# 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 'Han Vinh Huynh' _publ_contact_author_email CHMHHV@NUS.EDU.SG _publ_section_title ; Syntheses and catalytic activities of pseudo-pincer and CSC pincer-type Pd(II) complexes derived from benzannulated N-heterocyclic carbenes ; loop_ _publ_author_name 'Han Vinh Huynh' 'Yuan Han' 'Dan Yuan' # Attachment 'Complex1.cif' data_6308 _database_code_depnum_ccdc_archive 'CCDC 728532' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H30 Br2 N4 Pd S' _chemical_formula_weight 768.88 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' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.8217(9) _cell_length_b 11.8738(9) _cell_length_c 12.7681(9) _cell_angle_alpha 69.492(2) _cell_angle_beta 75.399(2) _cell_angle_gamma 64.8290(10) _cell_volume 1507.98(19) _cell_formula_units_Z 2 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 4075 _cell_measurement_theta_min 2.18 _cell_measurement_theta_max 27.51 _exptl_crystal_description BLOCK _exptl_crystal_colour COLOURLESS _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 'Not Measured' _exptl_crystal_density_diffrn 1.693 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 764 _exptl_absorpt_coefficient_mu 3.363 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4991 _exptl_absorpt_correction_T_max 0.7297 _exptl_absorpt_process_details 'Sadabs, (Sheldrick 2001)' _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 15898 _diffrn_reflns_av_R_equivalents 0.0557 _diffrn_reflns_av_sigmaI/netI 0.0605 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.72 _diffrn_reflns_theta_max 25.00 _reflns_number_total 5301 _reflns_number_gt 4384 _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^)+(0.0800P)^2^+2.2425P] 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 5301 _refine_ls_number_parameters 361 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.0890 _refine_ls_R_factor_gt 0.0732 _refine_ls_wR_factor_ref 0.1697 _refine_ls_wR_factor_gt 0.1630 _refine_ls_goodness_of_fit_ref 1.215 _refine_ls_restrained_S_all 1.215 _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 0.53364(5) 1.03366(5) 0.20599(5) 0.0241(2) Uani 1 1 d . . . Br1 Br 0.43745(9) 0.87534(9) 0.23429(9) 0.0504(3) Uani 1 1 d . . . Br2 Br 0.32933(8) 1.21936(8) 0.18624(8) 0.0404(3) Uani 1 1 d . . . S1 S 0.85928(19) 1.0902(2) -0.03142(19) 0.0365(5) Uani 1 1 d . . . N1 N 0.7395(6) 0.7915(6) 0.3105(6) 0.0323(15) Uani 1 1 d . . . N2 N 0.7743(6) 0.8438(6) 0.1290(6) 0.0302(15) Uani 1 1 d . . . N3 N 0.6570(6) 1.1764(6) 0.2641(6) 0.0330(16) Uani 1 1 d . . . N4 N 0.6211(6) 1.2535(6) 0.0913(6) 0.0285(15) Uani 1 1 d . . . C1 C 0.6919(6) 0.8841(6) 0.2159(6) 0.0233(16) Uani 1 1 d . . . C2 C 0.8507(7) 0.6967(7) 0.2826(7) 0.0322(19) Uani 1 1 d . . . C3 C 0.9331(9) 0.5841(9) 0.3497(9) 0.048(2) Uani 1 1 d . . . H3 H 0.9198 0.5632 0.4288 0.058 Uiso 1 1 calc R . . C4 C 1.0334(9) 0.5069(10) 0.2937(10) 0.062(3) Uani 1 1 d . . . H4 H 1.0901 0.4308 0.3361 0.075 Uiso 1 1 calc R . . C5 C 1.0548(9) 0.5349(9) 0.1802(11) 0.065(3) Uani 1 1 d . . . H5 H 1.1251 0.4777 0.1464 0.078 Uiso 1 1 calc R . . C6 C 0.9746(9) 0.6475(9) 0.1111(9) 0.048(2) Uani 1 1 d . . . H6 H 0.9882 0.6672 0.0321 0.058 Uiso 1 1 calc R . . C7 C 0.8740(7) 0.7275(8) 0.1677(7) 0.0328(19) Uani 1 1 d . . . C8 C 0.6771(9) 0.7913(8) 0.4241(7) 0.041(2) Uani 1 1 d . . . H8A H 0.5947 0.8624 0.4194 0.050 Uiso 1 1 calc R . . H8B H 0.7267 0.8089 0.4631 0.050 Uiso 1 1 calc R . . C9 C 0.6580(8) 0.6666(8) 0.4945(7) 0.0334(19) Uani 1 1 d . . . C10 C 0.6448(9) 0.6408(9) 0.6091(8) 0.049(2) Uani 1 1 d . . . H10 H 0.6497 0.6992 0.6403 0.059 Uiso 1 1 calc R . . C11 C 0.6246(12) 0.5316(12) 0.6798(9) 0.076(4) Uani 1 1 d . . . H11 H 0.6139 0.5169 0.7583 0.091 Uiso 1 1 calc R . . C12 C 0.6200(11) 0.4436(11) 0.6347(10) 0.066(3) Uani 1 1 d . . . H12 H 0.6077 0.3677 0.6819 0.079 Uiso 1 1 calc R . . C13 C 0.6337(9) 0.4691(9) 0.5202(10) 0.054(3) Uani 1 1 d . . . H13 H 0.6317 0.4092 0.4888 0.065 Uiso 1 1 calc R . . C14 C 0.6503(9) 0.5805(9) 0.4498(8) 0.045(2) Uani 1 1 d . . . H14 H 0.6564 0.5977 0.3713 0.054 Uiso 1 1 calc R . . C16 C 0.6946(7) 1.2822(8) 0.2193(7) 0.0325(18) Uani 1 1 d . . . C17 C 0.7483(10) 1.3353(10) 0.2664(8) 0.050(2) Uani 1 1 d . . . H17 H 0.7688 1.2978 0.3406 0.059 Uiso 1 1 calc R . . C18 C 0.7692(11) 1.4437(10) 0.1991(9) 0.058(3) Uani 1 1 d . . . H18 H 0.8041 1.4829 0.2280 0.069 Uiso 1 1 calc R . . C19 C 0.7407(10) 1.4978(10) 0.0901(9) 0.055(3) Uani 1 1 d . . . H19 H 0.7559 1.5736 0.0474 0.066 Uiso 1 1 calc R . . C20 C 0.6903(8) 1.4451(8) 0.0405(8) 0.040(2) Uani 1 1 d . . . H20 H 0.6715 1.4821 -0.0343 0.049 Uiso 1 1 calc R . . C21 C 0.6696(7) 1.3333(7) 0.1098(7) 0.0302(18) Uani 1 1 d . . . C22 C 0.6636(8) 1.0999(8) 0.3831(7) 0.0332(19) Uani 1 1 d . . . H22A H 0.6090 1.0505 0.4029 0.040 Uiso 1 1 calc R . . H22B H 0.6303 1.1596 0.4302 0.040 Uiso 1 1 calc R . . C23 C 0.7928(8) 1.0081(8) 0.4105(7) 0.0338(19) Uani 1 1 d . . . C24 C 0.8162(10) 0.9585(9) 0.5223(8) 0.048(2) Uani 1 1 d . . . H24 H 0.7529 0.9881 0.5787 0.058 Uiso 1 1 calc R . . C25 C 0.9318(12) 0.8662(12) 0.5507(10) 0.074(4) Uani 1 1 d . . . H25 H 0.9488 0.8367 0.6258 0.089 Uiso 1 1 calc R . . C26 C 1.0235(11) 0.8165(12) 0.4689(11) 0.072(3) Uani 1 1 d . . . H26 H 1.0997 0.7486 0.4892 0.086 Uiso 1 1 calc R . . C27 C 1.0018(10) 0.8671(10) 0.3586(9) 0.059(3) Uani 1 1 d . . . H27 H 1.0650 0.8368 0.3024 0.071 Uiso 1 1 calc R . . C28 C 0.8878(8) 0.9622(9) 0.3294(8) 0.044(2) Uani 1 1 d . . . H28 H 0.8742 0.9966 0.2532 0.052 Uiso 1 1 calc R . . C29 C 0.7526(8) 0.9019(8) 0.0107(7) 0.0348(19) Uani 1 1 d . . . H29A H 0.6687 0.9705 0.0062 0.042 Uiso 1 1 calc R . . H29B H 0.7535 0.8357 -0.0189 0.042 Uiso 1 1 calc R . . C30 C 0.8496(8) 0.9592(8) -0.0640(7) 0.0338(19) Uani 1 1 d . . . H30A H 0.8311 0.9897 -0.1419 0.041 Uiso 1 1 calc R . . H30B H 0.9328 0.8892 -0.0605 0.041 Uiso 1 1 calc R . . C31 C 0.7294(8) 1.2293(8) -0.0956(7) 0.0353(19) Uani 1 1 d . . . H31A H 0.7525 1.3056 -0.1210 0.042 Uiso 1 1 calc R . . H31B H 0.7174 1.2150 -0.1625 0.042 Uiso 1 1 calc R . . C32 C 0.6042(7) 1.2588(8) -0.0193(6) 0.0312(18) Uani 1 1 d . . . H32A H 0.5455 1.3452 -0.0539 0.037 Uiso 1 1 calc R . . H32B H 0.5674 1.1958 -0.0115 0.037 Uiso 1 1 calc R . . C15 C 0.6130(6) 1.1584(6) 0.1859(6) 0.0196(15) Uani 1 1 d U . . 