# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Oznur Dogan' _publ_contact_author_email IOZDEMIR@INONU.EDU.TR _publ_section_title ; Synthesis, characterization and catalytic activity of novel N-heterocyclic carbene-palladium complexes ; loop_ _publ_author_name O.Dogan O.Buyukgungorc 'Bekir Cetinkaya' N.Gurbuz I.Ozdemir 'Onur Sahin' # Attachment '2d_CCDC.cif' data_2d _database_code_depnum_ccdc_archive 'CCDC 716524' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C60 H56 Br2 N4 O6 Pd, 2(C H Cl3)' _chemical_formula_sum 'C62 H58 Br2 Cl6 N4 O6 Pd' _chemical_formula_weight 1434.04 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 '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 triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.692(5) _cell_length_b 12.829(6) _cell_length_c 13.904(5) _cell_angle_alpha 65.559(5) _cell_angle_beta 88.175(5) _cell_angle_gamma 67.876(4) _cell_volume 1591.0(11) _cell_formula_units_Z 1 _cell_measurement_temperature 296 _cell_measurement_reflns_used 36044 _cell_measurement_theta_min 1.89 _cell_measurement_theta_max 28.01 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.44 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.497 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 724 _exptl_absorpt_coefficient_mu 1.851 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.3726 _exptl_absorpt_correction_T_max 0.7022 _exptl_absorpt_process_details '(X-RED32; Stoe & Cie, 2002)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 296 _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'STOE IPDS 2' _diffrn_measurement_method 'w scan rotation' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2 _diffrn_reflns_number 36044 _diffrn_reflns_av_R_equivalents 0.0496 _diffrn_reflns_av_sigmaI/netI 0.0289 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.89 _diffrn_reflns_theta_max 26.50 _reflns_number_total 6603 _reflns_number_gt 5446 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'X-AREA (Stoe & Cie, 2002)' _computing_cell_refinement 'X-AREA (Stoe & Cie, 2002)' _computing_data_reduction 'X-RED (Stoe & Cie, 2002)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX (Farrugia, 1998)' _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^)+(0.0430P)^2^+0.4530P] 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 6603 _refine_ls_number_parameters 370 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0468 _refine_ls_R_factor_gt 0.0350 _refine_ls_wR_factor_ref 0.0843 _refine_ls_wR_factor_gt 0.0801 _refine_ls_goodness_of_fit_ref 1.045 _refine_ls_restrained_S_all 1.045 _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 C1 C 0.2975(2) 0.5575(2) 0.50652(18) 0.0386(5) Uani 1 1 d . . . C2 C 0.0977(3) 0.5632(3) 0.5663(2) 0.0433(6) Uani 1 1 d . . . C3 C -0.0035(3) 0.5354(3) 0.6235(2) 0.0549(7) Uani 1 1 d . . . H3 H 0.0163 0.4601 0.6835 0.066 Uiso 1 1 calc R . . C4 C -0.1351(3) 0.6255(4) 0.5865(3) 0.0634(8) Uani 1 1 d . . . H4 H -0.2060 0.6104 0.6220 0.076 Uiso 1 1 calc R . . C5 C -0.1633(3) 0.7373(4) 0.4980(3) 0.0634(8) Uani 1 1 d . . . H5 H -0.2532 0.7956 0.4758 0.076 Uiso 1 1 calc R . . C6 C -0.0629(3) 0.7661(3) 0.4410(2) 0.0538(7) Uani 1 1 d . . . H6 H -0.0831 0.8421 0.3816 0.065 Uiso 1 1 calc R . . C7 C 0.0699(3) 0.6752(3) 0.4774(2) 0.0433(6) Uani 1 1 d . . . C8 C 0.2234(3) 0.7616(2) 0.3482(2) 0.0449(6) Uani 1 1 d . . . H8 H 0.3206 0.7426 0.3622 0.054 Uiso 1 1 calc R . . C9 C 0.1484(3) 0.8934(3) 0.3382(2) 0.0524(7) Uani 1 1 d . . . C10 C 0.1697(4) 0.9167(4) 0.4232(3) 0.0730(9) Uani 1 1 d . . . H10 H 0.2239 0.8511 0.4861 0.088 Uiso 1 1 calc R . . C11 C 0.1116(5) 1.0363(5) 0.4162(4) 0.0988(14) Uani 1 1 d . . . H11 H 0.1274 1.0507 0.4740 0.119 Uiso 1 1 calc R . . C12 C 0.0318(6) 1.1324(4) 0.3254(5) 0.1102(17) Uani 1 1 d . . . H12 H -0.0069 1.2130 0.3204 0.132 Uiso 1 1 calc R . . C13 C 0.0086(6) 1.1105(4) 0.2418(4) 0.1130(17) Uani 1 1 d . . . H13 H -0.0467 1.1765 0.1796 0.136 Uiso 1 1 calc R . . C14 C 0.0661(4) 0.9911(3) 0.2476(3) 0.0806(11) Uani 1 1 d . . . H14 H 0.0487 0.9775 0.1896 0.097 Uiso 1 1 calc R . . C15 C 0.2070(3) 0.7442(3) 0.2485(2) 