1 107.9(3) . . ? F2 C15 F3 107.5(3) . . ? F1 C15 F3 108.4(3) . . ? F2 C15 S1 111.3(3) . . ? F1 C15 S1 110.8(3) . . ? F3 C15 S1 110.9(3) . . ? 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 O3 S1 O1 Pd1 -10.7(2) . . . . ? O2 S1 O1 Pd1 125.55(17) . . . . ? C15 S1 O1 Pd1 -122.36(17) . . . . ? C6 Pd1 O1 S1 -152.4(13) . . . . ? N2 Pd1 O1 S1 92.84(16) . . . . ? N1 Pd1 O1 S1 -86.65(16) . . . . ? C6 Pd1 N1 C9 -149.1(2) . . . . ? N2 Pd1 N1 C9 -139.3(11) . . . . ? O1 Pd1 N1 C9 34.7(2) . . . . ? C6 Pd1 N1 C8 88.4(2) . . . . ? N2 Pd1 N1 C8 98.2(11) . . . . ? O1 Pd1 N1 C8 -87.8(2) . . . . ? C6 Pd1 N1 C7 -29.28(18) . . . . ? N2 Pd1 N1 C7 -19.4(12) . . . . ? O1 Pd1 N1 C7 154.50(18) . . . . ? C6 Pd1 N2 C14 -108.4(2) . . . . ? N1 Pd1 N2 C14 -118.2(11) . . . . ? O1 Pd1 N2 C14 67.9(2) . . . . ? C6 Pd1 N2 C10 70.0(2) . . . . ? N1 Pd1 N2 C10 60.2(12) . . . . ? O1 Pd1 N2 C10 -113.7(2) . . . . ? C6 C1 C2 C3 -1.1(4) . . . . ? C7 C1 C2 C3 177.1(3) . . . . ? C1 C2 C3 C4 1.9(4) . . . . ? C2 C3 C4 C5 -1.1(5) . . . . ? C3 C4 C5 C6 -0.6(5) . . . . ? C4 C5 C6 C1 1.4(4) . . . . ? C4 C5 C6 Pd1 179.4(2) . . . . ? C2 C1 C6 C5 -0.6(4) . . . . ? C7 C1 C6 C5 -178.9(3) . . . . ? C2 C1 C6 Pd1 -178.9(2) . . . . ? C7 C1 C6 Pd1 2.8(3) . . . . ? N2 Pd1 C6 C5 18.1(3) . . . . ? N1 Pd1 C6 C5 -162.7(3) . . . . ? O1 Pd1 C6 C5 -96.5(13) . . . . ? N2 Pd1 C6 C1 -163.8(2) . . . . ? N1 Pd1 C6 C1 15.4(2) . . . . ? O1 Pd1 C6 C1 81.6(14) . . . . ? C2 C1 C7 N1 153.9(3) . . . . ? C6 C1 C7 N1 -27.8(4) . . . . ? C9 N1 C7 C1 160.4(3) . . . . ? C8 N1 C7 C1 -80.6(3) . . . . ? Pd1 N1 C7 C1 37.2(3) . . . . ? C14 N2 C10 C11 0.4(5) . . . . ? Pd1 N2 C10 C11 -178.1(3) . . . . ? N2 C10 C11 C12 0.0(5) . . . . ? C10 C11 C12 C13 -0.1(5) . . . . ? C11 C12 C13 C14 -0.3(5) . . . . ? C10 N2 C14 C13 -0.8(5) . . . . ? Pd1 N2 C14 C13 177.7(3) . . . . ? C12 C13 C14 N2 0.7(5) . . . . ? O3 S1 C15 F2 56.5(3) . . . . ? O2 S1 C15 F2 -65.9(3) . . . . ? O1 S1 C15 F2 175.8(3) . . . . ? O3 S1 C15 F1 -63.5(3) . . . . ? O2 S1 C15 F1 174.1(3) . . . . ? O1 S1 C15 F1 55.8(3) . . . . ? O3 S1 C15 F3 176.1(3) . . . . ? O2 S1 C15 F3 53.7(3) . . . . ? O1 S1 C15 F3 -64.6(3) . . . . ? _diffrn_measured_fraction_theta_max 0.907 _diffrn_reflns_theta_full 28.31 _diffrn_measured_fraction_theta_full 0.907 _refine_diff_density_max 0.685 _refine_diff_density_min -0.645 _refine_diff_density_rms 0.082 data_rs01 _database_code_depnum_ccdc_archive 'CCDC 278463' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C14 H17 Cl N2 Pd' _chemical_formula_weight 355.15 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pbca loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 