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 0.0230(3) 0.0164(3) 0.0325(3) -0.0083(2) -0.0047(2) -0.0049(2) Br1 0.0472(6) 0.0319(5) 0.0813(7) -0.0110(5) -0.0213(5) -0.0196(4) Br2 0.0310(5) 0.0296(5) 0.0565(6) -0.0193(4) -0.0093(4) 0.0003(4) S1 0.0293(11) 0.0301(11) 0.0468(13) -0.0085(10) -0.0088(9) -0.0075(9) N1 0.031(4) 0.024(3) 0.044(4) -0.009(3) -0.009(3) -0.010(3) N2 0.025(3) 0.011(3) 0.046(4) -0.002(3) -0.006(3) -0.003(3) N3 0.037(4) 0.026(4) 0.035(4) -0.005(3) -0.004(3) -0.013(3) N4 0.023(3) 0.016(3) 0.043(4) -0.007(3) -0.002(3) -0.006(3) C1 0.016(4) 0.013(3) 0.038(4) -0.009(3) -0.003(3) 0.000(3) C2 0.020(4) 0.022(4) 0.049(5) -0.005(4) -0.010(4) -0.003(3) C3 0.042(5) 0.034(5) 0.056(6) 0.001(4) -0.016(5) -0.010(4) C4 0.037(6) 0.039(6) 0.083(8) 0.007(6) -0.015(6) -0.002(5) C5 0.037(6) 0.022(5) 0.099(9) -0.004(5) 0.007(6) 0.004(4) C6 0.042(5) 0.035(5) 0.058(6) -0.012(5) 0.000(5) -0.009(4) C7 0.027(4) 0.024(4) 0.043(5) -0.007(4) -0.001(4) -0.009(3) C8 0.052(6) 0.037(5) 0.040(5) -0.018(4) -0.007(4) -0.014(4) C9 0.034(5) 0.025(4) 0.035(5) -0.004(4) -0.008(4) -0.006(4) C10 0.060(6) 0.043(6) 0.039(5) -0.011(4) -0.010(5) -0.013(5) C11 0.095(10) 0.074(8) 0.042(6) 0.017(6) -0.017(6) -0.038(8) C12 0.076(8) 0.044(6) 0.071(8) 0.020(6) -0.029(6) -0.034(6) C13 0.055(6) 0.033(5) 0.082(8) -0.016(5) -0.016(6) -0.018(5) C14 0.049(6) 0.043(5) 0.046(5) -0.015(4) -0.003(4) -0.019(5) C16 0.030(4) 0.026(4) 0.041(5) -0.011(4) -0.003(4) -0.009(4) C17 0.064(7) 0.056(6) 0.045(6) -0.019(5) -0.009(5) -0.033(5) C18 0.086(8) 0.051(6) 0.060(7) -0.023(5) 0.000(6) -0.047(6) C19 0.068(7) 0.047(6) 0.064(7) -0.016(5) 0.003(5) -0.040(6) C20 0.048(5) 0.029(5) 0.044(5) -0.008(4) -0.005(4) -0.017(4) C21 0.031(4) 0.025(4) 0.036(5) -0.014(3) -0.003(3) -0.007(3) C22 0.041(5) 0.025(4) 0.033(4) -0.006(3) -0.002(4) -0.015(4) C23 0.035(5) 0.034(5) 0.037(5) -0.009(4) -0.007(4) -0.017(4) C24 0.064(7) 0.044(6) 0.039(5) -0.009(4) -0.004(5) -0.025(5) C25 0.089(9) 0.074(8) 0.050(7) 0.006(6) -0.040(7) -0.022(7) C26 0.057(7) 0.059(7) 0.083(9) -0.009(7) -0.027(7) -0.005(6) C27 0.054(7) 0.057(7) 0.062(7) -0.016(6) 0.000(5) -0.020(6) C28 0.039(5) 0.042(5) 0.046(5) -0.005(4) -0.009(4) -0.016(4) C29 0.037(5) 0.029(4) 0.037(5) -0.011(4) -0.006(4) -0.009(4) C30 0.032(4) 0.031(4) 0.031(4) -0.011(4) -0.002(4) -0.004(4) C31 0.038(5) 0.027(4) 0.036(5) -0.004(4) -0.010(4) -0.009(4) C32 0.029(4) 0.028(4) 0.035(5) -0.007(4) -0.010(4) -0.008(4) C15 0.020(2) 0.018(2) 0.024(2) -0.0046(16) -0.0014(16) -0.0109(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 1.951(7) . ? Pd1 C15 1.984(6) . ? Pd1 Br1 2.4684(10) . ? Pd1 Br2 2.4792(9) . ? S1 C30 1.799(8) . ? S1 C31 1.812(8) . ? N1 C1 1.368(10) . ? N1 C2 1.381(10) . ? N1 C8 1.451(11) . ? N2 C1 1.357(10) . ? N2 C7 1.403(10) . ? N2 C29 1.462(10) . ? N3 C15 1.348(9) . ? N3 C16 1.395(10) . ? N3 C22 1.474(10) . ? N4 C15 1.349(9) . ? N4 C21 1.404(10) . ? N4 C32 1.452(10) . ? C2 C7 1.366(12) . ? C2 C3 1.408(11) . ? C3 C4 1.366(14) . ? C4 C5 1.350(16) . ? C5 C6 1.408(13) . ? C6 C7 1.387(12) . ? C8 C9 1.518(11) . ? C9 C10 1.367(12) . ? C9 C14 1.377(12) . ? C10 C11 1.374(14) . ? C11 C12 1.382(17) . ? C12 C13 1.367(15) . ? C13 C14 1.377(13) . ? C16 C21 1.368(11) . ? C16 C17 1.400(12) . ? C17 C18 1.358(13) . ? C18 C19 1.374(14) . ? C19 C20 1.390(13) . ? C20 C21 1.396(11) . ? C22 C23 1.493(11) . ? C23 C28 1.385(12) . ? C23 C24 1.391(12) . ? C24 C25 1.378(15) . ? C25 C26 1.390(17) . ? C26 C27 1.367(15) . ? C27 C28 1.376(14) . ? C29 C30 1.531(11) . ? C31 C32 1.528(11) . ? 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 C15 94.5(3) . . ? C1 Pd1 Br1 84.7(2) . . ? C15 Pd1 Br1 178.8(2) . . ? C1 Pd1 Br2 176.8(2) . . ? C15 Pd1 Br2 87.8(2) . . ? Br1 Pd1 Br2 93.06(4) . . ? C30 S1 C31 102.9(4) . . ? C1 N1 C2 110.9(7) . . ? C1 N1 C8 123.8(7) . . ? C2 N1 C8 125.3(7) . . ? C1 N2 C7 111.4(6) . . ? C1 N2 C29 124.4(6) . . ? C7 N2 C29 123.6(7) . . ? C15 N3 C16 111.2(6) . . ? C15 N3 C22 126.6(6) . . ? C16 N3 C22 122.2(7) . . ? C15 N4 C21 111.0(6) . . ? C15 N4 C32 124.4(6) . . ? C21 N4 C32 123.8(6) . . ? N2 C1 N1 104.7(6) . . ? N2 C1 Pd1 127.0(5) . . ? N1 C1 Pd1 128.1(5) . . ? C7 C2 N1 107.5(7) . . ? C7 C2 C3 120.9(8) . . ? N1 C2 C3 131.6(9) . . ? C4 C3 C2 116.4(9) . . ? C5 C4 C3 123.0(9) . . ? C4 C5 C6 121.8(10) . . ? C7 C6 C5 115.4(9) . . ? C2 C7 C6 122.5(8) . . ? C2 C7 N2 105.5(7) . . ? C6 C7 N2 131.9(8) . . ? N1 C8 C9 115.2(7) . . ? C10 C9 C14 118.6(8) . . ? C10 C9 C8 117.5(8) . . ? C14 C9 C8 123.8(8) . . ? C9 C10 C11 121.7(10) . . ? C10 C11 C12 119.5(10) . . ? C13 C12 C11 118.8(9) . . ? C12 C13 C14 121.4(10) . . ? C13 C14 C9 119.9(9) . . ? C21 C16 N3 106.3(7) . . ? C21 C16 C17 121.8(8) . . ? N3 C16 C17 131.8(8) . . ? C18 C17 C16 116.5(9) . . ? C17 C18 C19 122.0(9) . . ? C18 C19 C20 122.7(9) . . ? C19 C20 C21 115.1(9) . . ? C16 C21 C20 121.9(8) . . ? C16 C21 N4 106.0(7) . . ? C20 C21 N4 132.2(8) . . ? N3 C22 C23 114.5(7) . . ? C28 C23 C24 118.5(8) . . ? C28 C23 C22 122.3(7) . . ? C24 C23 C22 119.1(8) . . ? C25 C24 C23 120.2(10) . . ? C24 C25 C26 120.3(10) . . ? C27 C26 C25 119.5(10) . . ? C26 C27 C28 120.2(10) . . ? C27 C28 C23 121.1(9) . . ? N2 C29 C30 114.0(7) . . ? C29 C30 S1 117.2(6) . . ? C32 C31 S1 115.1(6) . . ? N4 C32 C31 111.2(6) . . ? N3 C15 N4 105.5(6) . . ? N3 C15 Pd1 128.4(5) . . ? N4 C15 Pd1 125.7(5) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 2.060 _refine_diff_density_min -0.902 _refine_diff_density_rms 0.176 # Attachment 'Complex2.cif' data_7589a _database_code_depnum_ccdc_archive 'CCDC 728533' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C33.50 H33.50 Br2 N4.50 O1.50 Pd S' _chemical_formula_weight 821.43 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.0762(5) _cell_length_b 12.6526(6) _cell_length_c 13.6890(7) _cell_angle_alpha 90.2190(10) _cell_angle_beta 106.6060(10) _cell_angle_gamma 97.6760(10) _cell_volume 1820.15(15) _cell_formula_units_Z 2 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 2906 _cell_measurement_theta_min 2.20 _cell_measurement_theta_max 21.48 _exptl_crystal_description BLOCK _exptl_crystal_colour COLOURLESS _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas 'Not Measured' _exptl_crystal_density_diffrn 1.499 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 820 _exptl_absorpt_coefficient_mu 2.795 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.6331 _exptl_absorpt_correction_T_max 0.6633 _exptl_absorpt_process_details 'Sadabs, (Sheldrick 2001)' _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 24120 _diffrn_reflns_av_R_equivalents 0.0569 _diffrn_reflns_av_sigmaI/netI 0.0705 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _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 1.63 _diffrn_reflns_theta_max 27.49 _reflns_number_total 8345 _reflns_number_gt 5632 _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. Although the final R values are good, the DMF atoms have large thermal parameters. This could be due to the loose packing or disorder of the DMF, or partial replacement of the DMF by other solvent e.g. water. ; _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^)+(0.0837P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 8345 _refine_ls_number_parameters 415 _refine_ls_number_restraints 37 _refine_ls_R_factor_all 0.0904 _refine_ls_R_factor_gt 0.0562 _refine_ls_wR_factor_ref 0.1614 _refine_ls_wR_factor_gt 0.1463 _refine_ls_goodness_of_fit_ref 1.044 _refine_ls_restrained_S_all 1.050 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1X O 0.627(2) 0.4671(18) 0.2927(12) 0.194(10) Uani 0.50 1 d PDU . . N1X N 0.8017(18) 0.5063(15) 0.3316(14) 0.181(11) Uani 0.50 1 d PDU . . C1X C 0.7127(18) 0.4472(19) 0.2544(18) 0.185(13) Uani 0.50 1 d PDU . . H1X H 0.7144 0.4079 0.1966 0.222 Uiso 0.50 1 calc PR . . C2X C 0.858(2) 0.4279(17) 0.3982(14) 0.225(16) Uani 0.50 1 d PDU . . H2X1 H 0.9277 0.4631 0.4539 0.337 Uiso 0.50 1 calc PR . . H2X2 H 0.8911 0.3792 0.3604 0.337 Uiso 0.50 1 calc PR . . H2X3 H 0.7950 0.3882 0.4254 0.337 Uiso 0.50 1 calc PR . . C3X C 0.884(2) 0.5661(16) 0.2822(18) 0.138(9) Uani 0.50 1 d PDU . . H3X1 H 0.9514 0.6104 0.3326 0.207 Uiso 0.50 1 calc PR . . H3X2 H 0.8355 0.6110 0.2330 0.207 Uiso 0.50 1 calc PR . . H3X3 H 0.9201 0.5176 0.2474 0.207 Uiso 0.50 1 calc PR . . Pd1 Pd 0.47999(4) 0.94821(3) 0.28273(3) 0.03280(14) Uani 1 1 d . . . Br1 Br 0.58664(6) 1.13099(5) 0.34375(5) 0.04803(19) Uani 1 1 d . . . Br2 Br 0.26664(5) 1.00397(5) 0.23139(4) 0.04551(18) Uani 1 1 d . . . S1 S 0.61914(18) 0.67248(13) 0.47009(13) 0.0579(5) Uani 1 1 d . . . O1 O 0.6741(5) 0.5817(4) 0.5270(5) 0.0872(18) Uani 1 1 d . . . N1 N 0.7337(4) 0.9081(4) 0.2660(3) 0.0386(11) Uani 1 1 d . . . N2 N 0.7258(4) 0.8952(4) 0.4218(3) 0.0377(11) Uani 1 1 d . . . N3 N 0.3472(4) 0.7614(4) 0.1376(3) 0.0398(11) Uani 1 1 d . . . N4 N 0.3593(5) 0.7228(4) 0.2939(4) 0.0462(12) Uani 1 1 d . . . C1 C 0.6559(5) 0.9105(4) 0.3249(4) 0.0361(12) Uani 1 1 d . . . C2 C 0.8551(5) 0.8898(5) 0.3237(5) 0.0422(14) Uani 1 1 d . . . C3 C 0.9665(6) 0.8846(5) 0.2988(5) 0.0521(16) Uani 1 1 d . . . H3 H 0.9710 0.8921 0.2316 0.063 Uiso 1 1 calc R . . C4 C 1.0705(6) 0.8679(6) 0.3774(6) 0.0608(19) Uani 1 1 d . . . H4 H 1.1477 0.8623 0.3634 0.073 Uiso 1 1 calc R . . C5 C 1.0643(6) 0.8591(6) 0.4763(6) 0.063(2) Uani 1 1 d . . . H5 H 1.1378 0.8477 0.5278 0.075 Uiso 1 1 calc R . . C6 C 0.9553(6) 0.8664(5) 0.5023(5) 0.0509(16) Uani 1 1 d . . . H6 H 0.9521 0.8616 0.5700 0.061 Uiso 1 1 calc R . . C7 C 0.8496(5) 0.8814(4) 0.4226(4) 0.0396(13) Uani 1 1 d . . . C8 C 0.6995(6) 0.9266(5) 0.1560(4) 0.0409(13) Uani 1 1 d . . . H8A H 0.7698 0.9735 0.1418 0.049 Uiso 1 1 calc R . . H8B H 0.6248 0.9642 0.1383 0.049 Uiso 1 1 calc R . . C9 C 0.6707(5) 0.8274(5) 0.0883(5) 0.0448(14) Uani 1 1 d . . . C10 C 0.6455(6) 0.7272(5) 0.1224(5) 0.0536(16) Uani 1 1 d . . . H10 H 0.6522 0.7174 0.1916 0.064 Uiso 1 1 calc R . . C11 C 0.6103(7) 0.6413(6) 0.0531(6) 0.072(2) Uani 1 1 d . . . H11 H 0.5933 0.5723 0.0757 0.086 Uiso 1 1 calc R . . C12 C 0.5995(8) 0.6550(7) -0.0494(7) 0.080(2) Uani 1 1 d . . . H12 H 0.5762 0.5956 -0.0956 0.096 Uiso 1 1 calc R . . C13 C 0.6228(8) 0.7551(7) -0.0829(6) 0.074(2) Uani 1 1 d . . . H13 H 0.6126 0.7649 -0.1527 0.088 Uiso 1 1 calc R . . C14 C 0.6608(6) 0.8400(6) -0.0157(5) 0.0577(18) Uani 1 1 d . . . H14 H 0.6807 0.9082 -0.0387 0.069 Uiso 1 1 calc R . . C15 C 0.6783(6) 0.8930(5) 0.5106(4) 0.0423(14) Uani 1 1 d . . . H15A H 0.5907 0.9094 0.4903 0.051 Uiso 1 1 calc R . . H15B H 0.7304 0.9482 0.5612 0.051 Uiso 1 1 calc R . . C16 C 0.6809(6) 0.7843(5) 0.5590(4) 0.0477(15) Uani 1 1 d . . . H16A H 0.6316 0.7816 0.6083 0.057 Uiso 1 1 calc R . . H16B H 0.7690 0.7778 0.5969 0.057 Uiso 1 1 calc R . . C17 C 0.3931(5) 0.8016(4) 0.2351(4) 0.0358(12) Uani 1 1 d . . . C18 C 0.2849(6) 0.6575(5) 0.1342(5) 0.0465(15) Uani 1 1 d . . . C19 C 0.2217(7) 0.5852(5) 0.0516(6) 0.0622(19) Uani 1 1 d . . . H19 H 0.2177 0.6011 -0.0162 0.075 Uiso 1 1 calc R . . C20 C 0.1659(8) 0.4892(6) 0.0768(6) 0.082(3) Uani 1 1 d . . . H20 H 0.1222 0.4382 0.0242 0.098 Uiso 1 1 calc R . . C21 C 0.1714(8) 0.4653(6) 0.1745(7) 0.089(3) Uani 1 1 d . . . H21 H 0.1319 0.3982 0.1866 0.107 Uiso 1 1 calc R . . C22 C 0.2334(7) 0.5362(6) 0.2580(6) 0.071(2) Uani 1 1 d . . . H22 H 0.2361 0.5199 0.3255 0.085 Uiso 1 1 calc R . . C23 C 0.2911(6) 0.6334(5) 0.2325(5) 0.0532(17) Uani 1 1 d . . . C24 C 0.3583(5) 0.8183(5) 0.0481(4) 0.0456(15) Uani 1 1 d . . . H24A H 0.4155 0.7853 0.0184 0.055 Uiso 1 1 calc R . . H24B H 0.3969 0.8921 0.0692 0.055 Uiso 1 1 calc R . . C25 C 0.2330(5) 0.8191(5) -0.0325(4) 0.0415(14) Uani 1 1 d . . . C26 C 0.2267(6) 0.8000(5) -0.1342(4) 0.0509(16) Uani 1 1 d . . . H26 H 0.2984 0.7831 -0.1513 0.061 Uiso 1 1 calc R . . C27 C 0.1140(7) 0.8060(6) -0.2101(5) 0.066(2) Uani 1 1 d . . . H27 H 0.1093 0.7914 -0.2786 0.079 Uiso 1 1 calc R . . C28 C 0.0102(7) 0.8327(6) -0.1866(5) 0.065(2) Uani 1 1 d . . . H28 H -0.0647 0.8379 -0.2390 0.078 Uiso 1 1 calc R . . C29 C 0.0143(6) 0.8521(6) -0.0863(6) 0.0632(19) Uani 1 1 d . . . H29 H -0.0581 0.8689 -0.0702 0.076 Uiso 1 1 calc R . . C30 C 0.1275(6) 0.8465(6) -0.0085(5) 0.0544(17) Uani 1 1 d . . . H30 H 0.1317 0.8614 0.0598 0.065 Uiso 1 1 calc R . . C31 C 0.3750(6) 0.7367(5) 0.4036(4) 0.0499(16) Uani 1 1 d . . . H31A H 0.2907 0.7287 0.4145 0.060 Uiso 1 1 calc R . . H31B H 0.4165 0.8095 0.4264 0.060 