0.0482(6) Uani 1 1 d . . . C16 C 0.0921(4) 0.7360(4) 0.2157(3) 0.0748(10) Uani 1 1 d . . . H16 H 0.0198 0.7425 0.2550 0.090 Uiso 1 1 calc R . . C17 C 0.0829(5) 0.7181(5) 0.1250(3) 0.0923(13) Uani 1 1 d . . . H17 H 0.0051 0.7122 0.1039 0.111 Uiso 1 1 calc R . . C18 C 0.1882(5) 0.7092(5) 0.0665(3) 0.0953(13) Uani 1 1 d . . . H18 H 0.1824 0.6968 0.0057 0.114 Uiso 1 1 calc R . . C19 C 0.3021(4) 0.7183(5) 0.0972(3) 0.0927(13) Uani 1 1 d . . . H19 H 0.3733 0.7134 0.0568 0.111 Uiso 1 1 calc R . . C20 C 0.3118(3) 0.7349(4) 0.1884(3) 0.0694(9) Uani 1 1 d . . . H20 H 0.3903 0.7398 0.2093 0.083 Uiso 1 1 calc R . . C21 C 0.3080(3) 0.3682(2) 0.6653(2) 0.0472(6) Uani 1 1 d . . . H21A H 0.4020 0.3352 0.6537 0.057 Uiso 1 1 calc R . . H21B H 0.2657 0.3150 0.6611 0.057 Uiso 1 1 calc R . . C22 C 0.3060(3) 0.3634(2) 0.7757(2) 0.0452(6) Uani 1 1 d . . . C23 C 0.2958(3) 0.2609(3) 0.8587(2) 0.0546(7) Uani 1 1 d . . . H23 H 0.2870 0.1982 0.8459 0.066 Uiso 1 1 calc R . . C24 C 0.2987(4) 0.2528(3) 0.9613(2) 0.0613(8) Uani 1 1 d . . . C25 C 0.3100(3) 0.3464(3) 0.9804(2) 0.0579(7) Uani 1 1 d . . . C26 C 0.3227(3) 0.4475(3) 0.8975(2) 0.0538(7) Uani 1 1 d . . . C27 C 0.3203(3) 0.4560(3) 0.7941(2) 0.0503(6) Uani 1 1 d . . . H27 H 0.3283 0.5240 0.7380 0.060 Uiso 1 1 calc R . . C28 C 0.2936(6) 0.0511(4) 1.0385(3) 0.1026(15) Uani 1 1 d . . . H28A H 0.2141 0.0740 0.9917 0.154 Uiso 1 1 calc R . . H28B H 0.2955 -0.0123 1.1073 0.154 Uiso 1 1 calc R . . H28C H 0.3741 0.0196 1.0092 0.154 Uiso 1 1 calc R . . C29 C 0.1916(6) 0.3873(6) 1.1153(4) 0.132(2) Uani 1 1 d . . . H29A H 0.1402 0.4701 1.0610 0.198 Uiso 1 1 calc R . . H29B H 0.2072 0.3910 1.1811 0.198 Uiso 1 1 calc R . . H29C H 0.1413 0.3364 1.1250 0.198 Uiso 1 1 calc R . . C30 C 0.3833(5) 0.6205(4) 0.8493(3) 0.0837(12) Uani 1 1 d . . . H30A H 0.4657 0.5774 0.8281 0.126 Uiso 1 1 calc R . . H30B H 0.4007 0.6682 0.8813 0.126 Uiso 1 1 calc R . . H30C H 0.3143 0.6755 0.7878 0.126 Uiso 1 1 calc R . . C31 C 0.4928(5) 0.9288(4) 0.7387(3) 0.0876(12) Uani 1 1 d . . . H31 H 0.5712 0.8658 0.7937 0.105 Uiso 1 1 calc R . . N1 N 0.2372(2) 0.4938(2) 0.58088(16) 0.0405(4) Uani 1 1 d . . . N2 N 0.1962(2) 0.6685(2) 0.44224(16) 0.0407(4) Uani 1 1 d . . . O1 O 0.2894(4) 0.1565(2) 1.04935(18) 0.0923(9) Uani 1 1 d . . . O2 O 0.3191(3) 0.3346(3) 1.08341(17) 0.0830(8) Uani 1 1 d . . . O3 O 0.3380(3) 0.5329(2) 0.92406(18) 0.0781(7) Uani 1 1 d . . . Cl1 Cl 0.52262(15) 1.06390(12) 0.67198(13) 0.1193(4) Uani 1 1 d . . . Cl2 Cl 0.4731(2) 0.87166(17) 0.65135(12) 0.1604(8) Uani 1 1 d . . . Cl3 Cl 0.3469(2) 0.96196(16) 0.80025(14) 0.1394(6) Uani 1 1 d . . . Br1 Br 0.48994(3) 0.36644(3) 0.42071(3) 0.05767(10) Uani 1 1 d . . . Pd1 Pd 0.5000 0.5000 0.5000 0.03641(8) Uani 1 2 d S . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0427(13) 0.0449(13) 0.0376(12) -0.0230(10) 0.0109(10) -0.0218(11) C2 0.0431(13) 0.0596(15) 0.0427(13) -0.0305(12) 0.0144(10) -0.0278(12) C3 0.0556(17) 0.079(2) 0.0499(15) -0.0346(15) 0.0219(13) -0.0405(15) C4 0.0480(17) 0.102(3) 0.0659(19) -0.050(2) 0.0247(14) -0.0421(17) C5 0.0396(15) 0.093(2) 0.072(2) -0.051(2) 0.0140(14) -0.0241(15) C6 0.0452(15) 0.0647(18) 0.0554(16) -0.0328(14) 0.0091(12) -0.0184(13) C7 0.0408(13) 0.0589(15) 0.0446(13) -0.0315(12) 0.0133(10) -0.0249(12) C8 0.0464(14) 0.0505(14) 0.0430(13) -0.0205(11) 0.0127(11) -0.0249(12) C9 0.0552(17) 0.0494(15) 0.0579(16) -0.0248(13) 0.0162(13) -0.0252(13) C10 0.082(2) 0.070(2) 0.077(2) -0.0436(19) 0.0116(18) -0.0282(19) C11 0.120(4) 0.089(3) 0.121(4) -0.073(3) 0.032(3) -0.046(3) C12 0.141(5) 0.065(3) 0.130(4) -0.054(3) 0.043(4) -0.035(3) C13 0.146(5) 0.054(2) 0.096(3) -0.019(2) 0.009(3) -0.010(2) C14 0.102(3) 0.0541(19) 0.067(2) -0.0212(17) 0.007(2) -0.0168(19) C15 0.0546(16) 0.0465(14) 0.0400(13) -0.0171(11) 0.0105(11) -0.0188(12) C16 0.081(2) 0.113(3) 0.066(2) -0.055(2) 0.0295(18) -0.058(2) C17 0.101(3) 0.137(4) 0.077(3) -0.067(3) 0.022(2) -0.064(3) C18 0.113(4) 0.122(4) 0.060(2) -0.056(2) 0.020(2) -0.039(3) C19 0.079(3) 0.134(4) 0.059(2) -0.053(2) 0.0257(19) -0.025(3) C20 0.0571(19) 0.092(2) 0.0511(17) -0.0305(17) 0.0134(14) -0.0229(17) C21 