9.5463(18) _cell_length_b 16.258(4) _cell_length_c 18.117(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2811.7(11) _cell_formula_units_Z 8 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour colorless _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.2 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.678 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1424 _exptl_absorpt_coefficient_mu 1.493 _exptl_absorpt_correction_type 'Empirical (Bruker SADABS)' _exptl_absorpt_correction_T_min 0.7774 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 18463 _diffrn_reflns_av_R_equivalents 0.0478 _diffrn_reflns_av_sigmaI/netI 0.0506 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.25 _diffrn_reflns_theta_max 28.28 _reflns_number_total 3377 _reflns_number_gt 2284 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _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^)+(0.0300P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3377 _refine_ls_number_parameters 231 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0577 _refine_ls_R_factor_gt 0.0329 _refine_ls_wR_factor_ref 0.0641 _refine_ls_wR_factor_gt 0.0595 _refine_ls_goodness_of_fit_ref 0.928 _refine_ls_restrained_S_all 0.928 _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 Pd1 Pd 0.90179(2) 0.052354(14) 0.265092(12) 0.02178(8) Uani 1 1 d . . . Cl1 Cl 0.95113(8) 0.14703(5) 0.36567(4) 0.03289(19) Uani 1 1 d . . . N1 N 0.9308(2) 0.14033(16) 0.18296(13) 0.0233(6) Uani 1 1 d . . . N2 N 0.8744(2) -0.04002(15) 0.34015(13) 0.0240(6) Uani 1 1 d . . . C1 C 0.8524(3) 0.0223(2) 0.11163(17) 0.0253(7) Uani 1 1 d . . . C2 C 0.8359(3) -0.0191(2) 0.0458(2) 0.0313(8) Uani 1 1 d . . . H2 H 0.822(2) 0.0051(17) 0.0031(15) 0.010(7) Uiso 1 1 d . . . C3 C 0.8383(3) -0.1046(2) 0.04329(19) 0.0352(8) Uani 1 1 d . . . H3 H 0.818(3) -0.133(2) -0.0009(17) 0.035(9) Uiso 1 1 d . . . C4 C 0.8598(3) -0.1478(2) 0.10834(19) 0.0315(8) Uani 1 1 d . . . H4 H 0.862(3) -0.200(2) 0.1053(17) 0.031(10) Uiso 1 1 d . . . C5 C 0.8764(3) -0.1059(2) 0.17496(19) 0.0287(8) Uani 1 1 d . . . H5 H 0.892(3) -0.138(2) 0.2165(17) 0.029(9) Uiso 1 1 d . . . C6 C 0.8723(3) -0.0202(2) 0.17816(17) 0.0242(7) Uani 1 1 d . . . C7 C 0.8476(3) 0.1133(2) 0.11724(18) 0.0279(7) Uani 1 1 d . . . H7A H 0.750(3) 0.1312(16) 0.1241(13) 0.014(7) Uiso 1 1 d . . . H7B H 0.886(3) 0.142(2) 0.0744(17) 0.033(9) Uiso 1 1 d . . . C8 C 0.8927(4) 0.2259(2) 0.2025(2) 0.0351(8) Uani 1 1 d . . . H8A H 0.797(3) 0.226(2) 0.2169(16) 0.035(9) Uiso 1 1 d . . . H8B H 0.907(3) 0.266(2) 0.156(2) 0.047(10) Uiso 1 1 d . . . H8C H 0.946(4) 0.243(3) 