# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Han Vinh Huynh' _publ_contact_author_address ; Department of Chemistry National University of Singapore 3 Science Drive Singapore 117534 SINGAPORE ; _publ_contact_author_email CHMHHV@NUS.EDU.SG _publ_section_title ; Hemilabile Behavior of a Thioether-functionalized N-Heterocyclic Carbene Ligand ; loop_ _publ_author_name 'Huynh Han Vinh' 'Geok Kheng Tan' 'Chun Hui Yeo' # Attachment 'Complex 2revised.cif' data_6054 _database_code_depnum_ccdc_archive 'CCDC 610655' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H14 Br2 N2 Pd S' _chemical_formula_weight 484.53 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' 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' Br Br -0.2901 2.4595 '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 8.6338(5) _cell_length_b 9.6410(6) _cell_length_c 9.7985(6) _cell_angle_alpha 107.453(1) _cell_angle_beta 103.622(1) _cell_angle_gamma 101.368(1) _cell_volume 723.96(8) _cell_formula_units_Z 2 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 3737 _cell_measurement_theta_min 2.30 _cell_measurement_theta_max 27.42 _exptl_crystal_description BLOCK _exptl_crystal_colour ORANGE _exptl_crystal_size_max 0.16 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 2.223 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 464 _exptl_absorpt_coefficient_mu 6.928 _exptl_absorpt_correction_type 'Sadabs, (Sheldrick 2001)' _exptl_absorpt_correction_T_min 0.4036 _exptl_absorpt_correction_T_max 0.5442 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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 9558 _diffrn_reflns_av_R_equivalents 0.0232 _diffrn_reflns_av_sigmaI/netI 0.0270 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.30 _diffrn_reflns_theta_max 27.50 _reflns_number_total 3324 _reflns_number_gt 2887 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _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^)+(0.0376P)^2^+0.2516P] 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 3324 _refine_ls_number_parameters 165 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0322 _refine_ls_R_factor_gt 0.0267 _refine_ls_wR_factor_ref 0.0708 _refine_ls_wR_factor_gt 0.0683 _refine_ls_goodness_of_fit_ref 1.075 _refine_ls_restrained_S_all 1.075 _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 0.24073(3) -0.08099(2) 0.09841(2) 0.02482(8) Uani 1 1 d . . . Br1 Br 0.29121(5) -0.32590(4) 0.08250(4) 0.04155(11) Uani 1 1 d . . . Br2 Br 0.24779(5) -0.11378(4) -0.16065(3) 0.03887(10) Uani 1 1 d . . . S1 S 0.20739(9) 0.15519(9) 0.11807(8) 0.02686(16) Uani 1 1 d . . . N1 N 0.1029(3) -0.1496(3) 0.3323(3) 0.0278(5) Uani 1 1 d . . . N2 N 0.3240(3) 0.0376(3) 0.4299(3) 0.0268(5) Uani 1 1 d . . . C1 C 0.2189(4) -0.0632(3) 0.2983(3) 0.0262(6) Uani 1 1 d . . . C2 C 0.1372(4) -0.1021(4) 0.4865(3) 0.0327(7) Uani 1 1 d . . . H2 H 0.0753 -0.1449 0.5385 0.039 Uiso 1 1 calc R . . C3 C 0.2749(4) 0.0164(4) 0.5487(3) 0.0309(7) Uani 1 1 d . . . H3 H 0.3275 0.0734 0.6519 0.037 Uiso 1 1 calc R . . C4 C -0.0401(4) -0.2731(4) 0.2239(4) 0.0402(8) Uani 1 1 d . . . H4A H -0.0579 -0.2656 0.1252 0.060 Uiso 1 1 calc R . . H4B H -0.1381 -0.2666 0.2547 0.060 Uiso 1 1 calc R . . H4C H -0.0197 -0.3695 0.2195 0.060 Uiso 1 1 calc R . . C5 C 0.4426(4) 0.1771(3) 0.4425(3) 0.0285(6) Uani 1 1 d . . . H5A H 0.4896 0.1562 0.3593 0.034 Uiso 1 1 calc R . . H5B H 0.5339 0.2155 0.5377 0.034 Uiso 1 1 calc R . . C6 C 0.3487(4) 0.2928(3) 0.4367(3) 0.0263(6) Uani 1 1 d . . . C7 C 0.3605(4) 0.4023(3) 0.5713(4) 0.0320(7) Uani 1 1 d . . . H7 H 0.4310 0.4056 0.6621 0.038 Uiso 1 1 calc R . . C8 C 0.2707(4) 0.5069(4) 0.5748(4) 0.0386(8) Uani 1 1 d . . . H8 H 0.2788 0.5795 0.6671 0.046 Uiso 1 1 calc R . . C9 C 0.1688(4) 0.5032(4) 0.4407(4) 0.0399(8) Uani 1 1 d . . . H9 H 0.1105 