0.0574(16) 0.0476(14) 0.0421(13) -0.0200(11) 0.0135(12) -0.0265(13) C22 0.0491(15) 0.0491(14) 0.0414(13) -0.0198(11) 0.0115(11) -0.0238(12) C23 0.0710(19) 0.0532(16) 0.0477(15) -0.0192(13) 0.0151(13) -0.0365(15) C24 0.082(2) 0.0604(18) 0.0417(15) -0.0142(13) 0.0169(14) -0.0384(17) C25 0.077(2) 0.0605(17) 0.0387(14) -0.0204(13) 0.0138(13) -0.0318(16) C26 0.0694(19) 0.0573(16) 0.0453(14) -0.0260(13) 0.0153(13) -0.0324(15) C27 0.0660(18) 0.0505(15) 0.0408(13) -0.0184(12) 0.0156(12) -0.0321(14) C28 0.170(5) 0.080(3) 0.072(2) -0.019(2) 0.032(3) -0.081(3) C29 0.172(6) 0.138(5) 0.079(3) -0.063(3) 0.056(3) -0.041(4) C30 0.137(4) 0.084(2) 0.068(2) -0.044(2) 0.032(2) -0.072(3) C31 0.123(4) 0.065(2) 0.067(2) -0.0285(18) 0.001(2) -0.028(2) N1 0.0427(11) 0.0497(12) 0.0372(10) -0.0215(9) 0.0125(8) -0.0243(10) N2 0.0396(11) 0.0481(11) 0.0391(10) -0.0212(9) 0.0116(8) -0.0204(9) O1 0.164(3) 0.0773(17) 0.0490(12) -0.0173(12) 0.0323(15) -0.0748(19) O2 0.131(2) 0.0882(17) 0.0378(11) -0.0261(11) 0.0189(13) -0.0534(17) O3 0.135(2) 0.0820(16) 0.0537(12) -0.0416(12) 0.0333(14) -0.0685(17) Cl1 0.1150(10) 0.0906(8) 0.1520(12) -0.0395(8) 0.0065(8) -0.0541(7) Cl2 0.300(3) 0.1416(13) 0.0997(9) -0.0758(10) 0.0446(12) -0.1248(16) Cl3 0.1746(15) 0.1306(12) 0.1377(12) -0.0685(10) 0.0647(11) -0.0778(11) Br1 0.05644(19) 0.0746(2) 0.0711(2) -0.05088(18) 0.01987(15) -0.03501(16) Pd1 0.03682(15) 0.04408(15) 0.03561(14) -0.02076(11) 0.01108(10) -0.02010(12) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 N1 1.345(3) . ? C1 N2 1.359(3) . ? C1 Pd1 2.020(3) . ? C2 C7 1.382(4) . ? C2 N1 1.388(3) . ? C2 C3 1.390(4) . ? C3 C4 1.381(4) . ? C3 H3 0.9300 . ? C4 C5 1.378(5) . ? C4 H4 0.9300 . ? C5 C6 1.385(4) . ? C5 H5 0.9300 . ? C6 C7 1.394(4) . ? C6 H6 0.9300 . ? C7 N2 1.405(3) . ? C8 N2 1.472(3) . ? C8 C15 1.517(4) . ? C8 C9 1.520(4) . ? C8 H8 0.9800 . ? C9 C14 1.366(5) . ? C9 C10 1.378(4) . ? C10 C11 1.383(5) . ? C10 H10 0.9300 . ? C11 C12 1.353(7) . ? C11 H11 0.9300 . ? C12 C13 1.353(7) . ? C12 H12 0.9300 . ? C13 C14 1.387(6) . ? C13 H13 0.9300 . ? C14 H14 0.9300 . ? C15 C20 1.375(4) . ? C15 C16 1.379(4) . ? C16 C17 1.385(5) . ? C16 H16 0.9300 . ? C17 C18 1.365(6) . ? C17 H17 0.9300 . ? C18 C19 1.365(6) . ? C18 H18 0.9300 . ? C19 C20 1.382(5) . ? C19 H19 0.9300 . ? C20 H20 0.9300 . ? C21 N1 1.455(3) . ? C21 C22 1.510(4) . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C22 C27 1.376(4) . ? C22 C23 1.385(4) . ? C23 C24 1.387(4) . ? C23 H23 0.9300 . ? C24 O1 1.368(4) . ? C24 C25 1.378(5) . ? C25 O2 1.380(3) . ? C25 C26 1.384(4) . ? C26 O3 1.355(4) . ? C26 C27 1.396(4) . ? C27 H27 0.9300 . ? C28 O1 1.404(5) . ? C28 H28A 0.9600 . ? C28 H28B 0.9600 . ? C28 H28C 0.9600 . ? C29 O2 1.424(6) . ? C29 H29A 0.9600 . ? C29 H29B 0.9600 . ? C29 H29C 0.9600 . ? C30 O3 1.410(4) . ? C30 H30A 0.9600 . ? C30 H30B 0.9600 . ? C30 H30C 0.9600 . ? C31 Cl2 1.711(4) . ? C31 Cl1 1.741(4) . ? C31 Cl3 1.750(5) . ? C31 H31 0.9800 . ? Br1 Pd1 2.4232(7) . ? Pd1 C1 2.020(3) 2_666 ? Pd1 Br1 2.4232(7) 2_666 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 N2 106.2(2) . . ? N1 C1 Pd1 125.72(18) . . ? N2 C1 Pd1 128.03(17) . . ? C7 C2 N1 106.7(2) . . ? C7 C2 C3 122.3(3) . . ? N1 C2 C3 130.9(3) . . ? C4 C3 C2 116.5(3) . . ? C4 C3 H3 121.7 . . ? C2 C3 H3 121.7 . . ? C5 C4 C3 121.4(3) . . ? C5 C4 H4 119.3 . . ? C3 C4 H4 119.3 . . ? C4 C5 C6 122.5(3) . . ? C4 C5 H5 118.7 . . ? C6 C5 H5 118.7 . . ? C5 C6 C7 116.4(3) . . ? C5 C6 H6 121.8 . . ? C7 C6 H6 121.8 . . ? C2 C7 C6 120.9(2) . . ? C2 C7 N2 105.7(2) . . ? C6 C7 N2 133.5(3) . . ? N2 C8 C15 111.6(2) . . ? N2 C8 C9 112.0(2) . . ? C15 C8 C9 115.9(2) . . ? N2 C8 H8 105.4 . . ? C15 C8 H8 105.4 . . ? C9 C8 H8 105.4 . . ? C14 C9 C10 118.3(3) . . ? C14 C9 C8 123.4(3) . . ? C10 C9 C8 118.2(3) . . ? C9 C10 C11 120.9(4) . . ? C9 C10 H10 119.6 . . ? C11 C10 H10 119.6 . . ? C12 C11 C10 120.1(4) . . ? C12 C11 H11 119.9 . . ? C10 C11 H11 119.9 . . ? C11 C12 C13 119.6(4) . . ? C11 C12 H12 120.2 . . ? C13 C12 H12 120.2 . . ? C12 C13 C14 121.0(5) . . ? C12 C13 H13 119.5 . . ? C14 C13 H13 119.5 . . ? C9 C14 C13 120.1(4) . . ? C9 