Uiso 1 1 calc R . . C32 C 0.4536(6) 0.6576(5) 0.4696(5) 0.061(2) Uani 1 1 d . . . H32A H 0.4138 0.5848 0.4449 0.074 Uiso 1 1 calc R . . H32B H 0.4504 0.6665 0.5399 0.074 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 O1X 0.30(2) 0.188(18) 0.074(10) -0.021(11) 0.062(14) -0.047(17) N1X 0.214(19) 0.177(17) 0.166(17) -0.046(14) 0.058(15) 0.068(15) C1X 0.22(2) 0.173(19) 0.16(2) -0.021(15) 0.010(15) 0.114(17) C2X 0.13(2) 0.25(3) 0.28(3) -0.19(3) 0.04(2) 0.01(2) C3X 0.128(17) 0.155(19) 0.146(19) 0.104(16) 0.039(15) 0.073(15) Pd1 0.0271(2) 0.0403(3) 0.0259(2) 0.00841(16) 0.00086(16) 0.00177(17) Br1 0.0397(3) 0.0448(4) 0.0512(4) 0.0032(3) 0.0023(3) 0.0005(3) Br2 0.0330(3) 0.0654(4) 0.0350(3) 0.0053(3) 0.0031(2) 0.0109(3) S1 0.0638(11) 0.0464(9) 0.0500(10) 0.0111(7) -0.0053(8) 0.0075(8) O1 0.086(4) 0.057(3) 0.097(4) 0.025(3) -0.011(3) 0.014(3) N1 0.031(2) 0.049(3) 0.035(2) 0.011(2) 0.007(2) 0.005(2) N2 0.033(2) 0.043(3) 0.029(2) 0.009(2) -0.0012(19) -0.002(2) N3 0.032(2) 0.044(3) 0.035(3) 0.002(2) -0.002(2) 0.001(2) N4 0.042(3) 0.047(3) 0.037(3) 0.008(2) -0.006(2) -0.002(2) C1 0.035(3) 0.033(3) 0.033(3) 0.008(2) 0.001(2) 0.000(2) C2 0.031(3) 0.044(3) 0.047(3) 0.014(3) 0.005(3) 0.002(2) C3 0.038(3) 0.060(4) 0.058(4) 0.017(3) 0.012(3) 0.006(3) C4 0.034(4) 0.062(4) 0.082(5) 0.018(4) 0.011(3) 0.005(3) C5 0.031(3) 0.063(4) 0.081(5) 0.022(4) -0.005(3) 0.009(3) C6 0.034(3) 0.049(4) 0.053(4) 0.011(3) -0.009(3) -0.005(3) C7 0.031(3) 0.038(3) 0.041(3) 0.008(3) 0.001(2) -0.002(2) C8 0.042(3) 0.045(3) 0.035(3) 0.014(3) 0.010(3) 0.007(3) C9 0.033(3) 0.056(4) 0.044(3) 0.010(3) 0.010(3) 0.005(3) C10 0.050(4) 0.051(4) 0.054(4) -0.001(3) 0.004(3) 0.010(3) C11 0.070(5) 0.056(5) 0.078(6) 0.000(4) 0.005(4) 0.001(4) C12 0.089(6) 0.077(6) 0.067(5) -0.020(5) 0.008(5) 0.013(5) C13 0.082(6) 0.088(6) 0.048(4) -0.006(4) 0.018(4) 0.003(5) C14 0.056(4) 0.068(5) 0.051(4) 0.008(4) 0.020(3) 0.005(3) C15 0.043(3) 0.051(4) 0.028(3) 0.000(3) 0.004(2) 0.003(3) C16 0.043(3) 0.064(4) 0.029(3) 0.014(3) 0.000(3) 0.004(3) C17 0.026(3) 0.039(3) 0.034(3) 0.010(2) -0.003(2) 0.001(2) C18 0.040(3) 0.042(3) 0.045(3) 0.008(3) -0.007(3) 0.004(3) C19 0.063(5) 0.054(4) 0.054(4) -0.003(3) -0.009(3) 0.008(3) C20 0.086(6) 0.058(5) 0.069(5) -0.006(4) -0.019(5) -0.009(4) C21 0.096(6) 0.045(4) 0.087(6) 0.012(4) -0.021(5) -0.025(4) C22 0.073(5) 0.054(4) 0.063(5) 0.020(4) -0.008(4) -0.012(4) C23 0.047(4) 0.041(3) 0.054(4) 0.007(3) -0.010(3) -0.004(3) C24 0.033(3) 0.065(4) 0.032(3) 0.010(3) -0.001(2) 0.004(3) C25 0.040(3) 0.048(3) 0.027(3) 0.002(2) -0.003(2) 0.001(3) C26 0.060(4) 0.053(4) 0.035(3) 0.002(3) 0.005(3) 0.011(3) C27 0.068(5) 0.082(5) 0.033(3) -0.011(3) -0.012(3) 0.015(4) C28 0.059(5) 0.072(5) 0.044(4) 0.000(3) -0.016(3) 0.004(4) C29 0.042(4) 0.080(5) 0.061(5) 0.001(4) 0.001(3) 0.017(3) C30 0.042(4) 0.078(5) 0.037(3) 0.001(3) 0.001(3) 0.009(3) C31 0.044(4) 0.065(4) 0.033(3) 0.014(3) 0.005(3) -0.005(3) C32 0.063(4) 0.058(4) 0.044(4) 0.020(3) -0.006(3) -0.015(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 O1X C1X 1.255(10) . ? N1X C1X 1.359(10) . ? N1X C3X 1.423(10) . ? N1X C2X 1.434(10) . ? Pd1 C17 1.987(5) . ? Pd1 C1 1.991(6) . ? Pd1 Br2 2.4649(7) . ? Pd1 Br1 2.4765(7) . ? S1 O1 1.490(5) . ? S1 C16 1.790(6) . ? S1 C32 1.817(7) . ? N1 C1 1.340(7) . ? N1 C2 1.401(7) . ? N1 C8 1.472(7) . ? N2 C1 1.360(6) . ? N2 C7 1.401(7) . ? N2 C15 1.457(7) . ? N3 C17 1.355(7) . ? N3 C18 1.394(7) . ? N3 C24 1.450(7) . ? N4 C17 1.365(7) . ? N4 C23 1.399(8) . ? N4 C31 1.467(7) . ? C2 C7 1.377(8) . ? C2 C3 1.380(8) . ? C3 C4 1.374(9) . ? C4 C5 1.379(10) . ? C5 C6 1.366(9) . ? C6 C7 1.388(8) . ? C8 C9 1.499(8) . ? C9 C10 1.374(9) . ? C9 C14 1.407(9) . ? C10 C11 1.378(9) . ? C11 C12 1.388(11) . ? C12 C13 1.365(11) . ? C13 C14 1.352(10) . ? C15 C16 1.529(8) . ? C18 C23 1.365(9) . ? C18 C19 1.406(9) . ? C19 C20 1.378(10) . ? C20 C21 1.359(11) . ? C21 C22 1.399(10) . ? C22 C23 1.402(9) . ? C24 C25 1.507(7) . ? C25 C30 1.386(9) . ? C25 C26 1.392(8) . ? C26 C27 1.389(9) . ? C27 C28 1.361(10) . ? C28 C29 1.381(10) . ? C29 C30 1.404(8) . ? C31 C32 1.538(9) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1X N1X C3X 104.1(9) . . ? C1X N1X C2X 103.8(9) . . ? C3X N1X C2X 114.9(11) . . ? O1X C1X N1X 89.8(19) . . ? C17 Pd1 C1 96.1(2) . . ? C17 Pd1 Br2 86.57(15) . . ? C1 Pd1 Br2 177.24(15) . . ? C17 Pd1 Br1 179.25(17) . . ? C1 Pd1 Br1 84.28(15) . . ? Br2 Pd1 Br1 93.03(3) . . ? O1 S1 C16 103.8(3) . . ? O1 S1 C32 106.3(3) . . ? C16 S1 C32 99.3(3) . . ? C1 N1 C2 111.1(5) . . ? C1 N1 C8 125.2(5) . . ? C2 N1 C8 123.7(5) . . ? C1 N2 C7 109.7(5) . . ? C1 N2 C15 124.8(5) . . ? C7 N2 C15 125.4(5) . . ? C17 N3 C18 110.7(5) . . ? C17 N3 C24 125.2(5) . . ? C18 N3 C24 124.1(5) . . ? C17 N4 C23 110.2(5) . . ? C17 N4 C31 124.2(5) . . ? C23 N4 C31 125.0(5) . . ? N1 C1 N2 106.5(5) . . ? N1 C1 Pd1 126.8(4) . . ? N2 C1 Pd1 126.3(4) . . ? C7 C2 C3 121.6(5) . . ? C7 C2 N1 105.8(5) . . ? C3 C2 N1 132.6(6) . . ? C4 C3 C2 116.5(6) . . ? C3 C4 C5 121.6(7) . . ? C6 C5 C4 122.4(6) . . ? C5 C6 C7 116.0(6) . . ? C2 C7 C6 121.8(6) . . ? C2 C7 N2 106.9(5) . . ? C6 C7 N2 131.3(6) . . ? N1 C8 C9 114.8(5) . . ? C10 C9 C14 119.5(6) . . ? C10 C9 C8 122.7(6) . . ? C14 C9 C8 117.6(6) . . ? C9 C10 C11 118.8(7) . . ? C10 C11 C12 121.0(8) . . ? C13 C12 C11 119.8(7) . . ? C14 C13 C12 120.0(7) . . ? C13 C14 C9 120.7(7) . . ? N2 C15 C16 111.9(5) . . ? C15 C16 S1 114.5(4) . . ? N3 C17 N4 105.7(5) . . ? N3 C17 Pd1 127.5(4) . . ? N4 C17 Pd1 126.6(4) . . ? C23 C18 N3 106.8(5) . . ? C23 C18 C19 121.9(6) . . ? N3 C18 C19 131.3(6) . . ? C20 C19 C18 115.4(7) . . ? C21 C20 C19 122.7(7) . . ? C20 C21 C22 123.0(7) . . ? C21 C22 C23 114.3(7) . . ? C18 C23 N4 106.6(5) . . ? C18 C23 C22 122.7(6) . . ? N4 C23 C22 130.7(6) . . ? N3 C24 C25 113.7(5) . . ? C30 C25 C26 119.5(5) . . ? C30 C25 C24 121.5(5) . . ? C26 C25 C24 118.8(6) . . ? C27 C26 C25 119.7(7) . . ? C28 C27 C26 120.8(7) . . ? C27 C28 C29 120.5(6) . . ? C28 C29 C30 119.5(7) . . ? C25 C30 C29 120.0(6) . . ? N4 C31 C32 114.1(6) . . ? C31 C32 S1 114.5(4) . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 1.013 _refine_diff_density_min -0.471 _refine_diff_density_rms 0.136 # Attachment 'Complex3.cif' data_7580a _database_code_depnum_ccdc_archive 'CCDC 728534' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H30 Br N5 O3 Pd S' _chemical_formula_weight 750.98 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 Orthorhombic _symmetry_space_group_name_H-M Pbcn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 31.2166(19) _cell_length_b 11.1730(7) _cell_length_c 17.0257(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 5938.3(6) _cell_formula_units_Z 8 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 1712 _cell_measurement_theta_min 2.28 _cell_measurement_theta_max 20.03 _exptl_crystal_description Block _exptl_crystal_colour Yellow _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas 'Not Measured' _exptl_crystal_density_diffrn 1.680 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3024 _exptl_absorpt_coefficient_mu 2.085 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.7054 _exptl_absorpt_correction_T_max 0.8510 _exptl_absorpt_process_details 'Sadabs, (Sheldrick 2001)' _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 32991 _diffrn_reflns_av_R_equivalents 0.1100 _diffrn_reflns_av_sigmaI/netI 0.0711 _diffrn_reflns_limit_h_min -37 _diffrn_reflns_limit_h_max 37 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.30 _diffrn_reflns_theta_max 25.00 _reflns_number_total 5235 _reflns_number_gt 3337 _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. The Rint value at 0.11 is relatively high. We have solved the structure in monoclinic cell as well. The Rint was also high for the monoclinic case and R values were not as good. We have decided that Pbcn is the correct space group. The high Rint could be due to the disorder of the NO3. For the disordered NO3 anion, restraints in bond lengths and thermal parameters were applied to keep them in acceptable values. ; _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^)+(0.0658P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5235 _refine_ls_number_parameters 413 _refine_ls_number_restraints 56 _refine_ls_R_factor_all 0.0977 _refine_ls_R_factor_gt 0.0530 _refine_ls_wR_factor_ref 0.1342 _refine_ls_wR_factor_gt 0.1173 _refine_ls_goodness_of_fit_ref 1.020 _refine_ls_restrained_S_all 1.031 _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 0.640000(14) 0.72518(4) 0.57830(3) 0.02995(16) Uani 1 1 d . . . S1 S 0.67960(5) 0.70946(16) 0.46430(10) 0.0395(4) Uani 1 1 d . . . Br1 Br 0.59676(2) 0.77416(7) 0.69284(4) 0.0421(2) Uani 1 1 d . . . N1 N 0.67528(16) 0.5286(5) 0.6912(3) 0.0351(13) Uani 1 1 d . . . N2 N 0.72439(16) 0.6321(5) 0.6334(3) 0.0379(13) Uani 1 1 d . . . N3 N 0.55982(16) 0.8198(4) 0.4954(3) 0.0317(12) Uani 1 1 d . . . N4 N 0.61596(15) 0.9283(4) 0.4770(3) 0.0330(13) Uani 1 1 d . . . C1 C 0.68130(18) 0.6212(6) 0.6405(4) 0.0317(15) Uani 1 1 d . . . C2 C 0.7146(2) 0.4807(6) 0.7155(4) 0.0392(17) Uani 1 1 d . . . C3 C 0.7244(3) 0.3850(7) 0.7640(4) 0.053(2) Uani 1 1 d . . . H3 H 0.7031 0.3385 0.7880 0.064 Uiso 1 1 calc R . . C4 C 0.7676(3) 0.3620(8) 0.7751(4) 0.062(2) Uani 1 1 d . . . H4 H 0.7759 0.2977 0.8073 0.074 Uiso 1 1 calc R . . C5 C 0.7983(2) 0.4309(8) 0.7400(5) 0.062(2) Uani 1 1 d . . . H5 H 0.8272 0.4133 0.7502 0.074 Uiso 1 1 calc R . . C6 C 0.7890(2) 0.5242(7) 0.6910(4) 0.050(2) Uani 1 1 d . . . H6 H 0.8106 0.5701 0.6669 0.060 Uiso 1 1 calc R . . C7 C 0.7459(2) 0.5468(6) 0.6789(4) 0.0400(18) Uani 1 1 d . . . C8 C 0.6342(2) 0.4853(6) 0.7221(4) 0.0422(17) Uani 1 1 d . . . H8A H 0.6114 0.5389 0.7040 0.051 Uiso 1 1 calc R . . H8B H 0.6350 0.4895 0.7796 0.051 Uiso 1 1 calc R . . C9 C 0.62313(19) 0.3594(6) 0.6983(4) 0.0361(16) Uani 1 1 d . . . C10 C 0.6047(2) 0.2829(7) 0.7524(5) 0.056(2) Uani 1 1 d . . . H10 H 0.6002 0.3082 0.8044 0.067 Uiso 1 1 calc R . . C11 C 0.5928(2) 0.1663(8) 0.7290(6) 0.064(2) Uani 1 1 d . . . H11 H 0.5802 0.1141 0.7656 0.077 Uiso 1 1 calc R . . C12 C 0.5995(2) 0.1292(7) 0.6544(5) 0.056(2) Uani 1 1 d . . . H12 H 0.5918 0.0511 0.6396 0.068 Uiso 1 1 calc R . . C13 C 0.6176(2) 0.2060(7) 0.5996(5) 0.056(2) Uani 1 1 d . . . H13 H 0.6221 0.1806 0.5476 0.068 Uiso 1 1 calc R . . C14 C 0.6288(2) 0.3198(7) 0.6225(5) 0.0485(19) Uani 1 1 d . . . H14 H 0.6408 0.3721 0.5852 0.058 Uiso 1 1 calc R . . C15 C 0.7450(2) 0.7114(6) 0.5757(4) 0.0464(18) Uani 1 1 d . . . H15A H 0.7762 0.7085 0.5824 0.056 Uiso 1 1 calc R . . H15B H 0.7356 0.7941 0.5844 0.056 Uiso 1 1 calc R . . C16 C 0.73350(19) 0.6732(7) 0.4933(4) 0.0444(18) Uani 1 1 d . . . H16A H 0.7375 0.5865 0.4890 0.053 Uiso 1 1 calc R . . H16B H 0.7534 0.7113 0.4565 0.053 Uiso 1 1 calc R . . C17 C 0.60164(19) 0.8296(6) 0.5138(3) 0.0307(15) Uani 1 1 d . . . C18 C 0.54716(19) 0.9110(6) 0.4445(4) 0.0330(15) Uani 1 1 d . . . C19 C 0.5086(2) 0.9373(6) 0.4092(4) 0.0435(18) Uani 1 1 d . . . H19 H 0.4845 0.8882 0.4168 0.052 Uiso 1 1 calc R . . C20 C 0.5064(2) 1.0376(6) 0.3626(4) 0.0451(18) Uani 1 1 d . . . H20 H 0.4805 1.0582 0.3379 0.054 Uiso 1 1 calc R . . C21 C 0.5424(2) 1.1084(6) 0.3518(4) 0.0447(18) Uani 1 1 d . . . H21 H 0.5401 1.1763 0.3196 0.054 Uiso 1 1 calc R . . C22 C 0.5816(2) 1.0840(6) 0.3862(4) 0.0407(17) Uani 1 1 d . . . H22 H 0.6057 1.1331 0.3782 0.049 Uiso 1 1 calc R . . C23 C 0.5832(2) 0.9826(6) 0.4331(4) 0.0331(15) Uani 1 1 d . . . C24 C 0.5318(2) 0.7203(6) 0.5194(4) 0.0375(16) Uani 1 1 d . . . H24A H 0.5027 0.7507 0.5282 0.045 Uiso 1 1 calc R . . H24B H 0.5422 0.6866 0.5690 0.045 Uiso 1 1 calc R . . C25 C 0.53052(19) 0.6231(6) 0.4577(4) 0.0356(16) Uani 1 1 d . . . C26 C 0.5636(2) 0.5419(6) 0.4499(5) 0.048(2) Uani 1 1 d . . . H26 H 0.5874 0.5479 0.4834 0.058 Uiso 1 1 calc R . . C27 C 0.5627(3) 0.4536(7) 0.3952(5) 0.056(2) Uani 1 1 d . . . H27 H 0.5852 0.3980 0.3919 0.067 Uiso 1 1 calc R . . C28 C 0.5278(3) 0.4466(7) 0.3440(5) 0.060(2) Uani 1 1 d . . . H28 H 0.5274 0.3878 0.3046 0.071 Uiso 1 1 calc R . . C29 C 0.4943(3) 0.5247(7) 0.3508(5) 0.058(2) Uani 1 1 d . . . H29 H 0.4706 0.5189 0.3170 0.070 Uiso 1 1 calc R . . C30 C 0.4958(2) 0.6128(6) 0.4085(4) 0.0452(18) Uani 1 1 d . . . H30 H 0.4727 0.6662 0.4139 0.054 Uiso 1 1 calc R . . C31 C 0.6616(2) 0.9576(6) 0.4745(4) 0.0414(17) Uani 1 1 d . . . H31A H 0.6728 0.9626 0.5281 0.050 Uiso 1 1 calc R . . H31B H 0.6655 1.0357 0.4493 0.050 Uiso 1 1 calc R . . C32 C 