0.5760 0.4418 0.048 Uiso 1 1 calc R . . C10 C 0.1521(4) 0.3935(4) 0.3053(4) 0.0353(7) Uani 1 1 d . . . H10 H 0.0810 0.3904 0.2149 0.042 Uiso 1 1 calc R . . C11 C 0.2410(4) 0.2876(3) 0.3033(3) 0.0270(6) Uani 1 1 d . . . C12 C 0.3808(4) 0.2559(4) 0.0771(4) 0.0355(7) Uani 1 1 d . . . H12A H 0.3718 0.3564 0.0846 0.053 Uiso 1 1 calc R . . H12B H 0.3789 0.2003 -0.0241 0.053 Uiso 1 1 calc R . . H12C H 0.4845 0.2648 0.1490 0.053 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 Pd1 0.03303(14) 0.02298(13) 0.01872(12) 0.00775(9) 0.00908(9) 0.00725(9) Br1 0.0609(2) 0.02802(18) 0.0458(2) 0.01580(15) 0.02731(18) 0.01800(16) Br2 0.0545(2) 0.0397(2) 0.02229(16) 0.01043(14) 0.01466(14) 0.01176(16) S1 0.0298(4) 0.0277(4) 0.0242(4) 0.0115(3) 0.0071(3) 0.0092(3) N1 0.0328(13) 0.0295(13) 0.0249(13) 0.0126(11) 0.0106(11) 0.0107(11) N2 0.0356(14) 0.0270(13) 0.0216(12) 0.0101(10) 0.0095(10) 0.0147(11) C1 0.0326(15) 0.0234(14) 0.0250(14) 0.0101(12) 0.0089(12) 0.0113(12) C2 0.0444(18) 0.0388(18) 0.0283(16) 0.0200(14) 0.0183(14) 0.0207(15) C3 0.0477(19) 0.0335(17) 0.0208(14) 0.0131(13) 0.0139(13) 0.0229(15) C4 0.0377(18) 0.045(2) 0.0352(18) 0.0188(16) 0.0093(15) 0.0033(15) C5 0.0298(15) 0.0256(15) 0.0253(15) 0.0059(12) 0.0053(12) 0.0068(12) C6 0.0262(14) 0.0216(14) 0.0304(15) 0.0082(12) 0.0105(12) 0.0053(12) C7 0.0342(16) 0.0258(16) 0.0287(16) 0.0033(13) 0.0092(13) 0.0039(13) C8 0.0452(19) 0.0257(16) 0.044(2) 0.0065(15) 0.0211(16) 0.0084(15) C9 0.0424(19) 0.0288(17) 0.055(2) 0.0143(16) 0.0220(17) 0.0170(15) C10 0.0339(17) 0.0320(17) 0.0419(19) 0.0153(15) 0.0109(14) 0.0121(14) C11 0.0291(15) 0.0228(15) 0.0300(16) 0.0096(12) 0.0117(12) 0.0066(12) C12 0.0403(18) 0.0338(17) 0.0330(17) 0.0146(14) 0.0138(14) 0.0054(14) _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 C1 1.971(3) . ? Pd1 S1 2.3079(8) . ? Pd1 Br1 2.4508(4) . ? Pd1 Br2 2.4792(4) . ? S1 C11 1.795(3) . ? S1 C12 1.813(3) . ? N1 C1 1.343(4) . ? N1 C2 1.378(4) . ? N1 C4 1.454(4) . ? N2 C1 1.335(4) . ? N2 C3 1.385(4) . ? N2 C5 1.473(4) . ? C2 C3 1.339(5) . ? C5 C6 1.509(4) . ? C6 C7 1.387(4) . ? C6 C11 1.395(4) . ? C7 C8 1.385(5) . ? C8 C9 1.384(5) . ? C9 C10 1.381(5) . ? C10 C11 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 C1 Pd1 S1 93.65(9) . . ? C1 Pd1 Br1 86.53(8) . . ? S1 Pd1 Br1 177.14(2) . . ? C1 Pd1 Br2 176.06(9) . . ? S1 Pd1 Br2 86.94(2) . . ? Br1 Pd1 Br2 93.070(13) . . ? C11 S1 C12 98.38(14) . . ? C11 S1 Pd1 117.46(10) . . ? C12 S1 Pd1 106.77(11) . . ? C1 N1 C2 109.9(3) . . ? C1 N1 C4 125.6(3) . . ? C2 N1 C4 124.5(3) . . ? C1 N2 C3 110.8(3) . . ? C1 N2 C5 122.8(2) . . ? C3 N2 C5 124.0(3) . . ? N2 C1 N1 105.8(3) . . ? N2 C1 Pd1 125.5(2) . . ? N1 C1 Pd1 128.6(2) . . ? C3 C2 N1 107.5(3) . . ? C2 C3 N2 106.0(3) . . ? N2 C5 C6 107.6(2) . . ? C7 C6 C11 118.5(3) . . ? C7 C6 C5 118.4(3) . . ? C11 C6 C5 122.9(3) . . ? C8 C7 C6 121.4(3) . . ? C9 C8 C7 119.2(3) . . ? C10 C9 C8 120.6(3) . . ? C9 C10 C11 119.7(3) . . ? C10 C11 C6 120.5(3) . . ? C10 C11 S1 113.9(2) . . ? C6 C11 S1 125.5(2) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.771 _refine_diff_density_min -0.435 _refine_diff_density_rms 0.106 # Attachment 'Complex 3.cif' data_6202 _database_code_depnum_ccdc_archive 'CCDC 610656' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H29 Br2 N2 P Pd S' _chemical_formula_weight 746.80 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' 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 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 9.1662(7) _cell_length_b 15.3599(12) _cell_length_c 20.4797(15) _cell_angle_alpha 90.00 _cell_angle_beta 91.949(2) _cell_angle_gamma 90.00 _cell_volume 2881.7(4) _cell_formula_units_Z 4 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 4820 _cell_measurement_theta_min 2.22 _cell_measurement_theta_max 25.84 _exptl_crystal_description