C14 H14 119.9 . . ? C13 C14 H14 119.9 . . ? C20 C15 C16 118.2(3) . . ? C20 C15 C8 118.8(3) . . ? C16 C15 C8 123.1(3) . . ? C15 C16 C17 120.9(3) . . ? C15 C16 H16 119.6 . . ? C17 C16 H16 119.6 . . ? C18 C17 C16 119.9(4) . . ? C18 C17 H17 120.0 . . ? C16 C17 H17 120.0 . . ? C19 C18 C17 120.0(4) . . ? C19 C18 H18 120.0 . . ? C17 C18 H18 120.0 . . ? C18 C19 C20 120.1(4) . . ? C18 C19 H19 120.0 . . ? C20 C19 H19 120.0 . . ? C15 C20 C19 121.0(4) . . ? C15 C20 H20 119.5 . . ? C19 C20 H20 119.5 . . ? N1 C21 C22 113.1(2) . . ? N1 C21 H21A 109.0 . . ? C22 C21 H21A 109.0 . . ? N1 C21 H21B 109.0 . . ? C22 C21 H21B 109.0 . . ? H21A C21 H21B 107.8 . . ? C27 C22 C23 120.7(3) . . ? C27 C22 C21 120.7(2) . . ? C23 C22 C21 118.5(2) . . ? C22 C23 C24 119.3(3) . . ? C22 C23 H23 120.3 . . ? C24 C23 H23 120.3 . . ? O1 C24 C25 115.0(3) . . ? O1 C24 C23 124.5(3) . . ? C25 C24 C23 120.5(3) . . ? C24 C25 O2 120.0(3) . . ? C24 C25 C26 120.0(3) . . ? O2 C25 C26 119.8(3) . . ? O3 C26 C25 116.1(2) . . ? O3 C26 C27 124.1(3) . . ? C25 C26 C27 119.8(3) . . ? C22 C27 C26 119.7(3) . . ? C22 C27 H27 120.2 . . ? C26 C27 H27 120.2 . . ? O1 C28 H28A 109.5 . . ? O1 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? O1 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? O2 C29 H29A 109.5 . . ? O2 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? O2 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? O3 C30 H30A 109.5 . . ? O3 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? O3 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? Cl2 C31 Cl1 110.3(2) . . ? Cl2 C31 Cl3 110.4(3) . . ? Cl1 C31 Cl3 109.5(2) . . ? Cl2 C31 H31 108.9 . . ? Cl1 C31 H31 108.9 . . ? Cl3 C31 H31 108.9 . . ? C1 N1 C2 111.1(2) . . ? C1 N1 C21 124.7(2) . . ? C2 N1 C21 124.2(2) . . ? C1 N2 C7 110.4(2) . . ? C1 N2 C8 121.6(2) . . ? C7 N2 C8 128.0(2) . . ? C24 O1 C28 118.2(3) . . ? C25 O2 C29 114.5(3) . . ? C26 O3 C30 118.0(2) . . ? C1 Pd1 C1 180.00(14) . 2_666 ? C1 Pd1 Br1 88.97(7) . 2_666 ? C1 Pd1 Br1 91.03(7) 2_666 2_666 ? C1 Pd1 Br1 91.03(7) . . ? C1 Pd1 Br1 88.97(7) 2_666 . ? Br1 Pd1 Br1 180.0 2_666 . ? 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 C7 C2 C3 C4 0.5(4) . . . . ? N1 C2 C3 C4 -178.9(3) . . . . ? C2 C3 C4 C5 -0.6(4) . . . . ? C3 C4 C5 C6 0.2(5) . . . . ? C4 C5 C6 C7 0.4(4) . . . . ? N1 C2 C7 C6 179.6(2) . . . . ? C3 C2 C7 C6 0.0(4) . . . . ? N1 C2 C7 N2 -0.4(3) . . . . ? C3 C2 C7 N2 180.0(2) . . . . ? C5 C6 C7 C2 -0.4(4) . . . . ? C5 C6 C7 N2 179.6(3) . . . . ? N2 C8 C9 C14 -127.1(3) . . . . ? C15 C8 C9 C14 2.5(4) . . . . ? N2 C8 C9 C10 56.1(4) . . . . ? C15 C8 C9 C10 -174.2(3) . . . . ? C14 C9 C10 C11 -1.3(6) . . . . ? C8 C9 C10 C11 175.6(3) . . . . ? C9 C10 C11 C12 0.5(7) . . . . ? C10 C11 C12 C13 0.4(8) . . . . ? C11 C12 C13 C14 -0.4(9) . . . . ? C10 C9 C14 C13 1.3(6) . . . . ? C8 C9 C14 C13 -175.5(4) . . . . ? C12 C13 C14 C9 -0.5(8) . . . . ? N2 C8 C15 C20 -127.6(3) . . . . ? C9 C8 C15 C20 102.5(3) . . . . ? N2 C8 C15 C16 51.7(4) . . . . ? C9 C8 C15 C16 -78.2(4) . . . . ? C20 C15 C16 C17 0.3(6) . . . . ? C8 C15 C16 C17 -179.0(4) . . . . ? C15 C16 C17 C18 -0.4(7) . . . . ? C16 C17 C18 C19 -0.3(8) . . . . ? C17 C18 C19 C20 0.9(8) . . . . ? C16 C15 C20 C19 0.3(5) . . . . ? C8 C15 C20 C19 179.6(3) . . . . ? C18 C19 C20 C15 -0.9(7) . . . . ? N1 C21 C22 C27 -38.8(4) . . . . ? N1 C21 C22 C23 144.1(3) . . . . ? C27 C22 C23 C24 0.6(5) . . . . ? C21 C22 C23 C24 177.7(3) . . . . ? C22 C23 C24 O1 180.0(3) . . . . ? C22 C23 C24 C25 0.8(5) . . . . ? O1 C24 C25 O2 3.7(5) . . . . ? C23 C24 C25 O2 -177.0(3) . . . . ? O1 C24 C25 C26 178.8(3) . . . . ? C23 C24 C25 C26 -2.0(5) . . . . ? C24 C25 C26 O3 -177.8(3) . . . . ? O2 C25 C26 O3 -2.7(5) . . . . ? C24 C25 C26 C27 1.7(5) . . . . ? O2 C25 C26 C27 176.8(3) . . . . ? C23 C22 C27 C26 -0.8(4) . . . . ? C21 C22 C27 C26 -177.9(3) . . . . ? O3 C26 C27 C22 179.1(3) . . . . ? C25 C26 C27 C22 -0.4(5) . . . . ? N2 C1 N1 C2 -0.8(3) . . . . ? Pd1 C1 N1 C2 175.99(16) . . . . ? N2 C1 N1 C21 178.8(2) . . . . ? Pd1 C1 N1 C21 -4.4(3) . . . . ? C7 C2 N1 C1 0.8(3) . . . . ? C3 C2 N1 C1 -179.7(3) . . . . ? C7 