0.6860(2) 0.8626(6) 0.4288(4) 0.0486(19) Uani 1 1 d . . . H32A H 0.7165 0.8828 0.4300 0.058 Uiso 1 1 calc R . . H32B H 0.6767 0.8655 0.3739 0.058 Uiso 1 1 calc R . . N5A N 0.8146(3) 0.8636(13) 1.4377(7) 0.0331(16) Uani 0.613(13) 1 d PDU A 1 O1A O 0.8350(7) 0.7710(18) 1.4240(16) 0.091(8) Uani 0.613(13) 1 d PDU A 1 O2A O 0.7960(4) 0.9048(11) 1.4899(8) 0.118(5) Uani 0.613(13) 1 d PDU A 1 O3A O 0.8169(5) 0.9145(12) 1.3786(8) 0.118(5) Uani 0.613(13) 1 d PDU A 1 N5B N 0.8195(5) 0.8629(18) 1.4257(8) 0.0331(16) Uani 0.387(13) 1 d PDU A 2 O1B O 0.8265(9) 0.755(2) 1.4335(19) 0.051(7) Uani 0.387(13) 1 d PDU A 2 O2B O 0.7850(4) 0.8898(13) 1.3927(10) 0.070(6) Uani 0.387(13) 1 d PDU A 2 O3B O 0.8415(5) 0.9474(13) 1.4458(10) 0.082(6) Uani 0.387(13) 1 d PDU A 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 Pd1 0.0276(3) 0.0294(3) 0.0329(3) 0.0010(2) 0.0033(2) -0.0002(2) S1 0.0407(10) 0.0412(11) 0.0366(10) -0.0022(8) 0.0085(8) -0.0028(8) Br1 0.0410(4) 0.0436(4) 0.0416(4) -0.0011(3) 0.0064(3) 0.0053(3) N1 0.036(3) 0.036(3) 0.033(3) -0.001(3) 0.001(3) 0.006(3) N2 0.030(3) 0.039(3) 0.045(4) -0.003(3) 0.003(3) 0.001(3) N3 0.036(3) 0.025(3) 0.034(3) 0.005(2) 0.004(2) 0.000(2) N4 0.031(3) 0.029(3) 0.039(3) -0.002(3) 0.001(3) -0.002(2) C1 0.030(4) 0.030(4) 0.035(4) 0.003(3) -0.004(3) 0.003(3) C2 0.042(4) 0.043(5) 0.033(4) -0.002(3) 0.005(3) 0.007(3) C3 0.068(5) 0.054(5) 0.039(4) 0.011(4) 0.003(4) 0.014(4) C4 0.080(6) 0.072(6) 0.034(4) 0.005(4) -0.005(4) 0.040(5) C5 0.038(5) 0.095(7) 0.053(5) -0.009(5) -0.007(4) 0.024(5) C6 0.036(4) 0.075(6) 0.040(5) -0.010(4) 0.002(3) 0.008(4) C7 0.040(4) 0.046(5) 0.034(4) -0.010(3) -0.005(3) 0.011(3) C8 0.040(4) 0.043(4) 0.044(4) 0.010(3) 0.014(3) 0.004(3) C9 0.030(4) 0.035(4) 0.042(4) 0.004(3) 0.002(3) 0.009(3) C10 0.063(5) 0.055(5) 0.049(5) 0.017(4) 0.000(4) -0.006(4) C11 0.062(6) 0.052(6) 0.078(7) 0.021(5) 0.003(5) -0.018(4) C12 0.049(5) 0.036(5) 0.084(7) -0.001(5) -0.018(4) -0.002(4) C13 0.053(5) 0.047(6) 0.070(6) -0.015(4) 0.000(4) 0.003(4) C14 0.048(5) 0.043(4) 0.055(5) 0.009(4) 0.010(4) 0.009(4) C15 0.027(4) 0.054(5) 0.058(5) -0.002(4) 0.005(3) -0.002(3) C16 0.037(4) 0.042(4) 0.054(5) 0.001(4) 0.018(3) 0.004(3) C17 0.035(4) 0.031(4) 0.026(4) 0.000(3) 0.009(3) 0.000(3) C18 0.036(4) 0.031(4) 0.032(4) 0.001(3) 0.003(3) 0.003(3) C19 0.041(4) 0.045(5) 0.045(5) 0.005(4) 0.005(3) 0.000(3) C20 0.046(4) 0.050(5) 0.039(4) 0.009(4) 0.001(3) 0.012(4) C21 0.056(5) 0.037(4) 0.041(4) 0.008(3) 0.003(4) 0.013(4) C22 0.053(4) 0.033(4) 0.037(4) 0.001(3) 0.014(3) 0.003(3) C23 0.038(4) 0.031(4) 0.031(4) -0.002(3) -0.001(3) 0.004(3) C24 0.037(4) 0.033(4) 0.043(4) 0.004(3) 0.005(3) -0.009(3) C25 0.032(4) 0.032(4) 0.043(4) 0.010(3) 0.004(3) -0.007(3) C26 0.041(4) 0.034(4) 0.070(6) 0.004(4) 0.008(4) -0.008(3) C27 0.056(5) 0.037(5) 0.075(6) 0.001(4) 0.021(5) 0.000(4) C28 0.092(7) 0.040(5) 0.047(5) -0.001(4) 0.014(5) -0.013(5) C29 0.073(6) 0.051(5) 0.051(5) 0.004(4) -0.013(4) -0.007(5) C30 0.049(4) 0.037(4) 0.049(5) 0.002(4) 0.007(4) 0.001(4) C31 0.041(4) 0.031(4) 0.051(5) 0.007(3) -0.001(4) -0.011(3) C32 0.043(4) 0.054(5) 0.049(5) 0.012(4) 0.017(4) 0.004(4) N5A 0.033(3) 0.036(3) 0.030(3) 0.015(3) 0.002(2) -0.009(2) O1A 0.086(11) 0.076(10) 0.111(11) 0.006(7) 0.012(8) 0.013(7) O2A 0.143(7) 0.101(6) 0.110(7) 0.005(5) 0.032(5) 0.027(5) O3A 0.143(7) 0.101(6) 0.110(7) 0.005(5) 0.032(5) 0.027(5) N5B 0.033(3) 0.036(3) 0.030(3) 0.015(3) 0.002(2) -0.009(2) O1B 0.045(9) 0.040(10) 0.066(10) -0.001(7) 0.014(7) 0.004(7) O2B 0.039(7) 0.059(8) 0.111(10) 0.003(7) -0.010(7) -0.014(6) O3B 0.078(9) 0.057(9) 0.112(10) -0.008(7) -0.038(7) -0.014(7) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Pd1 C17 2.000(6) . ? Pd1 C1 2.033(6) . ? Pd1 S1 2.3078(18) . ? Pd1 Br1 2.4341(8) . ? S1 C16 1.800(7) . ? S1 C32 1.825(7) . ? N1 C1 1.361(8) . ? N1 C2 1.402(8) . ? N1 C8 1.468(7) . ? N2 C1 1.356(7) . ? N2 C7 1.400(8) . ? N2 C15 1.472(8) . ? N3 C17 1.347(7) . ? N3 C18 1.395(8) . ? N3 C24 1.472(8) . ? N4 C17 1.345(8) . ? N4 C23 1.404(7) . ? N4 C31 1.461(7) . ? C2 C7 1.375(9) . ? C2 C3 1.385(9) . ? C3 C4 1.384(9) . ? C4 C5 1.368(11) . ? C5 C6 1.366(11) . ? C6 C7 1.385(8) . ? C8 C9 1.503(9) . ? C9 C14 1.377(9) . ? C9 C10 1.382(9) . ? C10 C11 1.412(11) . ? C11 C12 1.352(11) . ? C12 C13 1.388(11) . ? C13 C14 1.376(10) . ? C15 C16 1.509(10) . ? C18 C19 1.377(9) . ? C18 C23 1.395(8) . ? C19 C20 1.375(9) . ? C20 C21 1.385(9) . ? C21 C22 1.384(9) . ? C22 C23 1.387(9) . ? C24 C25 1.511(9) . ? C25 C30 1.375(9) . ? C25 C26 1.381(9) . ? C26 C27 1.356(10) . ? C27 C28 1.397(11) . ? C28 C29 1.366(10) . ? C29 C30 1.392(10) . ? C31 C32 1.520(9) . ? N5A O2A 1.156(13) . ? N5A O3A 1.159(14) . ? N5A O1A 1.236(14) . ? N5B O3B 1.217(16) . ? N5B O1B 1.233(17) . ? N5B O2B 1.251(17) . ? 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 C17 Pd1 C1 177.3(2) . . ? C17 Pd1 S1 84.46(17) . . ? C1 Pd1 S1 93.16(18) . . ? C17 Pd1 Br1 88.66(17) . . ? C1 Pd1 Br1 93.59(18) . . ? S1 Pd1 Br1 171.10(5) . . ? C16 S1 C32 101.5(3) . . ? C16 S1 Pd1 106.7(2) . . ? C32 S1 Pd1 105.4(2) . . ? C1 N1 C2 110.9(5) . . ? C1 N1 C8 126.8(5) . . ? C2 N1 C8 122.2(5) . . ? C1 N2 C7 111.5(5) . . ? C1 N2 C15 123.2(5) . . ? C7 N2 C15 124.7(5) . . ? C17 N3 C18 111.1(5) . . ? C17 N3 C24 125.0(5) . . ? C18 N3 C24 123.7(5) . . ? C17 N4 C23 111.1(5) . . ? C17 N4 C31 121.4(5) . . ? C23 N4 C31 126.6(5) . . ? N2 C1 N1 105.2(5) . . ? N2 C1 Pd1 122.1(5) . . ? N1 C1 Pd1 132.6(4) . . ? C7 C2 C3 121.8(7) . . ? C7 C2 N1 106.5(6) . . ? C3 C2 N1 131.7(7) . . ? C4 C3 C2 116.2(7) . . ? C5 C4 C3 121.2(7) . . ? C6 C5 C4 123.2(7) . . ? C5 C6 C7 115.8(7) . . ? C2 C7 C6 121.7(7) . . ? C2 C7 N2 106.0(5) . . ? C6 C7 N2 132.3(7) . . ? N1 C8 C9 114.3(5) . . ? C14 C9 C10 118.7(7) . . ? C14 C9 C8 121.6(6) . . ? C10 C9 C8 119.6(6) . . ? C9 C10 C11 119.5(7) . . ? C12 C11 C10 120.5(8) . . ? C11 C12 C13 120.3(8) . . ? C14 C13 C12 119.0(8) . . ? C13 C14 C9 122.0(7) . . ? N2 C15 C16 110.2(6) . . ? C15 C16 S1 114.5(5) . . ? N4 C17 N3 106.3(5) . . ? N4 C17 Pd1 122.4(4) . . ? N3 C17 Pd1 131.3(5) . . ? C19 C18 C23 121.5(6) . . ? C19 C18 N3 132.4(6) . . ? C23 C18 N3 106.1(5) . . ? C20 C19 C18 118.0(7) . . ? C19 C20 C21 120.1(7) . . ? C22 C21 C20 123.3(7) . . ? C21 C22 C23 