BLOCK _exptl_crystal_colour ORANGE _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.721 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1480 _exptl_absorpt_coefficient_mu 3.568 _exptl_absorpt_correction_type 'Sadabs, (Sheldrick 2001)' _exptl_absorpt_correction_T_min 0.3295 _exptl_absorpt_correction_T_max 0.6741 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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 20290 _diffrn_reflns_av_R_equivalents 0.0385 _diffrn_reflns_av_sigmaI/netI 0.0450 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.66 _diffrn_reflns_theta_max 27.50 _reflns_number_total 6595 _reflns_number_gt 5271 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _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^)+(0.0502P)^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 6595 _refine_ls_number_parameters 336 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0507 _refine_ls_R_factor_gt 0.0366 _refine_ls_wR_factor_ref 0.0929 _refine_ls_wR_factor_gt 0.0880 _refine_ls_goodness_of_fit_ref 1.039 _refine_ls_restrained_S_all 1.039 _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 0.27521(2) 0.157050(15) 0.279715(11) 0.02649(8) Uani 1 1 d . . . Br1 Br 0.42804(4) 0.21945(2) 0.193891(17) 0.03825(10) Uani 1 1 d . . . Br2 Br 0.22440(5) 0.30463(2) 0.32229(2) 0.04792(12) Uani 1 1 d . . . P1 P 0.15397(9) 0.09520(5) 0.36231(4) 0.02649(18) Uani 1 1 d . . . S1 S -0.23108(11) 0.06359(8) 0.12464(6) 0.0564(3) Uani 1 1 d . . . N2 N 0.2116(3) -0.00117(17) 0.19835(14) 0.0339(6) Uani 1 1 d . . . N1 N 0.4298(3) -0.00641(18) 0.23911(14) 0.0362(7) Uani 1 1 d . . . C1 C 0.3076(3) 0.0426(2) 0.23752(15) 0.0287(7) Uani 1 1 d . . . C2 C 0.2735(4) -0.0763(2) 0.17572(19) 0.0480(10) Uani 1 1 d . . . H2 H 0.2288 -0.1171 0.1473 0.058 Uiso 1 1 calc R . . C3 C 0.4099(5) -0.0806(2) 0.20166(19) 0.0496(10) Uani 1 1 d . . . H3 H 0.4782 -0.1252 0.1956 0.060 Uiso 1 1 calc R . . C5 C 0.0662(3) 0.0283(2) 0.17800(16) 0.0336(7) Uani 1 1 d . . . H5A H 0.0341 0.0729 0.2086 0.040 Uiso 1 1 calc R . . H5B H -0.0018 -0.0207 0.1800 0.040 Uiso 1 1 calc R . . C6 C 0.0606(3) 0.0657(2) 0.10929(16) 0.0301(7) Uani 1 1 d . . . C7 C 0.1861(4) 0.0832(2) 0.07509(18) 0.0404(8) Uani 1 1 d . . . H7 H 0.2782 0.0733 0.0953 0.048 Uiso 1 1 calc R . . C8 C 0.1774(4) 0.1149(3) 0.0122(2) 0.0483(10) Uani 1 1 d . . . H8 H 0.2631 0.1256 -0.0104 0.058 Uiso 1 1 calc R . . C9 C 0.0451(5) 0.1306(3) -0.0172(2) 0.0502(10) Uani 1 1 d . . . H9 H 0.0397 0.1518 -0.0603 0.060 Uiso 1 1 calc R . . C10 C -0.0816(4) 0.1158(2) 0.01577(18) 0.0435(9) Uani 1 1 d . . . H10 H -0.1727 0.1278 -0.0048 0.052 Uiso 1 1 calc R . . C11 C -0.0753(4) 0.0832(2) 0.07897(17) 0.0333(7) Uani 1 1 d . . . C12 C -0.3802(5) 0.0813(4) 0.0680(3) 0.094(2) Uani 1 1 d . . . H12A H -0.3746 0.1398 0.0505 0.141 Uiso 1 1 calc R . . H12B H -0.4714 0.0742 0.0900 0.141 Uiso 1 1 calc R . . H12C H -0.3756 0.0395 0.0326 0.141 Uiso 1 1 calc R . . C4 C 0.5638(4) 0.0146(3) 0.2755(2) 0.0488(10) Uani 1 1 d . . . H4A H 0.6187 0.0572 0.2514 0.073 Uiso 1 1 calc R . . H4B H 0.6219 -0.0377 0.2816 0.073 Uiso 1 1 calc R . . H4C H 0.5404 0.0384 0.3178 0.073 Uiso 1 1 calc R . . C1A C 0.1098(3) -0.0203(2) 0.35355(15) 0.0287(7) Uani 1 1 d . . . C2A C 0.2212(4) -0.0812(2) 0.35129(18) 0.0402(8) Uani 1 1 d . . . H2A H 0.3189 -0.0626 0.3529 0.048 Uiso 1 1 calc R . . C3A C 0.1898(4) -0.1689(2) 0.3467(2) 0.0455(9) Uani 1 1 d . . . H3A H 0.2661 -0.2097 0.3461 0.055 Uiso 1 1 calc R . . C4A C 0.0478(5) -0.1964(2) 0.3431(2) 0.0488(10) Uani 1 1 d . . . H4A1 H 0.0270 -0.2563 0.3404 0.059 Uiso 1 1 calc R . . C5A C -0.0633(4) -0.1381(3) 0.3434(2) 0.0559(11) Uani 1 1 d . . . H5A1 H -0.1605 -0.1575 0.3398 0.067 Uiso 1 1 calc R . . C6A C -0.0337(4) -0.0497(2) 0.3491(2) 0.0443(9) Uani 1 1 d . . . H6A H -0.1110 -0.0095 