C2 N1 C21 -178.8(2) . . . . ? C3 C2 N1 C21 0.7(4) . . . . ? C22 C21 N1 C1 114.6(3) . . . . ? C22 C21 N1 C2 -65.8(3) . . . . ? N1 C1 N2 C7 0.5(3) . . . . ? Pd1 C1 N2 C7 -176.18(17) . . . . ? N1 C1 N2 C8 -177.4(2) . . . . ? Pd1 C1 N2 C8 5.9(3) . . . . ? C2 C7 N2 C1 0.0(3) . . . . ? C6 C7 N2 C1 180.0(3) . . . . ? C2 C7 N2 C8 177.8(2) . . . . ? C6 C7 N2 C8 -2.2(4) . . . . ? C15 C8 N2 C1 91.0(3) . . . . ? C9 C8 N2 C1 -137.1(2) . . . . ? C15 C8 N2 C7 -86.6(3) . . . . ? C9 C8 N2 C7 45.3(3) . . . . ? C25 C24 O1 C28 -172.7(4) . . . . ? C23 C24 O1 C28 8.1(6) . . . . ? C24 C25 O2 C29 -92.1(5) . . . . ? C26 C25 O2 C29 92.8(5) . . . . ? C25 C26 O3 C30 165.2(3) . . . . ? C27 C26 O3 C30 -14.3(5) . . . . ? N1 C1 Pd1 Br1 -100.3(2) . . . 2_666 ? N2 C1 Pd1 Br1 75.8(2) . . . 2_666 ? N1 C1 Pd1 Br1 79.7(2) . . . . ? N2 C1 Pd1 Br1 -104.2(2) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A C31 H31 O1 0.98 2.54 3.340(5) 139.1 2_667 C31 H31 O2 0.98 2.26 3.141(5) 148.4 2_667 _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 26.50 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.515 _refine_diff_density_min -0.563 _refine_diff_density_rms 0.050 # Attachment '2b_CCDC.cif' data_2b _database_code_depnum_ccdc_archive 'CCDC 716525' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C48 H48 Br2 N4 O2 Pd' _chemical_formula_sum 'C48 H48 Br2 N4 O2 Pd' _chemical_formula_weight 979.12 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' Br Br -0.2901 2.4595 '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 triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.9725(3) _cell_length_b 10.4541(4) _cell_length_c 12.0262(4) _cell_angle_alpha 81.773(3) _cell_angle_beta 86.671(3) _cell_angle_gamma 85.751(4) _cell_volume 1112.08(7) _cell_formula_units_Z 1 _cell_measurement_temperature 296 _cell_measurement_reflns_used 36722 _cell_measurement_theta_min 1.97 _cell_measurement_theta_max 28.02 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.44 _exptl_crystal_size_mid 0.29 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.462 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 496 _exptl_absorpt_coefficient_mu 2.256 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.4215 _exptl_absorpt_correction_T_max 0.6602 _exptl_absorpt_process_details '(X-RED32; Stoe & Cie, 2002)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 296 _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 'STOE IPDS 2' _diffrn_measurement_method 'w scan rotation' _diffrn_detector_area_resol_mean 6.67 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% <2 _diffrn_reflns_number 28000 _diffrn_reflns_av_R_equivalents 0.0684 _diffrn_reflns_av_sigmaI/netI 0.0360 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.97 _diffrn_reflns_theta_max 27.55 _reflns_number_total 5130 _reflns_number_gt 4487 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'X-AREA (Stoe & Cie, 2002)' _computing_cell_refinement 'X-AREA (Stoe & Cie, 2002)' _computing_data_reduction 'X-RED (Stoe & Cie, 2002)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX (Farrugia, 1998)' _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^)+(0.0501P)^2^+0.3601P] 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 5130 _refine_ls_number_parameters 269 _refine_ls_number_restraints 38 _refine_ls_R_factor_all 0.0450 _refine_ls_R_factor_gt 0.0381 _refine_ls_wR_factor_ref 0.0982 _refine_ls_wR_factor_gt 0.0947 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.059 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.4607(3) 0.6928(2) 0.4582(2) 0.0418(5) Uani 1 1 d . B . C2 C 0.3575(3) 0.8946(3) 0.4658(2) 0.0476(6) Uani 1 1 d . B . C3 C 0.2807(4) 1.0047(3) 0.4983(3) 0.0602(7) Uani 1 1 d . . . H3 H 0.2335 1.0043 0.5693 0.072 Uiso 1 1 calc R . . C4 C 0.2785(4) 1.1139(3) 0.4200(3) 0.0694(9) Uani 1 1 d . . . H4 H 0.2280 1.1897 0.4382 0.083 Uiso 1 1 calc R . . C5 C 0.3493(4) 1.1144(3) 0.3147(3) 0.0690(9) Uani 1 1 d . . . H5 H 0.3453 1.1906 0.2642 0.083 Uiso 1 1 calc R . . C6 C 0.4261(3) 1.0044(3) 0.2821(3) 0.0567(7) Uani 1 1 d . . . H6 H 0.4731 1.0052 0.2110 0.068 Uiso 1 1 calc