# Electronic Supplementary Material (ESI) for Catalysis Science & Technology # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full Cat.Sci.Tech. _journal_coden_cambridge 1486 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_address ;Inorganic & Physical Chemistry Division Indian Institute of Chemical Technology Hyderabad - 500 607 India ; ;Inorganic & Physical Chemistry Division Indian Institute of Chemical Technology Hyderabad - 500 607 India ; ;Inorganic & Physical Chemistry Division Indian Institute of Chemical Technology Hyderabad - 500 607 India ; ;Inorganic & Physical Chemistry Division Indian Institute of Chemical Technology Hyderabad - 500 607 India ; ;Laboratory of X-ray Crystallography Indian Institute of Chemical Technology Hyderabad - 500 607 India ; ;Inorganic & Physical Chemistry Division Indian Institute of Chemical Technology Hyderabad - 500 607 India ; '' '' '' '' '' _publ_contact_author_address ;Laboratory of X-ray Crystallography Indian Institute of Chemical Technology Hyderabad - 500 607 India ; _publ_contact_author_email sshiya@yahoo.com _publ_contact_author_fax 91-40-27193118 _publ_contact_author_phone 91-40-27193118 _publ_contact_author_name B.Sridhar loop_ _publ_author_name S.Keesara 'P. Srinivas' S.P.Parvathaneni B.Kodicherla ; S.Balasubramanian ; M.R.Mandapati data_ai _database_code_depnum_ccdc_archive 'CCDC 823203' # start Validation Reply Form _vrf_CHEMW03_ai ; PROBLEM: ALERT: The ratio of given/expected molecular weight as RESPONSE: The asymmetric unit also contains one acetic acid solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009). Acta Cryst. D65, 148,155]. ; _vrf_PLAT043_ai ; PROBLEM: Check Reported Molecular Weight ................ 664.84 RESPONSE: The asymmetric unit also contains one acetic acid solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009). Acta Cryst. D65, 148,155]. ; _vrf_PLAT044_ai ; PROBLEM: Calculated and Reported Dx Differ .............. ? RESPONSE: The asymmetric unit also contains one acetic acid solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009). Acta Cryst. D65, 148, 155]. ; # end Validation Reply Form _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_formula_moiety 'C23 H20 Br N3 O3 Pd S, C2 H4 O2' _chemical_formula_sum 'C25 H24 Br N3 O5 Pd S' _chemical_melting_point ? _exptl_crystal_description block _exptl_crystal_colour colorless _diffrn_ambient_temperature 294(2) _chemical_formula_weight 664.84 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' S S 0.1246 0.1234 '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_int_tables_number 2 _chemical_absolute_configuration ? _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.724(5) _cell_length_b 13.385(5) _cell_length_c 14.000(5) _cell_angle_alpha 68.935(5) _cell_angle_beta 83.939(5) _cell_angle_gamma 89.447(5) _cell_volume 1342.5(11) _cell_formula_units_Z 2 _cell_measurement_temperature 294(2) _cell_measurement_reflns_used 5032 _cell_measurement_theta_min 2.64 _cell_measurement_theta_max 27.95 _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.645 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 664 _exptl_absorpt_coefficient_mu 2.297 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_radiation_probe x-ray _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD Area Detector' _diffrn_measurement_device 'Bruker SMART APEX CCD area-detector' _diffrn_measurement_method '\w scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12886 _diffrn_reflns_av_R_equivalents 0.0207 _diffrn_reflns_av_sigmaI/netI 0.0218 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.63 _diffrn_reflns_theta_max 25.00 _reflns_number_total 4716 _reflns_number_gt 4381 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'SMART (Bruker, 2001)' _computing_cell_refinement 'SAINT (Bruker, 2001)' _computing_data_reduction SAINT _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'SHELXTL/PC (Sheldrick, 1990)' _computing_publication_material SHELXL97 _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^)+(0.0459P)^2^+0.5153P] 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 4716 _refine_ls_number_parameters 290 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0298 _refine_ls_R_factor_gt 0.0278 _refine_ls_wR_factor_ref 0.0784 _refine_ls_wR_factor_gt 0.0767 _refine_ls_goodness_of_fit_ref 1.077 _refine_ls_restrained_S_all 1.077 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 -0.011 0.500 0.000 264 62 ' ' _platon_squeeze_details ; The unit cell contains one acetic acid molecule which have been treated as a diffuse contribution to the overall scattering without specific atom positions by SQUEEZE/PLATON. ; 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 Br1 Br 0.87159(8) 0.62322(4) 0.54416(5) 0.1275(2) Uani 1 1 d . . . C1 C 0.7357(5) 0.4979(3) 0.6232(3) 0.0782(10) Uani 1 1 d . . . C2 C 0.7054(5) 0.4725(3) 0.7285(3) 0.0811(10) Uani 1 1 d . . . H2 H 0.7479 0.5167 0.7595 0.097 Uiso 1 1 calc R . . C3 C 0.6107(4) 0.3802(3) 0.7861(3) 0.0672(8) Uani 1 1 d . . . H3 H 0.5888 0.3621 0.8570 0.081 Uiso 1 1 calc R . . C4 C 0.5471(3) 0.3131(2) 0.7408(2) 0.0507(6) Uani 1 1 d . . . C5 C 0.5810(4) 0.3416(3) 0.6349(2) 0.0672(8) Uani 1 1 d . . . H5 H 0.5396 0.2976 0.6033 0.081 Uiso 1 1 calc R . . C6 C 0.6747(5) 0.4334(3) 0.5764(3) 0.0819(10) Uani 1 1 d . . . H6 