0.3499 0.053 Uiso 1 1 calc R . . C1B C 0.2558(3) 0.1003(2) 0.44031(16) 0.0303(7) Uani 1 1 d . . . C2B C 0.2655(6) 0.0305(3) 0.4820(2) 0.0678(14) Uani 1 1 d . . . H2B H 0.2220 -0.0228 0.4700 0.081 Uiso 1 1 calc R . . C3B C 0.3397(6) 0.0384(3) 0.5421(2) 0.0745(16) Uani 1 1 d . . . H3B H 0.3468 -0.0101 0.5701 0.089 Uiso 1 1 calc R . . C4B C 0.4017(4) 0.1148(3) 0.56107(19) 0.0464(9) Uani 1 1 d . . . H4B1 H 0.4509 0.1198 0.6019 0.056 Uiso 1 1 calc R . . C5B C 0.3913(5) 0.1833(3) 0.5201(2) 0.0590(12) Uani 1 1 d . . . H5B1 H 0.4328 0.2367 0.5333 0.071 Uiso 1 1 calc R . . C6B C 0.3216(5) 0.1774(3) 0.4596(2) 0.0524(11) Uani 1 1 d . . . H6B H 0.3188 0.2259 0.4315 0.063 Uiso 1 1 calc R . . C1C C -0.0221(3) 0.1456(2) 0.37691(16) 0.0300(7) Uani 1 1 d . . . C2C C -0.0761(4) 0.1515(2) 0.43889(18) 0.0406(8) Uani 1 1 d . . . H2C H -0.0179 0.1341 0.4752 0.049 Uiso 1 1 calc R . . C3C C -0.2169(4) 0.1833(3) 0.4478(2) 0.0520(11) Uani 1 1 d . . . H3C H -0.2537 0.1874 0.4900 0.062 Uiso 1 1 calc R . . C4C C -0.3017(5) 0.2085(3) 0.3939(3) 0.0582(12) Uani 1 1 d . . . H4C1 H -0.3972 0.2287 0.3994 0.070 Uiso 1 1 calc R . . C5C C -0.2476(4) 0.2041(2) 0.3329(2) 0.0496(10) Uani 1 1 d . . . H5C1 H -0.3058 0.2217 0.2966 0.059 Uiso 1 1 calc R . . C6C C -0.1066(4) 0.1739(2) 0.32385(19) 0.0419(9) Uani 1 1 d . . . H6C H -0.0689 0.1726 0.2817 0.050 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 Pd1 0.03034(13) 0.02559(14) 0.02367(14) -0.00008(9) 0.00280(9) -0.00523(9) Br1 0.03916(19) 0.0424(2) 0.0336(2) 0.00934(15) 0.00800(15) -0.00333(15) Br2 0.0718(3) 0.0290(2) 0.0440(2) -0.00554(16) 0.01783(19) -0.01089(17) P1 0.0283(4) 0.0263(4) 0.0250(4) -0.0007(3) 0.0025(3) -0.0056(3) S1 0.0340(5) 0.0846(8) 0.0509(6) 0.0045(6) 0.0043(4) 0.0024(5) N2 0.0381(15) 0.0299(15) 0.0333(16) -0.0027(12) -0.0060(12) 0.0054(12) N1 0.0354(15) 0.0394(16) 0.0338(16) 0.0052(13) -0.0007(12) 0.0102(12) C1 0.0328(16) 0.0306(17) 0.0225(16) 0.0020(13) 0.0000(13) 0.0035(13) C2 0.064(3) 0.034(2) 0.045(2) -0.0126(17) -0.0139(19) 0.0149(18) C3 0.064(3) 0.035(2) 0.050(2) -0.0065(17) -0.002(2) 0.0218(18) C5 0.0335(17) 0.0380(19) 0.0292(18) -0.0027(14) -0.0019(14) 0.0000(14) C6 0.0353(17) 0.0239(16) 0.0308(18) -0.0042(13) -0.0034(14) -0.0023(13) C7 0.0386(19) 0.044(2) 0.039(2) -0.0017(16) -0.0012(15) -0.0057(16) C8 0.052(2) 0.046(2) 0.048(2) 0.0031(19) 0.0102(18) -0.0115(18) C9 0.070(3) 0.044(2) 0.036(2) 0.0115(17) -0.002(2) -0.0054(19) C10 0.048(2) 0.044(2) 0.038(2) 0.0063(17) -0.0083(17) 0.0044(17) C11 0.0339(17) 0.0309(17) 0.0349(19) -0.0052(14) -0.0010(14) -0.0017(13) C12 0.031(2) 0.172(6) 0.078(4) -0.018(4) -0.006(2) 0.019(3) C4 0.0359(19) 0.063(3) 0.047(2) 0.008(2) -0.0059(17) 0.0054(18) C1A 0.0303(16) 0.0274(16) 0.0287(17) -0.0009(13) 0.0023(13) -0.0040(13) C2A 0.0378(19) 0.037(2) 0.045(2) 0.0091(16) -0.0001(16) -0.0018(15) C3A 0.051(2) 0.0325(19) 0.054(3) 0.0062(17) 0.0069(18) 0.0100(16) C4A 0.065(3) 0.0287(19) 0.053(3) -0.0080(17) 0.003(2) -0.0070(18) C5A 0.043(2) 0.041(2) 0.084(3) -0.015(2) -0.003(2) -0.0107(18) C6A 0.0316(18) 0.0301(18) 0.071(3) -0.0070(18) -0.0044(17) -0.0032(14) C1B 0.0280(16) 0.0350(18) 0.0279(17) -0.0009(14) 0.0015(13) -0.0053(13) C2B 0.114(4) 0.051(3) 0.038(2) 0.0092(19) -0.017(2) -0.034(3) C3B 0.124(5) 0.060(3) 0.039(3) 0.012(2) -0.022(3) -0.022(3) C4B 0.050(2) 0.057(2) 0.032(2) -0.0070(18) -0.0086(17) 0.0015(19) C5B 0.075(3) 0.043(2) 0.058(3) -0.005(2) -0.026(2) -0.014(2) C6B 0.071(3) 0.038(2) 0.046(2) -0.0010(18) -0.020(2) -0.0064(19) C1C 0.0311(16) 0.0245(16) 0.0349(19) -0.0015(13) 0.0058(14) -0.0023(13) C2C 0.047(2) 0.037(2) 0.039(2) 0.0048(16) 0.0096(16) -0.0022(16) C3C 0.053(2) 0.043(2) 0.062(3) 0.007(2) 0.029(2) 0.0063(19) C4C 0.044(2) 0.035(2) 0.097(4) 0.008(2) 0.018(2) 0.0091(17) C5C 0.047(2) 0.037(2) 0.064(3) -0.0003(19) -0.005(2) 0.0091(17) C6C 