115.8(7) . . ? C22 C23 C18 121.3(6) . . ? C22 C23 N4 133.3(6) . . ? C18 C23 N4 105.4(5) . . ? N3 C24 C25 111.4(5) . . ? C30 C25 C26 118.4(7) . . ? C30 C25 C24 120.2(6) . . ? C26 C25 C24 121.4(6) . . ? C27 C26 C25 122.0(7) . . ? C26 C27 C28 119.0(7) . . ? C29 C28 C27 120.5(8) . . ? C28 C29 C30 119.1(8) . . ? C25 C30 C29 121.0(7) . . ? N4 C31 C32 110.3(5) . . ? C31 C32 S1 115.5(5) . . ? O2A N5A O3A 120.2(17) . . ? O2A N5A O1A 137.5(17) . . ? O3A N5A O1A 102.4(17) . . ? O3B N5B O1B 129(2) . . ? O3B N5B O2B 115.2(19) . . ? O1B N5B O2B 115.9(19) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 1.176 _refine_diff_density_min -1.277 _refine_diff_density_rms 0.113 # Attachment 'SaltBx2HBr.cif' data_6301 _database_code_depnum_ccdc_archive 'CCDC 728535' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H33.50 Br2 N4 O S' _chemical_formula_weight 682.01 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' Br Br -0.2901 2.4595 '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' 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 11.504(3) _cell_length_b 11.595(3) _cell_length_c 12.552(3) _cell_angle_alpha 96.355(5) _cell_angle_beta 99.264(5) _cell_angle_gamma 98.275(5) _cell_volume 1619.7(7) _cell_formula_units_Z 2 _cell_measurement_temperature 243(2) _cell_measurement_reflns_used 3992 _cell_measurement_theta_min 2.23 _cell_measurement_theta_max 22.80 _exptl_crystal_description Block _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.398 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 695 _exptl_absorpt_coefficient_mu 2.597 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4231 _exptl_absorpt_correction_T_max 0.7812 _exptl_absorpt_process_details 'Sadabs, (Sheldrick 2001)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 243(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 16547 _diffrn_reflns_av_R_equivalents 0.0806 _diffrn_reflns_av_sigmaI/netI 0.0941 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.66 _diffrn_reflns_theta_max 24.99 _reflns_number_total 5687 _reflns_number_gt 4006 _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. One of the Br anions was found to be disordered into two positions at 64:36 occupancies. Three is also a water molecule with 0.8 occupancy. H atoms of the water molecule were located from differnt map and refined with restraints in bond length and thermal parameters. ; _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^)+(0.1204P)^2^+2.9141P] 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 5687 _refine_ls_number_parameters 378 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.1055 _refine_ls_R_factor_gt 0.0821 _refine_ls_wR_factor_ref 0.2451 _refine_ls_wR_factor_gt 0.2327 _refine_ls_goodness_of_fit_ref 1.062 _refine_ls_restrained_S_all 1.062 _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 Br1 Br 0.32434(7) 0.05854(7) 0.59741(6) 0.0563(3) Uani 1 1 d . . . Br2 Br 0.97315(17) 0.7496(2) 0.93994(18) 0.1133(9) Uani 0.636(3) 1 d P A 1 Br3 Br 0.9596(2) 0.9630(3) 0.8034(3) 0.0863(12) Uani 0.364(3) 1 d P A 2 S1 S 0.43091(19) 0.33401(17) 0.35575(16) 0.0563(5) Uani 1 1 d . . . N1 N 0.3507(4) 0.1612(4) 0.0055(4) 0.0364(11) Uani 1 1 d . . . N2 N 0.4091(5) 0.1175(4) 0.1688(4) 0.0392(12) Uani 1 1 d . . . N3 N 0.0665(5) 0.3462(5) 0.6666(5) 0.0482(14) Uani 1 1 d . . . N4 N 0.1539(5) 0.3534(5) 0.5230(5) 0.0490(14) Uani 1 1 d . . . C1 C 0.3167(6) 0.1396(5) 0.0990(5) 0.0385(14) Uani 1 1 d . . . H1 H 0.2392 0.1399 0.1137 0.046 Uiso 1 1 calc R . . C2 C 0.4717(5) 0.1536(5) 0.0134(5) 0.0342(13) Uani 1 1 d . . . C3 C 0.5502(6) 0.1680(5) -0.0612(5) 0.0398(14) Uani 1 1 d . . . H3 H 0.5252 0.1865 -0.1314 0.048 Uiso 1 1 calc R . . C4 C 0.6667(6) 0.1532(6) -0.0245(6) 0.0464(16) Uani 1 1 d . . . H4 H 0.7224 0.1618 -0.0714 0.056 Uiso 1 1 calc R . . C5 C 0.7042(6) 0.1257(6) 0.0806(6) 0.0446(16) Uani 1 1 d . . . H5 H 0.7843 0.1170 0.1017 0.054 Uiso 1 1 calc R . . C6 C 0.6279(6) 0.1111(5) 0.1538(6) 0.0401(14) Uani 1 1 d . . . H6 H 0.6540 0.0927 0.2238 0.048 Uiso 1 1 calc R . . C7 C 0.5089(5) 0.1249(5) 0.1185(5) 0.0357(13) Uani 1 1 d . . . C8 C 0.2728(6) 0.1898(5) -0.0915(5) 0.0409(15) Uani 1 1 d . . . H8A H 0.1893 0.1752 -0.0818 0.049 Uiso 1 1 calc R . . H8B H 0.2803 0.1382 -0.1564 0.049 Uiso 1 1 calc R . . C9 C 0.3061(5) 0.3180(5) -0.1084(5) 0.0373(14) Uani 1 1 d . . . C10 C 0.2927(8) 0.4081(6) -0.0315(6) 0.0555(19) Uani 1 1 d . . . H10 H 0.2638 0.3906 0.0318 0.067 Uiso 1 1 calc R . . C11 C 0.3221(9) 0.5252(7) -0.0484(7) 0.070(2) Uani 1 1 d . . . H11 H 0.3126 0.5866 0.0033 0.083 Uiso 1 1 calc R . . C12 C 0.3652(8) 0.5508(7) -0.1409(6) 0.063(2) Uani 1 1 d . . . H12 H 0.3861 0.6295 -0.1515 0.075 Uiso 1 1 calc R . . C13 C 0.3776(6) 0.4606(6) -0.2183(6) 0.0504(17) Uani 1 1 d . . . H13 H 0.4065 0.4786 -0.2814 0.060 Uiso 1 1 calc R . . C14 C 0.3475(6) 0.3436(6) -0.2034(6) 0.0446(15) Uani 1 1 d . . . H14 H 0.3550 0.2825 -0.2564 0.054 Uiso 1 1 calc R . . C15 C 0.4039(7) 0.0908(6) 0.2818(6) 0.0499(17) Uani 1 1 d . . . H15A H 0.4354 0.0177 0.2916 0.060 Uiso 1 1 calc R . . H15B H 0.3205 0.0784 0.2916 0.060 Uiso 1 1 calc R . . C16 C 0.4747(7) 0.1886(7) 0.3675(6) 0.0525(18) Uani 1 1 d . . . H16A H 0.5595 0.1941 0.3628 0.063 Uiso 1 1 calc R . . H16B H 0.4653 0.1679 0.4396 0.063 Uiso 1 1 calc R . . C17 C 0.1057(6) 0.2834(7) 0.5884(7) 0.0535(18) Uani 1 1 d . . . H17 H 0.1004 0.2011 0.5801 0.064 Uiso 1 1 calc R . . C18 C 0.0897(6) 0.4670(6) 0.6534(6) 0.0453(16) Uani 1 1 d . . . C19 C 0.0683(6) 0.5663(7) 0.7116(6) 0.0529(18) Uani 1 1 d . . . H19 H 0.0308 0.5624 0.7727 0.063 Uiso 1 1 calc R . . C20 C 0.1042(6) 0.6730(7) 0.6766(6) 0.0534(18) Uani 1 1 d . . . H20 H 0.0916 0.7431 0.7149 0.064 Uiso 1 1 calc R . . C21 C 0.1600(6) 0.6779(7) 0.5833(6) 0.0511(17) Uani 1 1 d . . . H21 H 0.1823 0.7512 0.5607 0.061 Uiso 1 1 calc R . . C22 C 0.1819(6) 0.5782(7) 0.5257(6) 0.0496(17) Uani 1 1 d . . . H22 H 0.2202 0.5816 0.4651 0.060 Uiso 1 1 calc R . . C23 C 0.1445(6) 0.4705(6) 0.5616(5) 0.0422(15) Uani 1 1 d . . . C24 C 0.0084(6) 0.2970(8) 0.7547(7) 0.057(2) Uani 1 1 d . . . H24A H 0.0433 0.3448 0.8250 0.068 Uiso 1 1 calc R . . H24B H 0.0242 0.2167 0.7592 0.068 Uiso 1 1 calc R . . C25 C -0.1263(6) 0.2958(7) 0.7323(6) 0.0480(17) Uani 