R . . C7 C 0.4293(3) 0.8932(2) 0.3606(2) 0.0455(5) Uani 1 1 d . B . C8 C 0.5892(3) 0.7184(3) 0.2682(2) 0.0475(6) Uani 1 1 d . B . H8 H 0.6173 0.6274 0.2956 0.057 Uiso 1 1 calc R . . C9 C 0.5061(4) 0.7181(3) 0.1616(2) 0.0566(7) Uani 1 1 d . . . C10 C 0.3560(4) 0.7459(4) 0.1551(3) 0.0663(8) Uani 1 1 d . . . H10 H 0.3001 0.7702 0.2172 0.080 Uiso 1 1 calc R . . C11 C 0.2855(5) 0.7384(5) 0.0571(4) 0.0866(12) Uani 1 1 d . . . H11 H 0.1832 0.7597 0.0536 0.104 Uiso 1 1 calc R . . C12 C 0.3636(6) 0.7002(6) -0.0345(4) 0.1067(17) Uani 1 1 d . . . H12 H 0.3154 0.6947 -0.0999 0.128 Uiso 1 1 calc R . . C13 C 0.5135(6) 0.6703(7) -0.0283(4) 0.126(2) Uani 1 1 d . . . H13 H 0.5679 0.6435 -0.0900 0.151 Uiso 1 1 calc R . . C14 C 0.5859(5) 0.6793(6) 0.0682(3) 0.0992(16) Uani 1 1 d . . . H14 H 0.6885 0.6593 0.0708 0.119 Uiso 1 1 calc R . . C15 C 0.7348(3) 0.7878(3) 0.2538(3) 0.0549(7) Uani 1 1 d . . . C16 C 0.7579(4) 0.8938(4) 0.1740(4) 0.0827(12) Uani 1 1 d . . . H16 H 0.6853 0.9231 0.1224 0.099 Uiso 1 1 calc R . . C17 C 0.8902(5) 0.9572(5) 0.1703(5) 0.1057(17) Uani 1 1 d . . . H17 H 0.9049 1.0293 0.1169 0.127 Uiso 1 1 calc R . . C18 C 0.9976(5) 0.9138(5) 0.2446(5) 0.1018(16) Uani 1 1 d . . . H18 H 1.0850 0.9570 0.2421 0.122 Uiso 1 1 calc R . . C19 C 0.9783(4) 0.8086(5) 0.3219(4) 0.0887(13) Uani 1 1 d . . . H19 H 1.0530 0.7786 0.3715 0.106 Uiso 1 1 calc R . . C20 C 0.8468(3) 0.7448(4) 0.3276(3) 0.0665(8) Uani 1 1 d . . . H20 H 0.8339 0.6727 0.3814 0.080 Uiso 1 1 calc R . . C21 C 0.3264(3) 0.7294(3) 0.6382(2) 0.0566(7) Uani 1 1 d . B . H21A H 0.3321 0.7999 0.6818 0.068 Uiso 1 1 calc R . . H21B H 0.3910 0.6570 0.6711 0.068 Uiso 1 1 calc R . . C22 C 0.1689(4) 0.6901(5) 0.6450(3) 0.0862(13) Uani 1 1 d . . . H22A H 0.1062 0.7540 0.5993 0.103 Uiso 1 1 calc R A 1 H22B H 0.1650 0.6071 0.6185 0.103 Uiso 1 1 calc R A 1 N1 N 0.3798(2) 0.7703(2) 0.52261(18) 0.0459(5) Uani 1 1 d . . . N2 N 0.4926(2) 0.7673(2) 0.35864(17) 0.0420(4) Uani 1 1 d . . . Br1 Br 0.71247(4) 0.52592(3) 0.60779(3) 0.07548(13) Uani 1 1 d . B . Pd1 Pd 0.5000 0.5000 0.5000 0.04090(9) Uani 1 2 d S . . C23A C -0.0165(13) 0.6311(13) 0.7776(9) 0.1082(16) Uani 0.504(7) 1 d PDU B 1 H23A H -0.0246 0.5680 0.7268 0.130 Uiso 0.504(7) 1 calc PR B 1 H23B H -0.0931 0.7003 0.7595 0.130 Uiso 0.504(7) 1 calc PR B 1 C24A C -0.0475(13) 0.5705(12) 0.8894(9) 0.1082(16) Uani 0.504(7) 1 d PDU B 1 H24A H -0.1464 0.5401 0.8955 0.162 Uiso 0.504(7) 1 calc PR B 1 H24B H -0.0409 0.6318 0.9409 0.162 Uiso 0.504(7) 1 calc PR B 1 H24C H 0.0241 0.4986 0.9073 0.162 Uiso 0.504(7) 1 calc PR B 1 O1A O 0.1207(6) 0.6818(6) 0.7572(4) 0.0667(14) Uani 0.504(7) 1 d PU B 1 C23B C 0.0176(13) 0.5637(12) 0.7902(10) 0.1082(16) Uani 0.496(7) 1 d PDU B 2 H23C H 0.0284 0.4775 0.8323 0.130 Uiso 0.496(7) 1 calc PR B 2 H23D H -0.0380 0.5592 0.7242 0.130 Uiso 0.496(7) 1 calc PR B 2 C24B C -0.0681(12) 0.6576(12) 0.8642(10) 0.1082(16) Uani 0.496(7) 1 d PDU B 2 H24D H -0.1651 0.6271 0.8869 0.162 Uiso 0.496(7) 1 calc PR B 2 H24E H -0.0794 0.7425 0.8218 0.162 Uiso 0.496(7) 1 calc PR B 2 H24F H -0.0130 0.6612 0.9296 0.162 Uiso 0.496(7) 1 calc PR B 2 O1B O 0.1582(7) 0.6085(7) 0.7576(5) 0.0784(17) Uani 0.496(7) 1 d PU 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 C1 0.0449(12) 0.0385(12) 0.0422(12) -0.0029(9) -0.0087(10) -0.0042(10) C2 0.0477(13) 0.0426(13) 0.0537(14) -0.0081(11) -0.0097(11) -0.0023(11) C3 0.0583(16) 0.0546(17) 0.0708(19) -0.0200(14) -0.0092(14) 0.0034(13) C4 0.0677(19) 0.0453(16) 0.097(3) -0.0170(16) -0.0145(18) 0.0086(14) C5 0.073(2) 0.0399(15) 0.092(2) 0.0036(15) -0.0187(18) 0.0000(14) C6 0.0584(16) 0.0456(15) 0.0630(17) 0.0059(12) -0.0082(13) -0.0049(12) C7 0.0463(13) 0.0386(13) 0.0517(13) -0.0034(10) -0.0103(11) -0.0025(10) C8 0.0484(14) 0.0463(14) 0.0465(13) -0.0042(10) -0.0023(11) 0.0008(11) C9 0.0595(16) 0.0652(18) 0.0452(14) -0.0050(12) -0.0040(12) -0.0082(14) C10 0.0639(18) 0.080(2) 0.0567(17) -0.0108(15) -0.0122(14) -0.0063(16) C11 0.084(3) 0.106(3) 0.073(2) -0.013(2) -0.029(2) -0.008(2) C12 0.113(4) 0.158(5) 0.055(2) -0.014(3) -0.026(2) -0.028(3) C13 0.111(4) 0.220(7) 0.057(2) -0.051(3) 