0.048(2) 0.0356(19) 0.041(2) -0.0019(16) -0.0016(17) 0.0072(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 C1 1.986(3) . ? Pd1 P1 2.2642(8) . ? Pd1 Br1 2.4775(4) . ? Pd1 Br2 2.4785(5) . ? P1 C1B 1.824(3) . ? P1 C1C 1.824(3) . ? P1 C1A 1.827(3) . ? S1 C11 1.760(4) . ? S1 C12 1.783(5) . ? N2 C1 1.350(4) . ? N2 C2 1.373(4) . ? N2 C5 1.455(4) . ? N1 C1 1.349(4) . ? N1 C3 1.382(5) . ? N1 C4 1.451(4) . ? C2 C3 1.343(5) . ? C5 C6 1.519(5) . ? C6 C7 1.393(5) . ? C6 C11 1.399(4) . ? C7 C8 1.376(5) . ? C8 C9 1.357(6) . ? C9 C10 1.383(6) . ? C10 C11 1.387(5) . ? C1A C2A 1.387(5) . ? C1A C6A 1.390(4) . ? C2A C3A 1.379(5) . ? C3A C4A 1.369(5) . ? C4A C5A 1.357(6) . ? C5A C6A 1.389(5) . ? C1B C2B 1.372(5) . ? C1B C6B 1.381(5) . ? C2B C3B 1.391(6) . ? C3B C4B 1.355(6) . ? C4B C5B 1.347(6) . ? C5B C6B 1.379(6) . ? C1C C2C 1.381(5) . ? C1C C6C 1.383(5) . ? C2C C3C 1.397(5) . ? C3C C4C 1.383(6) . ? C4C C5C 1.362(6) . ? C5C C6C 1.391(5) . ? 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 C1 Pd1 P1 92.18(9) . . ? C1 Pd1 Br1 86.41(9) . . ? P1 Pd1 Br1 174.92(2) . . ? C1 Pd1 Br2 174.55(9) . . ? P1 Pd1 Br2 91.03(2) . . ? Br1 Pd1 Br2 90.763(15) . . ? C1B P1 C1C 105.50(15) . . ? C1B P1 C1A 103.47(15) . . ? C1C P1 C1A 103.52(14) . . ? C1B P1 Pd1 112.76(10) . . ? C1C P1 Pd1 113.82(11) . . ? C1A P1 Pd1 116.54(11) . . ? C11 S1 C12 104.2(2) . . ? C1 N2 C2 110.5(3) . . ? C1 N2 C5 126.0(3) . . ? C2 N2 C5 123.4(3) . . ? C1 N1 C3 110.6(3) . . ? C1 N1 C4 125.2(3) . . ? C3 N1 C4 124.2(3) . . ? N1 C1 N2 105.1(3) . . ? N1 C1 Pd1 128.3(2) . . ? N2 C1 Pd1 126.5(2) . . ? C3 C2 N2 107.3(3) . . ? C2 C3 N1 106.4(3) . . ? N2 C5 C6 112.6(3) . . ? C7 C6 C11 118.5(3) . . ? C7 C6 C5 122.4(3) . . ? C11 C6 C5 119.0(3) . . ? C8 C7 C6 121.1(3) . . ? C9 C8 C7 120.1(4) . . ? C8 C9 C10 120.5(4) . . ? C9 C10 C11 120.4(3) . . ? C10 C11 C6 119.5(3) . . ? C10 C11 S1 123.3(3) . . ? C6 C11 S1 117.2(3) . . ? C2A C1A C6A 118.3(3) . . ? C2A C1A P1 119.8(2) . . ? C6A C1A P1 121.9(3) . . ? C3A C2A C1A 120.6(3) . . ? C4A C3A C2A 120.1(4) . . ? C5A C4A C3A 120.5(4) . . ? C4A C5A C6A 120.1(4) . . ? C5A C6A C1A 120.3(3) . . ? C2B C1B C6B 118.3(3) . . ? C2B C1B P1 122.2(3) . . ? C6B C1B P1 119.5(3) . . ? C1B C2B C3B 120.2(4) . . ? C4B C3B C2B 121.1(4) . . ? C5B C4B C3B 118.6(4) . . ? C4B C5B C6B 122.0(4) . . ? C5B C6B C1B 119.9(4) . . ? C2C C1C C6C 119.5(3) . . ? C2C C1C P1 121.7(3) . . ? C6C C1C P1 118.7(3) . . ? C1C C2C C3C 120.3(4) . . ? C4C C3C C2C 119.3(4) . . ? C5C C4C C3C 120.4(4) . . ? C4C C5C C6C 120.5(4) . . ? C1C C6C C5C 119.9(4) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 1.236 _refine_diff_density_min -0.471 _refine_diff_density_rms 0.101 # Attachment 'Complex cis-1revised.cif' data_4276 _database_code_depnum_ccdc_archive 'CCDC 610657' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H42 Br2 N6 O2 Pd S2' _chemical_formula_weight 849.04 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' 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' O O 0.0106 0.0060 '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 10.0059(6) _cell_length_b 11.4835(7) _cell_length_c 16.1385(10) _cell_angle_alpha 76.031(1) _cell_angle_beta 78.306(2) _cell_angle_gamma 84.751(1) _cell_volume 1760.40(19) _cell_formula_units_Z 2 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 3009 _cell_measurement_theta_min 2.49 _cell_measurement_theta_max 25.48 _exptl_crystal_description Plate _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.46 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.602 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 856 _exptl_absorpt_coefficient_mu 2.951 _exptl_absorpt_correction_type 'Sadabs, (Sheldrick 2001)' _exptl_absorpt_correction_T_min 0.3438 _exptl_absorpt_correction_T_max 0.7568 