H 0.6967 0.4519 0.5055 0.098 Uiso 1 1 calc R . . C7 C 0.4537(3) 0.2112(2) 0.8051(2) 0.0452(5) Uani 1 1 d . . . C8 C 0.3243(3) 0.0539(2) 0.80184(19) 0.0424(5) Uani 1 1 d . . . C9 C 0.3368(4) 0.0855(3) 0.5931(2) 0.0560(7) Uani 1 1 d . . . H9A H 0.2761 0.0662 0.5446 0.067 Uiso 1 1 calc R . . H9B H 0.2914 0.1530 0.5940 0.067 Uiso 1 1 calc R . . C10 C 0.5267(4) 0.1040(2) 0.5518(2) 0.0555(7) Uani 1 1 d . . . C11 C 0.5698(5) 0.1824(3) 0.4554(2) 0.0764(9) Uani 1 1 d . . . H11 H 0.4833 0.2227 0.4189 0.092 Uiso 1 1 calc R . . C12 C 0.7455(7) 0.2006(4) 0.4133(3) 0.0947(13) Uani 1 1 d . . . H12 H 0.7745 0.2522 0.3482 0.114 Uiso 1 1 calc R . . C13 C 0.8726(5) 0.1439(4) 0.4667(3) 0.0854(11) Uani 1 1 d . . . H13 H 0.9885 0.1578 0.4390 0.102 Uiso 1 1 calc R . . C14 C 0.8310(4) 0.0669(3) 0.5602(3) 0.0764(10) Uani 1 1 d . . . H14 H 0.9185 0.0271 0.5961 0.092 Uiso 1 1 calc R . . C15 C 0.6594(4) 0.0470(3) 0.6031(2) 0.0617(7) Uani 1 1 d . . . H15 H 0.6331 -0.0059 0.6677 0.074 Uiso 1 1 calc R . . C16 C 0.1960(4) -0.1038(2) 0.9395(2) 0.0487(6) Uani 1 1 d . . . H16A H 0.2805 -0.1538 0.9286 0.058 Uiso 1 1 calc R . . H16B H 0.0973 -0.1058 0.9027 0.058 Uiso 1 1 calc R . . C17 C 0.1375(3) -0.1355(2) 1.05203(19) 0.0456(5) Uani 1 1 d . . . C18 C 0.0407(4) -0.2282(2) 1.1068(2) 0.0577(7) Uani 1 1 d . . . H18 H 0.0056 -0.2727 1.0740 0.069 Uiso 1 1 calc R . . C19 C -0.0032(4) -0.2539(3) 1.2114(2) 0.0632(8) Uani 1 1 d . . . H19 H -0.0684 -0.3161 1.2498 0.076 Uiso 1 1 calc R . . C20 C 0.0494(4) -0.1876(3) 1.2577(2) 0.0615(7) Uani 1 1 d . . . H20 H 0.0225 -0.2048 1.3282 0.074 Uiso 1 1 calc R . . C21 C 0.1429(4) -0.0949(2) 1.1994(2) 0.0541(6) Uani 1 1 d . . . H21 H 0.1769 -0.0491 1.2310 0.065 Uiso 1 1 calc R . . C22 C 0.2781(4) 0.1930(2) 1.1304(2) 0.0570(7) Uani 1 1 d . . . C23 C 0.3452(7) 0.2431(4) 1.2005(4) 0.0973(13) Uani 1 1 d . . . H23A H 0.3741 0.3174 1.1625 0.146 Uiso 1 1 calc R . . H23B H 0.4472 0.2070 1.2275 0.146 Uiso 1 1 calc R . . H23C H 0.2570 0.2367 1.2563 0.146 Uiso 1 1 calc R . . N1 N 0.2748(3) 0.00490(16) 0.89985(15) 0.0411(4) Uani 1 1 d . . . N2 N 0.1862(3) -0.06911(17) 1.09777(16) 0.0439(5) Uani 1 1 d . . . N3 N 0.4031(3) 0.15111(17) 0.75613(16) 0.0462(5) Uani 1 1 d . . . O1 O 0.4366(2) 0.19351(15) 0.90195(14) 0.0514(4) Uani 1 1 d . . . O2 O 0.3654(3) 0.11989(17) 1.11617(15) 0.0583(5) Uani 1 1 d . . . O3 O 0.1430(4) 0.2246(3) 1.0925(3) 0.1042(10) Uani 1 1 d . . . Pd1 Pd 0.31412(2) 0.064085(14) 1.004161(13) 0.04116(8) Uani 1 1 d . . . S1 S 0.28087(9) -0.01445(6) 0.71888(5) 0.05245(17) 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 Br1 0.1267(4) 0.0648(3) 0.1531(5) -0.0056(3) 0.0307(3) -0.0327(3) C1 0.072(2) 