0.239(2) 0.051(12) Uiso 1 1 d . . . C9 C 1.0828(3) 0.1386(2) 0.1644(2) 0.0319(8) Uani 1 1 d . . . H9A H 1.139(3) 0.150(2) 0.2047(18) 0.032(9) Uiso 1 1 d . . . H9B H 1.108(3) 0.088(2) 0.1467(17) 0.029(9) Uiso 1 1 d . . . H9C H 1.105(3) 0.185(2) 0.1268(18) 0.033(9) Uiso 1 1 d . . . C10 C 0.7574(3) -0.0876(2) 0.34170(17) 0.0277(7) Uani 1 1 d . . . H10 H 0.689(3) -0.0741(16) 0.3032(14) 0.014(7) Uiso 1 1 d . . . C11 C 0.7390(4) -0.1483(2) 0.39351(19) 0.0335(8) Uani 1 1 d . . . H11 H 0.660(3) -0.174(2) 0.3911(16) 0.029(9) Uiso 1 1 d . . . C12 C 0.8411(4) -0.1610(2) 0.44595(19) 0.0348(9) Uani 1 1 d . . . H12 H 0.832(3) -0.196(2) 0.4783(18) 0.033(10) Uiso 1 1 d . . . C13 C 0.9592(4) -0.1131(2) 0.44506(18) 0.0329(8) Uani 1 1 d . . . H13 H 1.022(3) -0.1198(18) 0.4774(16) 0.023(8) Uiso 1 1 d . . . C14 C 0.9726(3) -0.0539(2) 0.39180(18) 0.0296(7) Uani 1 1 d . . . H14 H 1.053(3) -0.0175(18) 0.3898(16) 0.025(8) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Pd1 0.02154(11) 0.02083(13) 0.02296(13) 0.00306(10) -0.00172(10) -0.00061(10) Cl1 0.0402(4) 0.0279(5) 0.0306(5) -0.0025(4) -0.0073(3) -0.0011(4) N1 0.0223(13) 0.0224(15) 0.0252(15) 0.0024(11) -0.0010(10) -0.0012(10) N2 0.0291(13) 0.0212(15) 0.0216(14) -0.0009(11) -0.0008(10) -0.0005(11) C1 0.0209(14) 0.0279(19) 0.0270(19) 0.0045(14) 0.0006(12) -0.0031(12) C2 0.0340(18) 0.036(2) 0.024(2) 0.0064(16) -0.0010(15) -0.0021(15) C3 0.0379(19) 0.044(3) 0.024(2) -0.0063(17) 0.0044(16) -0.0052(16) C4 0.0362(18) 0.020(2) 0.038(2) -0.0050(16) 0.0075(14) -0.0011(15) C5 0.0278(17) 0.030(2) 0.029(2) 0.0055(15) 0.0017(14) -0.0019(14) C6 0.0187(15) 0.0290(18) 0.0249(18) -0.0003(13) 0.0001(12) -0.0004(12) C7 0.0281(16) 0.028(2) 0.027(2) 0.0057(15) -0.0032(14) -0.0010(14) C8 0.045(2) 0.024(2) 0.037(2) 0.0039(16) 0.0018(19) 0.0000(17) C9 0.0269(17) 0.034(2) 0.035(2) 0.0026(17) 0.0009(15) -0.0045(15) C10 0.0287(16) 0.0299(19) 0.0243(17) -0.0007(15) 0.0001(14) -0.0018(14) C11 0.0356(19) 0.028(2) 0.037(2) 0.0004(16) 0.0111(16) -0.0043(16) C12 0.054(2) 0.023(2) 0.027(2) 0.0072(16) 0.0152(17) 0.0082(17) C13 0.0403(19) 0.034(2) 0.024(2) 0.0046(16) -0.0051(16) 0.0100(17) C14 0.0298(16) 0.0301(19) 0.0288(18) 0.0010(16) -0.0030(13) 0.0023(16) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Pd1 C6 1.987(3) . ? Pd1 N2 2.043(2) . ? Pd1 N1 2.082(2) . ? Pd1 Cl1 2.4312(9) . ? N1 C8 1.480(4) . ? N1 C9 1.490(4) . ? N1 C7 1.497(4) . ? N2 C14 1.344(4) . ? N2 C10 1.359(4) . ? C1 C2 1.378(5) . ? C1 C6 1.402(4) . ? C1 C7 1.484(5) . ? C2 C3 1.391(5) . ? C3 C4 1.388(5) . ? C4 C5 1.395(5) . ? C5 C6 1.395(5) . ? C10 C11 1.373(4) . ? C11 C12 