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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 12426 _diffrn_reflns_av_R_equivalents 0.0269 _diffrn_reflns_av_sigmaI/netI 0.0564 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.83 _diffrn_reflns_theta_max 27.50 _reflns_number_total 8012 _reflns_number_gt 6199 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _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^)+(0.0506P)^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 8012 _refine_ls_number_parameters 396 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0571 _refine_ls_R_factor_gt 0.0408 _refine_ls_wR_factor_ref 0.1006 _refine_ls_wR_factor_gt 0.0946 _refine_ls_goodness_of_fit_ref 0.975 _refine_ls_restrained_S_all 0.975 _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 0.22822(2) 0.82055(2) 0.774141(16) 0.02713(8) Uani 1 1 d . . . Br1 Br 0.01945(4) 0.92433(4) 0.84029(3) 0.04147(11) Uani 1 1 d . . . Br2 Br 0.38465(4) 0.95486(4) 0.80335(3) 0.04546(12) Uani 1 1 d . . . S1 S 0.34642(11) 0.39405(9) 1.02117(6) 0.0470(3) Uani 1 1 d . . . S2 S 0.18853(10) 0.98382(10) 0.42953(6) 0.0452(2) Uani 1 1 d . . . N1 N 0.4774(3) 0.7717(3) 0.64607(18) 0.0320(6) Uani 1 1 d . . . N2 N 0.4562(3) 0.6331(2) 0.76231(17) 0.0296(6) Uani 1 1 d . . . N3 N 0.0325(3) 0.6244(3) 0.80746(18) 0.0323(6) Uani 1 1 d . . . N4 N 0.0653(3) 0.7157(3) 0.67303(17) 0.0314(6) Uani 1 1 d . . . C1 C 0.3945(3) 0.7354(3) 0.7237(2) 0.0261(7) Uani 1 1 d . . . C2 C 0.5893(3) 0.6931(3) 0.6362(2) 0.0376(8) Uani 1 1 d . . . H2 H 0.6614 0.6997 0.5881 0.045 Uiso 1 1 calc R . . C3 C 0.5750(4) 0.6052(3) 0.7091(2) 0.0371(8) Uani 1 1 d . . . H3 H 0.6345 0.5377 0.7214 0.045 Uiso 1 1 calc R . . C4 C 0.4605(4) 0.8840(3) 0.5835(2) 0.0406(9) Uani 1 1 d . . . H4A H 0.3813 0.9297 0.6065 0.061 Uiso 1 1 calc R . . H4B H 0.4477 0.8671 0.5296 0.061 Uiso 1 1 calc R . . H4C H 0.5413 0.9302 0.5725 0.061 Uiso 1 1 calc R . . C5 C 0.4079(3) 0.5610(3) 0.8483(2) 0.0303(7) Uani 1 1 d . . . H5A H 0.3415 0.6098 0.8807 0.036 Uiso 1 1 calc R . . H5B H 0.4852 0.5394 0.8787 0.036 Uiso 1 1 calc R . . C6 C 0.3418(3) 0.4469(3) 0.8493(2) 0.0297(7) Uani 1 1 d . . . C7 C 0.3111(4) 0.4252(4) 0.7750(2) 0.0375(8) Uani 1 1 d . . . H7 H 0.3308 0.4829 0.7223 0.045 Uiso 1 1 calc R . . C8 C 0.2524(4) 0.3210(4) 0.7761(3) 0.0524(11) Uani 1 1 d . . . H8 H 0.2333 0.3078 0.7244 0.063 Uiso 1 1 calc R . . C9 C 0.2217(4) 0.2367(4) 0.8519(3) 0.0520(11) Uani 1 1 d . . . H9 H 0.1824 0.1651 0.8525 0.062 Uiso 1 1 calc R . . C10 C 0.2485(4) 0.2568(3) 0.9282(3) 0.0427(9) Uani 1 1 d . . . H10 H 0.2255 0.1994 0.9806 0.051 Uiso 1 1 calc R . . C11 C 0.3089(3) 0.3604(3) 0.9275(2) 0.0334(8) Uani 1 1 d . . . C12 C 0.3233(5) 0.2552(4) 1.1016(3) 0.0640(13) Uani 1 1 d . . . H12A H 0.2303 0.2309 1.1096 0.096 Uiso 1 1 calc R . . H12B H 0.3406 0.2660 1.1562 0.096 Uiso 1 1 calc R . . H12C H 0.3865 0.1936 1.0824 0.096 Uiso 1 1 calc R . . C13 C 0.1041(3) 0.7123(3) 0.7494(2) 0.0289(7) Uani 1 1 d . . . C14 C -0.0511(4) 0.5749(4) 0.7687(3) 0.0416(9) Uani 1 1 d . . . H14 H -0.1108 0.5125 0.7958 0.050 Uiso 1 1 calc R . . C15 C -0.0314(4) 0.6325(3) 0.6851(2) 0.0399(9) Uani 1 1 d . . . H15 H -0.0755 0.6187 0.6424 0.048 Uiso 1 1 calc R . . C16 C 0.0342(4) 0.5906(4) 0.9001(2) 0.0415(9) Uani 1 1 d . . . H16A H 0.0805 0.5124 0.9140 0.062 Uiso 1 1 calc R . . H16B H -0.0589 0.5873 0.9324 0.062 Uiso 1 1 calc R . . H16C H 0.0820 0.6497 0.9156 0.062 Uiso 1 1 calc R . . C17 C 0.1084(4) 0.8031(3) 0.5929(2) 0.0326(8) Uani 1 1 d . . . H17A H 0.1511 0.8681 0.6062 0.039 Uiso 1 1 calc R . . H17B H 0.0272 0.8378 0.5690 0.039 Uiso 1 1 calc R . . C18 C 0.2080(3) 0.7543(3) 0.5234(2) 0.0323(8) Uani 1 1 d . . . C19 C 0.2547(4) 0.6355(3) 0.5365(3) 0.0421(9) Uani 1 1 d . . . H19 H 0.2243 0.5820 0.5899 0.051 Uiso 1 1 calc R . . C20 C 0.3462(5) 0.5945(4) 0.4716(3) 0.0582(12) Uani 1 1 