0.004(2) -0.022(4) C14 0.076(2) 0.166(5) 0.061(2) -0.037(3) 0.0019(19) -0.003(3) C15 0.0464(14) 0.0569(17) 0.0600(16) -0.0071(13) 0.0012(12) 0.0006(12) C16 0.0533(18) 0.082(3) 0.102(3) 0.020(2) 0.0044(18) -0.0044(17) C17 0.066(2) 0.084(3) 0.156(5) 0.017(3) 0.022(3) -0.015(2) C18 0.052(2) 0.103(4) 0.153(5) -0.026(3) 0.008(3) -0.016(2) C19 0.0476(18) 0.119(4) 0.103(3) -0.029(3) -0.0102(19) -0.001(2) C20 0.0505(16) 0.082(2) 0.0672(19) -0.0129(16) -0.0072(14) 0.0040(15) C21 0.0630(17) 0.0659(18) 0.0416(13) -0.0069(12) -0.0027(12) -0.0110(14) C22 0.073(2) 0.137(4) 0.0523(17) -0.012(2) -0.0009(16) -0.038(2) N1 0.0518(12) 0.0431(11) 0.0428(11) -0.0049(8) -0.0053(9) -0.0033(9) N2 0.0459(11) 0.0370(10) 0.0419(10) -0.0012(8) -0.0057(8) -0.0014(8) Br1 0.0835(3) 0.0536(2) 0.0922(3) 0.00247(17) -0.0487(2) -0.01299(17) Pd1 0.04860(16) 0.03520(14) 0.03851(14) -0.00036(9) -0.00970(10) -0.00359(10) C23A 0.1075(17) 0.1088(17) 0.1083(17) -0.0145(6) -0.0048(5) -0.0079(5) C24A 0.1075(17) 0.1088(17) 0.1083(17) -0.0145(6) -0.0048(5) -0.0079(5) O1A 0.0661(16) 0.0686(17) 0.0653(16) -0.0078(9) -0.0003(9) -0.0082(10) C23B 0.1075(17) 0.1088(17) 0.1083(17) -0.0145(6) -0.0048(5) -0.0079(5) C24B 0.1075(17) 0.1088(17) 0.1083(17) -0.0145(6) -0.0048(5) -0.0079(5) O1B 0.0769(18) 0.0811(19) 0.0768(18) -0.0091(10) -0.0023(10) -0.0085(10) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 N1 1.345(3) . ? C1 N2 1.359(3) . ? C1 Pd1 2.016(2) . ? C2 N1 1.385(3) . ? C2 C7 1.387(4) . ? C2 C3 1.390(4) . ? C3 C4 1.372(5) . ? C3 H3 0.9300 . ? C4 C5 1.383(5) . ? C4 H4 0.9300 . ? C5 C6 1.390(5) . ? C5 H5 0.9300 . ? C6 C7 1.389(4) . ? C6 H6 0.9300 . ? C7 N2 1.396(3) . ? C8 N2 1.477(3) . ? C8 C9 1.520(4) . ? C8 C15 1.530(4) . ? C8 H8 0.9800 . ? C9 C10 1.361(5) . ? C9 C14 1.391(5) . ? C10 C11 1.385(5) . ? C10 H10 0.9300 . ? C11 C12 1.362(6) . ? C11 H11 0.9300 . ? C12 C13 1.362(7) . ? C12 H12 0.9300 . ? C13 C14 1.381(6) . ? C13 H13 0.9300 . ? C14 H14 0.9300 . ? C15 C16 1.377(5) . ? C15 C20 1.387(5) . ? C16 C17 1.397(6) . ? C16 H16 0.9300 . ? C17 C18 1.361(7) . ? C17 H17 0.9300 . ? C18 C19 1.350(7) . ? C18 H18 0.9300 . ? C19 C20 1.391(5) . ? C19 H19 0.9300 . ? C20 H20 0.9300 . ? C21 N1 1.459(3) . ? C21 C22 1.494(4) . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C22 O1A 1.385(6) . ? C22 O1B 1.496(7) . ? C22 H22A 0.9700 . ? C22 H22B 0.9700 . ? Br1 Pd1 2.4191(3) . ? Pd1 C1 2.016(2) 2_666 ? Pd1 Br1 2.4191(3) 2_666 ? C23A O1A 1.372(12) . ? C23A C24A 1.424(13) . ? C23A H23A 0.9700 . ? C23A H23B 0.9700 . ? C24A H24A 0.9600 . ? C24A H24B 0.9600 . ? C24A H24C 0.9600 . ? C23B O1B 1.393(12) . ? C23B C24B 1.550(13) . ? C23B H23C 0.9700 . ? C23B H23D 0.9700 . ? C24B H24D 0.9600 . ? C24B H24E 0.9600 . ? C24B H24F 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 N2 106.5(2) . . ? N1 C1 Pd1 124.58(18) . . ? N2 C1 Pd1 128.56(18) . . ? N1 C2 C7 106.1(2) . . ? N1 C2 C3 131.1(3) . . ? C7 C2 C3 122.8(3) . . ? C4 C3 C2 116.3(3) . . ? C4 C3 H3 121.9 . . ? C2 C3 H3 121.9 . . ? C3 C4 C5 121.8(3) . . ? C3 C4 H4 119.1 . . ? C5 C4 H4 119.1 . . ? C4 C5 C6 122.0(3) . . ? C4 C5 H5 119.0 . . ? C6 C5 H5 119.0 . . ? C7 C6 C5 116.8(3) . . ? C7 C6 H6 121.6 . . ? C5 C6 H6 121.6 . . ? C2 C7 C6 120.3(3) . . ? C2 C7 N2 106.4(2) . . ? C6 C7 N2 133.3(3) . . ? N2 C8 C9 112.4(2) . . ? N2 C8 C15 109.5(2) . . ? C9 C8 C15 115.9(2) . . ? N2 C8 H8 106.1 . . ? C9 C8 H8 106.1 . . ? C15 C8 H8 106.1 . . ? C10 C9 C14 118.3(3) . . ? C10 C9 C8 123.4(3) . . ? C14 C9 C8 118.2(3) . . ? C9 C10 C11 120.7(4) . . ? C9 C10 H10 119.7 . . ? C11 C10 H10 119.7 . . ? C12 C11 C10 121.1(4) . . ? C12 C11 H11 119.5 . . ? C10 C11 H11 119.5 . . ? C11 C12 C13 118.7(4) . . ? C11 C12 H12 120.6 . . ? C13 C12 H12 120.6 . . ? C12 C13 C14 121.0(4) . . ? C12 C13 H13 119.5 . . ? C14 C13 H13 119.5 . . ? C13 C14 C9 120.3(4) . . ? C13 C14 H14 119.9 . . ? C9 C14 H14 119.9 . . ? C16 C15 C20 118.4(3) . . ? C16 C15 C8 123.3(3) . . ? C20 C15 C8 118.2(3) . . ? C15 C16 C17 120.1(4) . . ? C15 C16 H16 119.9 . . ? C17 C16 H16 119.9 . . ? C18 C17 C16 120.3(4) . . ? C18 C17 H17 119.9 . . ? C16 C17 H17 119.9 . . ? C19 C18 C17 