0.0440(16) 0.101(3) -0.0094(17) 0.0105(19) -0.0103(14) C2 0.088(2) 0.0528(18) 0.103(3) -0.0342(19) 0.009(2) -0.0141(17) C3 0.076(2) 0.0531(17) 0.076(2) -0.0307(16) 0.0045(16) -0.0081(14) C4 0.0466(14) 0.0461(14) 0.0579(15) -0.0185(12) -0.0004(11) 0.0000(11) C5 0.076(2) 0.0622(18) 0.0586(17) -0.0174(15) -0.0010(15) -0.0130(15) C6 0.088(2) 0.073(2) 0.067(2) -0.0077(17) 0.0075(18) -0.0135(19) C7 0.0406(12) 0.0482(14) 0.0497(14) -0.0215(11) -0.0034(10) 0.0019(10) C8 0.0396(12) 0.0502(14) 0.0433(13) -0.0239(11) -0.0041(10) -0.0001(10) C9 0.0596(16) 0.0729(18) 0.0385(13) -0.0225(13) -0.0089(11) -0.0030(13) C10 0.0656(17) 0.0679(17) 0.0421(13) -0.0316(13) -0.0011(12) -0.0090(14) C11 0.095(2) 0.079(2) 0.0490(16) -0.0172(16) 0.0012(16) -0.0088(19) C12 0.126(4) 0.088(3) 0.062(2) -0.028(2) 0.031(2) -0.036(3) C13 0.079(2) 0.106(3) 0.086(3) -0.059(2) 0.020(2) -0.030(2) C14 0.0587(18) 0.110(3) 0.080(2) -0.059(2) 0.0005(16) -0.0085(18) C15 0.0626(17) 0.080(2) 0.0490(15) -0.0317(15) -0.0038(13) -0.0072(15) C16 0.0559(14) 0.0460(14) 0.0475(14) -0.0218(11) -0.0015(11) -0.0070(11) C17 0.0421(13) 0.0491(14) 0.0465(13) -0.0181(11) -0.0053(10) 0.0035(10) C18 0.0601(16) 0.0516(16) 0.0595(16) -0.0181(13) -0.0047(13) -0.0056(13) C19 0.0608(17) 0.0586(17) 0.0576(17) -0.0083(14) 0.0029(14) -0.0051(14) C20 0.0623(17) 0.0691(19) 0.0443(14) -0.0119(14) 0.0020(12) 0.0009(14) C21 0.0567(15) 0.0635(17) 0.0423(14) -0.0200(13) -0.0025(11) 0.0026(13) C22 0.0650(17) 0.0584(17) 0.0527(15) -0.0254(13) -0.0092(13) 0.0003(14) C23 0.133(4) 0.093(3) 0.102(3) -0.069(3) -0.048(3) 0.025(3) N1 0.0413(10) 0.0449(11) 0.0413(11) -0.0210(9) -0.0024(8) -0.0041(8) N2 0.0412(11) 0.0501(12) 0.0423(11) -0.0194(9) -0.0030(8) 0.0020(9) N3 0.0471(11) 0.0492(12) 0.0431(11) -0.0185(9) -0.0012(9) -0.0043(9) O1 0.0605(11) 0.0510(10) 0.0472(10) -0.0238(8) -0.0018(8) -0.0106(8) O2 0.0722(12) 0.0627(12) 0.0534(11) -0.0343(10) -0.0172(9) 0.0069(10) O3 0.0897(18) 0.126(2) 0.147(3) -0.100(2) -0.0461(18) 0.0349(17) Pd1 0.04325(12) 0.04598(13) 0.03941(12) -0.02169(9) -0.00406(8) -0.00075(8) S1 0.0575(4) 0.0632(4) 0.0445(3) -0.0297(3) -0.0015(3) -0.0105(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br1 C1 1.895(3) . ? C1 C6 1.369(6) . ? C1 C2 1.383(6) . ? C2 C3 1.375(5) . ? C2 H2 0.9300 . ? C3 C4 1.390(4) . ? C3 H3 0.9300 . ? C4 C5 1.387(4) . ? C4 C7 1.481(4) . ? C5 C6 1.369(5) . ? C5 H5 0.9300 . ? C6 H6 0.9300 . ? C7 O1 1.282(3) . ? C7 N3 1.315(3) . ? C8 N1 1.306(3) . ? C8 N3 1.345(3) . ? C8 S1 1.775(2) . ? C9 C10 1.507(4) . ? C9 S1 1.799(3) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 C15 1.377(4) . ? C10 C11 1.388(4) . ? C11 C12 1.408(6) . ? C11 H11 0.9300 . ? C12 C13 1.353(6) . ? C12 H12 0.9300 . ? C13 C14 1.352(6) . ? C13 H13 0.9300 . ? C14 C15 1.383(5) . ? C14 H14 0.9300 . ? C15 H15 0.9300 . ? C16 N1 1.470(3) . ? C16 C17 1.497(4) . ? C16 H16A 0.9700 . ? C16 H16B 0.9700 . ? C17 N2 1.344(3) . ? C17 C18 1.378(4) . ? C18 C19 1.384(4) . ? C18 H18 0.9300 . ? C19 C20 1.360(5) . ? C19 H19 0.9300 . ? C20 C21 1.375(4) . ? C20 H20 0.9300 . ? C21 N2 1.343(3) . ? C21 H21 0.9300 . ? C22 O3 1.223(4) . ? C22 O2 1.245(4) . ? C22 C23 1.506(4) . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C23 H23C 0.9600 . ? N1 Pd1 1.945(2) . ? N2 Pd1 1.988(2) . ? O1 Pd1 1.9766(19) . ? O2 Pd1 2.0378(19) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 C1 C2 121.6(3) . . ? C6 C1 Br1 120.2(3) . . ? C2 C1 Br1 118.2(3) . . ? C3 C2 C1 118.2(3) . . ? C3 C2 H2 120.9 . . ? C1 C2 H2 120.9 . . ? C2 C3 C4 121.5(4) . . ? C2 C3 H3 119.3 . . ? C4 C3 H3 119.3 . . ? C5 C4 C3 118.4(3) . . ? C5 C4 C7 121.1(3) . . ? C3 C4 C7 120.4(3) . . ? C6 C5 C4 120.8(3) . . ? C6 C5 H5 119.6 . . ? C4 C5 H5 119.6 . . ? C5 C6 C1 119.5(4) . . ? C5 C6 H6 120.2 . . ? C1 C6 H6 120.2 . . ? O1 C7 N3 129.2(2) . . ? O1 C7 C4 114.5(2) . . ? N3 C7 C4 116.3(2) . . ? N1 C8 N3 127.4(2) . . ? N1 C8 S1 116.65(19) . . ? N3 C8 S1 115.99(18) . . ? C10 C9 S1 117.9(2) . . ? C10 C9 H9A 107.8 . . ? S1 C9 H9A 107.8 . . ? C10 C9 H9B 107.8 . . ? S1 C9 H9B 107.8 . . ? H9A C9 H9B 107.2 . . ? C15 C10 C11 118.1(3) . . ? C15 C10 C9 124.1(3) . . ? C11 C10 C9 117.8(3) . . ? C10 C11 C12 119.5(4) . . ? C10 C11 H11 120.2 . . ? C12 C11 H11 120.2 . . ? C13 C12 C11 120.6(4) . . ? C13 C12 H12 119.7 . . ? C11 C12 H12 119.7 . . ? C14 C13 C12 120.0(4) . . ? C14 C13 H13 120.0 . . ? C12 C13 H13 120.0 . . ? C13 C14 C15 120.5(4) . . ? C13 C14 H14 119.8 . . ? C15 C14 H14 119.8 . . ? C10 C15 C14 121.3(3) . . ? C10 C15 H15 119.4 . . ? C14 C15 H15 119.4 . . ? N1 C16 C17 109.6(2) . . ? N1 C16 H16A 109.7 . . ? C17 C16 H16A 109.7 . . ? N1 C16 H16B 109.7 . . ? C17 C16 H16B 109.7 . . ? H16A C16 H16B 108.2 . . ? N2 C17 C18 121.4(2) . . ? N2 C17 C16 116.4(2) . . ? C18 C17 C16 122.2(2) . . ? C17 C18 C19 118.8(3) . . ? C17 C18 H18 120.6 . . ? C19 C18 H18 120.6 . . ? C20 C19 C18 119.6(3) . . ? C20 C19 H19 120.2 . . ? C18 C19 H19 120.2 . . ? C19 C20 C21 119.4(3) . . ? C19 C20 H20 120.3 . . ? C21 C20 H20 120.3 . . ? N2 C21 C20 121.5(3) . . ? N2 C21 H21 119.2 . . ? C20 C21 H21 119.2 . . ? O3 C22 O2 124.3(3) . . ? O3 C22 C23 119.2(3) . . ? O2 C22 C23 116.5(3) . . ? C22 C23 H23A 109.5 . . ? C22 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C22 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C8 N1 C16 121.3(2) . . ? C8 N1 Pd1 123.32(17) . . ? C16 N1 Pd1 115.21(16) . . ? C21 N2 C17 119.3(2) . . ? C21 N2 Pd1 125.50(19) . . ? C17 N2 Pd1 115.20(17) . . ? C7 N3 C8 124.8(2) . . ? C7 O1 Pd1 122.41(16) . . ? C22 O2 Pd1 120.21(18) . . ? N1 Pd1 O1 92.74(8) . . ? N1 Pd1 N2 82.81(9) . . ? O1 Pd1 N2 175.50(7) . . ? N1 Pd1 O2 176.83(8) . . ? O1 Pd1 O2 88.19(8) . . ? N2 Pd1 O2 96.29(9) . . ? C8 S1 C9 102.66(13) . . ? 