d . . . H20 H 0.3760 0.5132 0.4804 0.070 Uiso 1 1 calc R . . C21 C 0.3925(5) 0.6728(5) 0.3949(3) 0.0602(12) Uani 1 1 d . . . H21 H 0.4555 0.6446 0.3516 0.072 Uiso 1 1 calc R . . C22 C 0.3492(4) 0.7924(4) 0.3792(3) 0.0499(11) Uani 1 1 d . . . H22 H 0.3837 0.8454 0.3264 0.060 Uiso 1 1 calc R . . C23 C 0.2534(4) 0.8338(3) 0.4431(2) 0.0363(8) Uani 1 1 d . . . C24 C 0.2458(4) 1.0516(4) 0.3165(2) 0.0509(11) Uani 1 1 d . . . H24A H 0.3448 1.0464 0.3029 0.076 Uiso 1 1 calc R . . H24B H 0.2140 1.1352 0.3045 0.076 Uiso 1 1 calc R . . H24C H 0.2094 1.0096 0.2811 0.076 Uiso 1 1 calc R . . N1S N 0.9520(3) 0.7437(3) 0.37193(19) 0.0398(7) Uani 1 1 d . . . O1S O 0.8685(3) 0.6432(3) 0.50934(18) 0.0611(8) Uani 1 1 d . . . C1S C 0.9485(4) 0.6524(4) 0.4399(3) 0.0472(10) Uani 1 1 d . . . H1S H 1.0132 0.5886 0.4346 0.057 Uiso 1 1 calc R . . C2S C 0.8576(5) 0.8464(4) 0.3768(3) 0.0655(14) Uani 1 1 d . . . H2S1 H 0.7991 0.8331 0.4337 0.098 Uiso 1 1 calc R . . H2S2 H 0.8021 0.8570 0.3325 0.098 Uiso 1 1 calc R . . H2S3 H 0.9085 0.9179 0.3674 0.098 Uiso 1 1 calc R . . C3S C 1.0529(4) 0.7483(4) 0.2936(3) 0.0574(12) Uani 1 1 d . . . H3S1 H 1.1086 0.6741 0.2991 0.086 Uiso 1 1 calc R . . H3S2 H 1.1105 0.8154 0.2846 0.086 Uiso 1 1 calc R . . H3S3 H 1.0074 0.7584 0.2445 0.086 Uiso 1 1 calc R . . N2S N 0.7094(3) 0.1957(3) 0.9120(2) 0.0426(8) Uani 1 1 d . . . O2S O 0.7015(3) 0.3874(3) 0.8324(2) 0.0604(8) Uani 1 1 d . . . C4S C 0.6607(4) 0.2855(4) 0.8560(3) 0.0489(10) Uani 1 1 d . . . H4S H 0.5879 0.2693 0.8323 0.059 Uiso 1 1 calc R . . C5S C 0.6587(6) 0.0763(4) 0.9333(4) 0.0765(16) Uani 1 1 d . . . H5S1 H 0.6264 0.0518 0.9955 0.115 Uiso 1 1 calc R . . H5S2 H 0.7316 0.0207 0.9154 0.115 Uiso 1 1 calc R . . H5S3 H 0.5841 0.0761 0.9032 0.115 Uiso 1 1 calc R . . C6S C 0.8205(5) 0.2112(5) 0.9521(3) 0.0787(16) Uani 1 1 d . . . H6S1 H 0.9006 0.1649 0.9310 0.118 Uiso 1 1 calc R . . H6S2 H 0.7949 0.1837 1.0147 0.118 Uiso 1 1 calc R . . H6S3 H 0.8408 0.2955 0.9377 0.118 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 Pd1 0.02653(14) 0.02656(14) 0.02600(14) -0.00254(10) -0.00372(10) -0.00132(10) Br1 0.0329(2) 0.0423(2) 0.0468(2) -0.01168(17) -0.00253(16) 0.00391(16) Br2 0.0372(2) 0.0445(2) 0.0596(3) -0.0214(2) -0.00692(18) -0.00602(17) S1 0.0604(6) 0.0448(6) 0.0347(5) 0.0067(4) -0.0169(5) -0.0211(5) S2 0.0471(6) 0.0469(6) 0.0312(5) 0.0009(4) 0.0009(4) 0.0064(5) N1 0.0328(15) 0.0305(16) 0.0285(15) -0.0003(12) -0.0035(12) -0.0024(12) N2 0.0319(15) 0.0267(15) 0.0273(15) -0.0021(12) -0.0041(12) -0.0002(12) N3 0.0308(15) 0.0339(16) 0.0282(15) -0.0013(12) -0.0030(12) -0.0013(12) N4 0.0335(15) 0.0353(16) 0.0245(14) -0.0047(12) -0.0049(12) -0.0032(13) C1 0.0261(16) 0.0241(17) 0.0258(16) -0.0016(13) -0.0033(13) -0.0040(13) C2 0.0273(18) 0.044(2) 0.039(2) -0.0125(17) 0.0044(15) -0.0020(16) C3 0.0312(18) 0.036(2) 0.042(2) -0.0093(17) -0.0045(16) 0.0034(15) C4 0.040(2) 0.045(2) 0.0298(19) 0.0082(16) -0.0065(16) -0.0095(17) C5 0.0364(18) 0.0262(17) 0.0286(17) -0.0031(14) -0.0093(14) -0.0038(14) C6 0.0274(17) 0.0269(18) 0.0326(18) -0.0040(14) -0.0049(14) 0.0017(13) C7 0.039(2) 0.043(2) 0.0324(19) -0.0108(16) -0.0068(16) -0.0064(16) C8 0.055(3) 0.060(3) 0.050(3) -0.026(2) -0.008(2) -0.011(2) C9 0.049(2) 0.038(2) 0.075(3) -0.023(2) -0.010(2) -0.0109(19) C10 0.040(2) 0.028(2) 0.056(2) -0.0031(17) -0.0065(18) -0.0037(16) C11 0.0280(17) 0.0293(19) 0.040(2) -0.0034(15) -0.0060(15) -0.0011(14) C12 0.068(3) 0.061(3) 0.053(3) 0.026(2) -0.026(2) -0.022(2) C13 0.0284(17) 0.0285(18) 0.0257(17) -0.0030(14) -0.0002(13) 0.0008(14) C14 0.035(2) 0.042(2) 0.047(2) -0.0084(18) -0.0049(17) -0.0104(17) C15 0.039(2) 0.045(2) 0.038(2) -0.0096(17) -0.0108(17) -0.0068(17) C16 0.040(2) 0.048(2) 0.0291(19) 0.0032(16) -0.0022(16) -0.0064(17) C17 0.0358(18) 0.0316(19) 0.0289(18) -0.0044(14) -0.0075(15) 