1.377(5) . ? C12 C13 1.370(5) . ? C13 C14 1.368(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 C6 Pd1 N2 94.20(12) . . ? C6 Pd1 N1 81.95(12) . . ? N2 Pd1 N1 176.05(10) . . ? C6 Pd1 Cl1 175.51(9) . . ? N2 Pd1 Cl1 89.51(7) . . ? N1 Pd1 Cl1 94.30(7) . . ? C8 N1 C9 108.1(3) . . ? C8 N1 C7 109.6(3) . . ? C9 N1 C7 109.4(3) . . ? C8 N1 Pd1 116.2(2) . . ? C9 N1 Pd1 106.10(19) . . ? C7 N1 Pd1 107.24(18) . . ? C14 N2 C10 117.6(3) . . ? C14 N2 Pd1 119.9(2) . . ? C10 N2 Pd1 122.5(2) . . ? C2 C1 C6 121.3(3) . . ? C2 C1 C7 122.8(3) . . ? C6 C1 C7 115.9(3) . . ? C1 C2 C3 120.9(3) . . ? C4 C3 C2 118.8(3) . . ? C3 C4 C5 120.2(4) . . ? C6 C5 C4 121.4(3) . . ? C5 C6 C1 117.4(3) . . ? C5 C6 Pd1 128.4(2) . . ? C1 C6 Pd1 114.1(2) . . ? C1 C7 N1 109.3(3) . . ? N2 C10 C11 121.9(3) . . ? C10 C11 C12 119.3(3) . . ? C13 C12 C11 119.2(3) . . ? C14 C13 C12 119.0(3) . . ? N2 C14 C13 123.0(3) . . ? 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 C6 Pd1 N1 C8 150.6(2) . . . . ? N2 Pd1 N1 C8 163.7(12) . . . . ? Cl1 Pd1 N1 C8 -31.9(2) . . . . ? C6 Pd1 N1 C9 -89.2(2) . . . . ? N2 Pd1 N1 C9 -76.1(13) . . . . ? Cl1 Pd1 N1 C9 88.3(2) . . . . ? C6 Pd1 N1 C7 27.60(19) . . . . ? N2 Pd1 N1 C7 40.7(13) . . . . ? Cl1 Pd1 N1 C7 -154.89(18) . . . . ? C6 Pd1 N2 C14 126.5(2) . . . . ? N1 Pd1 N2 C14 113.5(12) . . . . ? Cl1 Pd1 N2 C14 -51.0(2) . . . . ? C6 Pd1 N2 C10 -55.4(3) . . . . ? N1 Pd1 N2 C10 -68.5(13) . . . . ? Cl1 Pd1 N2 C10 127.1(2) . . . . ? C6 C1 C2 C3 0.1(5) . . . . ? C7 C1 C2 C3 -178.6(3) . . . . ? C1 C2 C3 C4 -1.0(5) . . . . ? C2 C3 C4 C5 1.0(5) . . . . ? C3 C4 C5 C6 -0.1(5) . . . . ? C4 C5 C6 C1 -0.8(4) . . . . ? C4 C5 C6 Pd1 -176.9(2) . . . . ? C2 C1 C6 C5 0.8(4) . . . . ? C7 C1 C6 C5 179.6(2) . . . . ? C2 C1 C6 Pd1 177.5(2) . . . . ? C7 C1 C6 Pd1 -3.7(3) . . . . ? N2 Pd1 C6 C5 -16.7(3) . . . . ? N1 Pd1 C6 C5 162.4(3) . . . . ? Cl1 Pd1 C6 C5 128.9(10) . . . . ? N2 Pd1 C6 C1 167.0(2) . . . . ? N1 Pd1 C6 C1 -13.9(2) . . . . ? Cl1 Pd1 C6 C1 -47.4(12) . . . . ? C2 C1 C7 N1 -154.0(3) . . . . ? C6 C1 C7 N1 27.2(4) . . . . ? C8 N1 C7 C1 -162.9(3) . . . . ? C9 N1 C7 C1 78.7(3) . . . . ? Pd1 N1 C7 C1 -35.9(3) . . . . ? C14 N2 C10 C11 -0.4(5) . . . . ? Pd1 N2 C10 C11 -178.5(2) . . . . ? N2 C10 C11 C12 0.6(5) . . . . ? C10 C11 C12 C13 -0.3(5) . . . . ? C11 C12 C13 C14 -0.3(5) . . . . ? C10 N2 C14 C13 -0.2(5) . . . . ? Pd1 N2 C14 C13 178.0(3) . . . . ? C12 C13 C14 N2 0.5(5) . . . . ? _diffrn_measured_fraction_theta_max 0.967 _diffrn_reflns_theta_full 28.28 _diffrn_measured_fraction_theta_full 0.967 _refine_diff_density_max 0.984 _refine_diff_density_min -0.630 _refine_diff_density_rms 0.111