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 C1 C2 C3 -0.3(6) . . . . ? Br1 C1 C2 C3 -178.3(3) . . . . ? C1 C2 C3 C4 0.3(6) . . . . ? C2 C3 C4 C5 -0.1(5) . . . . ? C2 C3 C4 C7 176.7(3) . . . . ? C3 C4 C5 C6 -0.1(5) . . . . ? C7 C4 C5 C6 -176.8(3) . . . . ? C4 C5 C6 C1 0.1(6) . . . . ? C2 C1 C6 C5 0.1(6) . . . . ? Br1 C1 C6 C5 178.1(3) . . . . ? C5 C4 C7 O1 177.7(3) . . . . ? C3 C4 C7 O1 1.0(4) . . . . ? C5 C4 C7 N3 -1.1(4) . . . . ? C3 C4 C7 N3 -177.8(3) . . . . ? S1 C9 C10 C15 2.1(4) . . . . ? S1 C9 C10 C11 -178.9(2) . . . . ? C15 C10 C11 C12 0.4(5) . . . . ? C9 C10 C11 C12 -178.7(3) . . . . ? C10 C11 C12 C13 -1.2(6) . . . . ? C11 C12 C13 C14 1.7(6) . . . . ? C12 C13 C14 C15 -1.3(6) . . . . ? C11 C10 C15 C14 0.0(4) . . . . ? C9 C10 C15 C14 179.0(3) . . . . ? C13 C14 C15 C10 0.4(5) . . . . ? N1 C16 C17 N2 -8.6(3) . . . . ? N1 C16 C17 C18 172.2(2) . . . . ? N2 C17 C18 C19 -1.4(4) . . . . ? C16 C17 C18 C19 177.7(3) . . . . ? C17 C18 C19 C20 0.0(5) . . . . ? C18 C19 C20 C21 1.2(5) . . . . ? C19 C20 C21 N2 -1.2(5) . . . . ? N3 C8 N1 C16 -177.5(2) . . . . ? S1 C8 N1 C16 3.2(3) . . . . ? N3 C8 N1 Pd1 -2.1(4) . . . . ? S1 C8 N1 Pd1 178.65(11) . . . . ? C17 C16 N1 C8 -174.8(2) . . . . ? C17 C16 N1 Pd1 9.5(3) . . . . ? C20 C21 N2 C17 -0.2(4) . . . . ? C20 C21 N2 Pd1 178.0(2) . . . . ? C18 C17 N2 C21 1.5(4) . . . . ? C16 C17 N2 C21 -177.7(2) . . . . ? C18 C17 N2 Pd1 -176.9(2) . . . . ? C16 C17 N2 Pd1 3.9(3) . . . . ? O1 C7 N3 C8 -2.0(4) . . . . ? C4 C7 N3 C8 176.7(2) . . . . ? N1 C8 N3 C7 4.4(4) . . . . ? S1 C8 N3 C7 -176.3(2) . . . . ? N3 C7 O1 Pd1 -2.1(4) . . . . ? C4 C7 O1 Pd1 179.14(16) . . . . ? O3 C22 O2 Pd1 11.9(5) . . . . ? C23 C22 O2 Pd1 -169.1(3) . . . . ? C8 N1 Pd1 O1 -1.3(2) . . . . ? C16 N1 Pd1 O1 174.42(17) . . . . ? C8 N1 Pd1 N2 178.1(2) . . . . ? C16 N1 Pd1 N2 -6.20(17) . . . . ? C7 O1 Pd1 N1 3.2(2) . . . . ? C7 O1 Pd1 O2 -179.9(2) . . . . ? C21 N2 Pd1 N1 -177.0(2) . . . . ? C17 N2 Pd1 N1 1.24(17) . . . . ? C21 N2 Pd1 O2 6.1(2) . . . . ? C17 N2 Pd1 O2 -175.70(17) . . . . ? C22 O2 Pd1 O1 77.1(2) . . . . ? C22 O2 Pd1 N2 -102.5(2) . . . . ? N1 C8 S1 C9 171.7(2) . . . . ? N3 C8 S1 C9 -7.7(2) . . . . ? C10 C9 S1 C8 79.8(2) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.462 _refine_diff_density_min -0.676 _refine_diff_density_rms 0.080