0.0029(15) C18 0.0272(17) 0.043(2) 0.0266(17) -0.0080(15) -0.0059(14) -0.0002(15) C19 0.041(2) 0.039(2) 0.046(2) -0.0080(18) -0.0093(18) 0.0011(17) C20 0.059(3) 0.049(3) 0.069(3) -0.027(2) -0.011(2) 0.018(2) C21 0.053(3) 0.072(3) 0.056(3) -0.027(3) 0.001(2) 0.012(2) C22 0.045(2) 0.068(3) 0.032(2) -0.016(2) 0.0047(18) 0.004(2) C23 0.0338(19) 0.045(2) 0.0297(19) -0.0076(16) -0.0082(15) 0.0033(16) C24 0.051(2) 0.061(3) 0.032(2) 0.0055(19) -0.0055(18) -0.009(2) N1S 0.0449(18) 0.0426(19) 0.0322(17) -0.0101(14) -0.0060(14) -0.0025(15) O1S 0.0583(19) 0.083(2) 0.0336(16) -0.0040(15) -0.0014(14) 0.0002(17) C1S 0.047(2) 0.054(3) 0.042(2) -0.013(2) -0.0107(19) 0.002(2) C2S 0.092(4) 0.049(3) 0.053(3) -0.014(2) -0.013(3) 0.015(3) C3S 0.050(3) 0.078(3) 0.041(2) -0.012(2) 0.003(2) -0.016(2) N2S 0.0474(19) 0.0341(18) 0.0410(18) -0.0001(14) -0.0054(15) -0.0044(14) O2S 0.0566(19) 0.0409(18) 0.071(2) 0.0055(15) -0.0044(16) -0.0012(14) C4S 0.037(2) 0.054(3) 0.051(2) -0.009(2) -0.0019(18) 0.0023(19) C5S 0.091(4) 0.048(3) 0.079(4) -0.003(3) 0.001(3) -0.013(3) C6S 0.083(4) 0.095(4) 0.059(3) 0.002(3) -0.033(3) -0.018(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 Pd1 C1 1.982(3) . ? Pd1 C13 1.992(3) . ? Pd1 Br2 2.4785(5) . ? Pd1 Br1 2.4856(4) . ? S1 C11 1.764(4) . ? S1 C12 1.796(4) . ? S2 C23 1.763(4) . ? S2 C24 1.798(4) . ? N1 C1 1.350(4) . ? N1 C2 1.381(4) . ? N1 C4 1.453(4) . ? N2 C1 1.348(4) . ? N2 C3 1.379(4) . ? N2 C5 1.446(4) . ? N3 C13 1.347(4) . ? N3 C14 1.373(5) . ? N3 C16 1.454(4) . ? N4 C13 1.357(4) . ? N4 C15 1.375(5) . ? N4 C17 1.447(4) . ? C2 C3 1.344(5) . ? C5 C6 1.517(5) . ? C6 C7 1.379(5) . ? C6 C11 1.405(5) . ? C7 C8 1.375(5) . ? C8 C9 1.364(6) . ? C9 C10 1.386(6) . ? C10 C11 1.381(5) . ? C14 C15 1.334(5) . ? C17 C18 1.520(5) . ? C18 C19 1.381(5) . ? C18 C23 1.409(5) . ? C19 C20 1.389(5) . ? C20 C21 1.364(7) . ? C21 C22 1.381(6) . ? C22 C23 1.400(5) . ? N1S C1S 1.319(5) . ? N1S C3S 1.441(5) . ? N1S C2S 1.449(5) . ? O1S C1S 1.226(5) . ? N2S C4S 1.324(5) . ? N2S C6S 1.439(6) . ? N2S C5S 1.444(6) . ? O2S C4S 1.220(5) . ? 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 C1 Pd1 C13 92.84(13) . . ? C1 Pd1 Br2 86.57(9) . . ? C13 Pd1 Br2 179.32(9) . . ? C1 Pd1 Br1 178.81(9) . . ? C13 Pd1 Br1 87.06(9) . . ? Br2 Pd1 Br1 93.539(16) . . ? C11 S1 C12 103.9(2) . . ? C23 S2 C24 105.12(19) . . ? C1 N1 C2 111.1(3) . . ? C1 N1 C4 125.4(3) . . ? C2 N1 C4 123.2(3) . . ? C1 N2 C3 111.0(3) . . ? C1 N2 C5 125.7(3) . . ? C3 N2 C5 123.3(3) . . ? C13 N3 C14 110.8(3) . . ? C13 N3 C16 125.5(3) . . ? C14 N3 C16 123.5(3) . . ? C13 N4 C15 110.1(3) . . ? C13 N4 C17 124.6(3) . . ? C15 N4 C17 124.9(3) . . ? N2 C1 N1 104.6(3) . . ? N2 C1 Pd1 127.5(2) . . ? N1 C1 Pd1 127.7(2) . . ? C3 C2 N1 106.5(3) . . ? C2 C3 N2 106.8(3) . . ? N2 C5 C6 114.4(3) . . ? C7 C6 C11 118.3(3) . . ? C7 C6 C5 121.7(3) . . ? C11 C6 C5 119.9(3) . . ? C8 C7 C6 121.5(4) . . ? C9 C8 C7 120.1(4) . . ? C8 C9 C10 119.9(4) . . ? C11 C10 C9 120.4(4) . . ? C10 C11 C6 119.8(3) . . ? C10 C11 S1 123.7(3) . . ? C6 C11 S1 116.6(3) . . ? N3 C13 N4 104.8(3) . . ? N3 C13 Pd1 126.8(3) . . ? N4 C13 Pd1 128.2(2) . . ? C15 C14 N3 106.8(3) . . ? C14 C15 N4 107.3(3) . . ? N4 C17 C18 115.1(3) . . ? C19 C18 C23 119.4(3) . . ? C19 C18 C17 122.2(3) . . ? C23 C18 C17 118.3(3) . . ? C18 C19 C20 120.5(4) . . ? C21 C20 C19 119.7(4) . . ? C20 C21 C22 121.7(4) . . ? C21 C22 C23 119.1(4) . . ? C22 C23 C18 119.5(4) . . ? C22 C23 S2 123.1(3) . . ? C18 C23 S2 117.4(3) . . ? C1S N1S C3S 122.0(4) . . ? C1S N1S C2S 119.8(4) . . ? C3S N1S C2S 118.2(4) . . ? O1S C1S N1S 125.9(4) . . ? C4S N2S C6S 121.4(4) . . ? C4S N2S C5S 122.3(4) . . ? C6S N2S C5S 116.3(4) . . ? O2S C4S N2S 126.0(4) . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.657 _refine_diff_density_min -0.408 _refine_diff_density_rms 0.102