1 1 d . . . C26 C -0.1794(6) 0.3851(7) 0.7793(6) 0.0529(18) Uani 1 1 d . . . H26 H -0.1325 0.4475 0.8291 0.063 Uiso 1 1 calc R . . C27 C -0.3015(7) 0.3805(8) 0.7518(6) 0.0572(19) Uani 1 1 d . . . H27 H -0.3371 0.4415 0.7818 0.069 Uiso 1 1 calc R . . C28 C -0.3726(6) 0.2872(7) 0.6806(6) 0.0529(18) Uani 1 1 d . . . H28 H -0.4555 0.2856 0.6634 0.064 Uiso 1 1 calc R . . C29 C -0.3232(6) 0.1978(7) 0.6354(6) 0.0508(17) Uani 1 1 d . . . H29 H -0.3722 0.1347 0.5879 0.061 Uiso 1 1 calc R . . C30 C -0.1992(6) 0.1997(6) 0.6595(6) 0.0474(16) Uani 1 1 d . . . H30 H -0.1648 0.1386 0.6281 0.057 Uiso 1 1 calc R . . C31 C 0.2135(6) 0.3168(7) 0.4309(6) 0.0520(17) Uani 1 1 d . . . H31A H 0.1845 0.3533 0.3672 0.062 Uiso 1 1 calc R . . H31B H 0.1951 0.2312 0.4111 0.062 Uiso 1 1 calc R . . C32 C 0.3479(6) 0.3555(7) 0.4661(6) 0.0501(17) Uani 1 1 d . . . H32A H 0.3769 0.3111 0.5241 0.060 Uiso 1 1 calc R . . H32B H 0.3638 0.4390 0.4963 0.060 Uiso 1 1 calc R . . O1W O 0.0406(12) 0.9711(16) 0.5980(16) 0.174(9) Uani 0.78(3) 1 d PD B 1 H2W H 0.003(18) 0.98(3) 0.650(14) 0.261 Uiso 0.78(3) 1 d PD . . H1W H 0.112(7) 0.99(3) 0.632(17) 0.261 Uiso 0.78(3) 1 d PD . . 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 0.0631(5) 0.0500(4) 0.0575(5) 0.0086(3) 0.0104(4) 0.0148(3) Br2 0.0799(12) 0.165(2) 0.1202(16) 0.0389(14) 0.0651(11) 0.0355(12) Br3 0.0522(15) 0.101(2) 0.119(2) 0.0593(18) 0.0222(14) 0.0135(13) S1 0.0686(13) 0.0516(10) 0.0596(11) 0.0137(9) 0.0348(10) 0.0153(9) N1 0.038(3) 0.031(3) 0.042(3) 0.007(2) 0.010(2) 0.006(2) N2 0.044(3) 0.032(3) 0.045(3) 0.008(2) 0.013(2) 0.011(2) N3 0.033(3) 0.059(4) 0.058(4) 0.019(3) 0.012(3) 0.012(3) N4 0.038(3) 0.056(4) 0.058(4) 0.013(3) 0.014(3) 0.014(3) C1 0.036(3) 0.028(3) 0.057(4) 0.009(3) 0.018(3) 0.007(3) C2 0.032(3) 0.027(3) 0.044(3) 0.004(2) 0.010(3) 0.003(2) C3 0.047(4) 0.033(3) 0.041(3) 0.007(3) 0.014(3) 0.002(3) C4 0.041(4) 0.038(3) 0.063(4) 0.005(3) 0.023(3) 0.003(3) C5 0.034(3) 0.035(3) 0.065(4) 0.002(3) 0.012(3) 0.005(3) C6 0.040(4) 0.032(3) 0.049(4) 0.005(3) 0.006(3) 0.010(3) C7 0.036(3) 0.029(3) 0.043(3) 0.010(3) 0.010(3) 0.002(2) C8 0.040(4) 0.036(3) 0.047(4) 0.005(3) 0.006(3) 0.007(3) C9 0.031(3) 0.041(3) 0.039(3) 0.008(3) 0.003(3) 0.007(3) C10 0.082(6) 0.040(4) 0.046(4) 0.006(3) 0.016(4) 0.013(4) C11 0.109(7) 0.037(4) 0.061(5) -0.001(4) 0.021(5) 0.010(4) C12 0.082(6) 0.040(4) 0.059(5) 0.011(3) 0.000(4) -0.001(4) C13 0.053(4) 0.051(4) 0.050(4) 0.018(3) 0.008(3) 0.008(3) C14 0.045(4) 0.046(4) 0.044(4) 0.006(3) 0.007(3) 0.011(3) C15 0.056(4) 0.054(4) 0.055(4) 0.028(3) 0.027(3) 0.022(3) C16 0.064(5) 0.064(5) 0.038(4) 0.011(3) 0.016(3) 0.027(4) C17 0.035(4) 0.061(4) 0.071(5) 0.022(4) 0.010(3) 0.020(3) C18 0.031(3) 0.059(4) 0.048(4) 0.013(3) 0.004(3) 0.013(3) C19 0.039(4) 0.074(5) 0.050(4) 0.013(4) 0.014(3) 0.012(4) C20 0.039(4) 0.061(5) 0.062(5) 0.005(4) 0.008(3) 0.016(3) C21 0.045(4) 0.053(4) 0.056(4) 0.013(3) 0.006(3) 0.009(3) C22 0.039(4) 0.061(4) 0.055(4) 0.018(4) 0.010(3) 0.018(3) C23 0.031(3) 0.048(4) 0.050(4) 0.011(3) 0.006(3) 0.009(3) C24 0.035(4) 0.077(5) 0.065(5) 0.036(4) 0.010(3) 0.013(4) C25 0.037(4) 0.064(4) 0.048(4) 0.026(3) 0.010(3) 0.008(3) C26 0.040(4) 0.074(5) 0.047(4) 0.014(4) 0.013(3) 0.007(4) C27 0.048(4) 0.078(5) 0.053(4) 0.015(4) 0.020(4) 0.021(4) C28 0.035(4) 0.081(5) 0.047(4) 0.021(4) 0.011(3) 0.010(4) C29 0.046(4) 0.056(4) 0.050(4) 0.017(3) 0.009(3) -0.001(3) C30 0.047(4) 0.046(4) 0.056(4) 0.021(3) 0.016(3) 0.010(3) C31 0.043(4) 0.054(4) 0.059(4) 0.005(3) 0.014(3) 0.006(3) C32 0.048(4) 0.062(4) 0.044(4) 0.005(3) 0.011(3) 0.018(3) O1W 0.086(9) 0.144(13) 0.29(2) 0.070(14) -0.002(10) 0.009(9) _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 S1 C32 1.819(7) . ? S1 C16 1.842(7) . ? N1 C1 1.333(8) . ? N1 C2 1.395(8) . ? N1 C8 1.489(8) . ? N2 C1 1.339(8) . ? N2 C7 1.392(8) . ? N2 C15 1.493(8) . ? N3 C17 1.333(10) . ? N3 C18 1.420(9) . ? N3 C24 1.505(9) . ? N4 C17 1.343(9) . ? N4 C23 1.415(9) . ? N4 C31 1.489(9) . ? C2 C3 1.408(9) . ? C2 C7 1.411(9) . ? C3 C4 1.387(10) . ? C4 C5 1.406(10) . ? C5 C6 1.376(9) . ? C6 C7 1.408(9) . ? C8 C9 1.528(9) . ? C9 C10 1.384(10) . ? C9 C14 1.399(9) . ? C10 C11 1.400(10) . ? C11 C12 1.378(12) . ? C12 C13 1.386(11) . ? C13 C14 1.392(10) . ? C15 C16 1.513(11) . ? C18 C19 1.369(10) . ? C18 C23 1.401(10) . ? C19 C20 1.388(11) . ? C20 C21 1.426(11) . ? C21 C22 1.371(11) . ? C22 C23 1.407(10) . ? C24 C25 1.528(9) . ? C25 C26 1.398(11) . ? C25 C30 1.427(11) . ? C26 C27 1.384(11) . ? C27 C28 1.391(12) . ? C28 C29 1.365(11) . ? C29 C30 1.405(10) . ? C31 C32 1.525(10) . ? 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 C32 S1 C16 103.5(3) . . ? C1 N1 C2 108.9(5) . . ? C1 N1 C8 125.7(5) . . ? C2 N1 C8 125.4(5) . . ? C1 N2 C7 108.6(5) . . ? C1 N2 C15 124.8(6) . . ? C7 N2 C15 126.7(5) . . ? C17 N3 C18 108.8(6) . . ? C17 N3 C24 125.4(6) . . ? C18 N3 C24 125.8(6) . . ? C17 N4 C23 107.5(6) . . ? C17 N4 C31 126.7(6) . . ? C23 N4 C31 125.7(6) . . ? N1 C1 N2 110.1(5) . . ? N1 C2 C3 131.9(6) . . ? N1 C2 C7 106.0(5) . . ? C3 C2 C7 122.1(6) . . ? C4 C3 C2 115.8(6) . . ? C3 C4 C5 122.2(6) . . ? C6 C5 C4 122.4(6) . . ? C5 C6 C7 116.7(6) . . ? N2 C7 C6 132.7(6) . . ? N2 C7 C2 106.5(5) . . ? C6 C7 C2 120.8(6) . . ? N1 C8 C9 111.5(5) . . ? C10 C9 C14 120.3(6) . . ? C10 C9 C8 120.2(6) . . ? C14 C9 C8 119.4(6) . . ? C9 C10 C11 119.7(7) . . ? C12 C11 C10 120.1(7) . . ? C11 C12 C13 120.1(7) . . ? C12 C13 C14 120.5(7) . . ? C13 C14 C9 119.1(7) . . ? N2 C15 C16 112.2(6) . . ? C15 C16 S1 114.5(5) . . ? N3 C17 N4 110.9(7) . . ? C19 C18 C23 122.4(7) . . ? C19 C18 N3 132.1(7) . . ? C23 C18 N3 105.5(6) . . ? C18 C19 C20 117.2(7) . . ? C19 C20 C21 121.0(7) . . ? C22 C21 C20 121.6(7) . . ? C21 C22 C23 116.9(7) . . ? C18 C23 C22 120.9(7) . . ? C18 C23 N4 107.4(6) . . ? C22 C23 N4 131.7(6) . . ? N3 C24 C25 111.2(5) . . ? C26 C25 C30 119.6(6) . . ? C26 C25 C24 122.5(7) . . ? C30 C25 C24 117.9(7) . . ? C27 C26 C25 119.2(8) . . ? C26 C27 C28 121.2(8) . . ? C29 C28 C27 120.6(7) . . ? C28 C29 C30 120.2(7) . . ? C29 C30 C25 119.1(7) . . ? N4 C31 C32 108.7(6) . . ? C31 C32 S1 113.5(5) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 2.224 _refine_diff_density_min -0.522 _refine_diff_density_rms 0.119