120.5(4) . . ? C19 C18 H18 119.8 . . ? C17 C18 H18 119.8 . . ? C18 C19 C20 120.1(4) . . ? C18 C19 H19 119.9 . . ? C20 C19 H19 119.9 . . ? C15 C20 C19 120.6(4) . . ? C15 C20 H20 119.7 . . ? C19 C20 H20 119.7 . . ? N1 C21 C22 112.2(3) . . ? N1 C21 H21A 109.2 . . ? C22 C21 H21A 109.2 . . ? N1 C21 H21B 109.2 . . ? C22 C21 H21B 109.2 . . ? H21A C21 H21B 107.9 . . ? O1A C22 C21 106.4(3) . . ? C21 C22 O1B 102.6(4) . . ? O1A C22 H22A 110.4 . . ? C21 C22 H22A 110.4 . . ? O1B C22 H22A 137.8 . . ? O1A C22 H22B 110.4 . . ? C21 C22 H22B 110.4 . . ? O1B C22 H22B 82.4 . . ? H22A C22 H22B 108.6 . . ? C1 N1 C2 111.1(2) . . ? C1 N1 C21 124.3(2) . . ? C2 N1 C21 124.6(2) . . ? C1 N2 C7 109.9(2) . . ? C1 N2 C8 122.5(2) . . ? C7 N2 C8 127.5(2) . . ? C1 Pd1 C1 180.000(1) 2_666 . ? C1 Pd1 Br1 87.31(7) 2_666 . ? C1 Pd1 Br1 92.69(7) . . ? C1 Pd1 Br1 92.69(7) 2_666 2_666 ? C1 Pd1 Br1 87.31(7) . 2_666 ? Br1 Pd1 Br1 180.0 . 2_666 ? O1A C23A C24A 115.9(10) . . ? O1A C23A H23A 108.3 . . ? C24A C23A H23A 108.3 . . ? O1A C23A H23B 108.3 . . ? C24A C23A H23B 108.3 . . ? H23A C23A H23B 107.4 . . ? C23A C24A H24A 109.5 . . ? C23A C24A H24B 109.5 . . ? H24A C24A H24B 109.5 . . ? C23A C24A H24C 109.5 . . ? H24A C24A H24C 109.5 . . ? H24B C24A H24C 109.5 . . ? C23A O1A C22 112.5(6) . . ? O1B C23B C24B 109.1(9) . . ? O1B C23B H23C 109.9 . . ? C24B C23B H23C 109.9 . . ? O1B C23B H23D 109.9 . . ? C24B C23B H23D 109.9 . . ? H23C C23B H23D 108.3 . . ? C23B C24B H24D 109.5 . . ? C23B C24B H24E 109.5 . . ? H24D C24B H24E 109.5 . . ? C23B C24B H24F 109.5 . . ? H24D C24B H24F 109.5 . . ? H24E C24B H24F 109.5 . . ? C23B O1B C22 115.4(7) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N1 C2 C3 C4 -179.2(3) . . . . ? C7 C2 C3 C4 0.3(5) . . . . ? C2 C3 C4 C5 -0.3(5) . . . . ? C3 C4 C5 C6 0.3(6) . . . . ? C4 C5 C6 C7 -0.3(5) . . . . ? N1 C2 C7 C6 179.2(2) . . . . ? C3 C2 C7 C6 -0.4(4) . . . . ? N1 C2 C7 N2 -0.1(3) . . . . ? C3 C2 C7 N2 -179.8(3) . . . . ? C5 C6 C7 C2 0.4(4) . . . . ? C5 C6 C7 N2 179.5(3) . . . . ? N2 C8 C9 C10 -7.0(4) . . . . ? C15 C8 C9 C10 -134.0(3) . . . . ? N2 C8 C9 C14 177.4(3) . . . . ? C15 C8 C9 C14 50.4(5) . . . . ? C14 C9 C10 C11 -1.4(6) . . . . ? C8 C9 C10 C11 -177.0(3) . . . . ? C9 C10 C11 C12 1.5(7) . . . . ? C10 C11 C12 C13 -0.5(9) . . . . ? C11 C12 C13 C14 -0.5(10) . . . . ? C12 C13 C14 C9 0.6(10) . . . . ? C10 C9 C14 C13 0.4(8) . . . . ? C8 C9 C14 C13 176.2(5) . . . . ? N2 C8 C15 C16 -96.5(4) . . . . ? C9 C8 C15 C16 31.8(5) . . . . ? N2 C8 C15 C20 80.9(3) . . . . ? C9 C8 C15 C20 -150.7(3) . . . . ? C20 C15 C16 C17 -1.5(6) . . . . ? C8 C15 C16 C17 176.0(4) . . . . ? C15 C16 C17 C18 0.8(8) . . . . ? C16 C17 C18 C19 0.6(8) . . . . ? C17 C18 C19 C20 -1.2(8) . . . . ? C16 C15 C20 C19 0.9(6) . . . . ? C8 C15 C20 C19 -176.7(3) . . . . ? C18 C19 C20 C15 0.4(6) . . . . ? N1 C21 C22 O1A -167.0(4) . . . . ? N1 C21 C22 O1B 159.6(4) . . . . ? N2 C1 N1 C2 0.5(3) . . . . ? Pd1 C1 N1 C2 -172.78(18) . . . . ? N2 C1 N1 C21 -177.9(2) . . . . ? Pd1 C1 N1 C21 8.8(4) . . . . ? C7 C2 N1 C1 -0.2(3) . . . . ? C3 C2 N1 C1 179.4(3) . . . . ? C7 C2 N1 C21 178.2(2) . . . . ? C3 C2 N1 C21 -2.2(5) . . . . ? C22 C21 N1 C1 -96.1(4) . . . . ? C22 C21 N1 C2 85.7(4) . . . . ? N1 C1 N2 C7 -0.6(3) . . . . ? Pd1 C1 N2 C7 172.33(18) . . . . ? N1 C1 N2 C8 175.7(2) . . . . ? Pd1 C1 N2 C8 -11.4(3) . . . . ? C2 C7 N2 C1 0.4(3) . . . . ? C6 C7 N2 C1 -178.8(3) . . . . ? C2 C7 N2 C8 -175.6(2) . . . . ? C6 C7 N2 C8 5.2(5) . . . . ? C9 C8 N2 C1 117.4(3) . . . . ? C15 C8 N2 C1 -112.3(3) . . . . ? C9 C8 N2 C7 -67.0(3) . . . . ? C15 C8 N2 C7 63.3(3) . . . . ? N1 C1 Pd1 Br1 -84.9(2) . . . . ? N2 C1 Pd1 Br1 103.4(2) . . . . ? N1 C1 Pd1 Br1 95.1(2) . . . 2_666 ? N2 C1 Pd1 Br1 -76.6(2) . . . 2_666 ? C24A C23A O1A C22 155.2(11) . . . . ? C21 C22 O1A C23A -172.5(7) . . . . ? O1B C22 O1A C23A -84.8(8) . . . . ? C24B C23B O1B C22 -95.0(11) . . . . ? O1A C22 O1B C23B 75.5(8) . . . . ? C21 C22 O1B C23B 176.3(6) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.55 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.576 _refine_diff_density_min -0.675 _refine_diff_density_rms 0.065