# Copyright The Royal society of Chemistry, 1998 ##################### # Manuscript ref: 7/09113C/DAP ##################### #Title: # #Chemoselective homogeneous hydrogenation of phenylacetylene using #thiosemicarbazone and thiobenzoylhydrazone palladium(ii) #complexes as catalysts. #by Alessia Bacchi, Mauro Carcelli, Mirco Costa, Andrea Leporati, #Paolo Pelagatti, Corrado Pelizzi, Giancarlo Pelizzi, #and Andrea Venturini data_1a #################################################################### # References relative to the crystallographic experimental section # #################################################################### _publ_section_references ; Altomare A. , Cascarano G. , Giacovazzo C. , Guagliardi A. Burla M.C. , Polidori G. , Camalli M. , J. Appl. Crystallogr., 1994, 27, 435 Nardelli, M, J. Appl. Crystallogr., 1995, 28, 659 Sheldrick, G., SHELXL-93. Program for structure refinement. 1993, University of Goettingen, Germany Walker, N. Stuart, D, Acta Crystallogr., 1983, A39, 158 Zsolnai, L. Pritzkow, H., ZORTEP. ORTEP original program modified for PC. 1994, University of Heidelberg, Germany. Allen,F.H. Kennard,O., Chemical Design Automation News, 1993, 8, 1 and 31 ; _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C13 H11 Cl N4 Pd S' _chemical_formula_weight 397.17 _chemical_melting_point ? _chemical_compound_source ? 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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Pd' 'Pd' -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'monoclinic' _symmetry_space_group_name_H-M 'C2/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 12.089(4) _cell_length_b 21.801(7) _cell_length_c 11.480(4) _cell_angle_alpha 90.00 _cell_angle_beta 108.35(3) _cell_angle_gamma 90.00 _cell_volume 2872(2) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description 'prisms' _exptl_crystal_colour 'orange' _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.837 _exptl_crystal_density_method ? _exptl_crystal_F_000 1568 _exptl_absorpt_coefficient_mu 1.617 _exptl_absorpt_correction_type 'Walker&Stuart (1983)' _exptl_absorpt_correction_T_min 0.94 _exptl_absorpt_correction_T_max 1.01 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite' _diffrn_measurement_device 'Siemens AED diffractometer' _diffrn_measurement_method '\q/2\q scan' _diffrn_standards_number 1 _diffrn_standards_interval_count 100 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 4368 _diffrn_reflns_av_R_equivalents 0.0255 _diffrn_reflns_av_sigmaI/netI 0.0201 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 30 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.10 _diffrn_reflns_theta_max 29.98 _reflns_number_total 4184 _reflns_number_observed 3188 _reflns_observed_criterion >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SIR92 (Altomare et al, 1992)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ZORTEP (Zsolnai & Pritzkow, H., 1994)' _computing_publication_material 'PARST95 (Nardelli, 1995)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 5 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[s^2^(Fo^2^)+( 0.0322P)^2^+13.5503P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment iso _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4179 _refine_ls_number_parameters 224 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0568 _refine_ls_R_factor_obs 0.0365 _refine_ls_wR_factor_all 0.1055 _refine_ls_wR_factor_obs 0.0830 _refine_ls_goodness_of_fit_all 1.117 _refine_ls_goodness_of_fit_obs 1.022 _refine_ls_restrained_S_all 1.125 _refine_ls_restrained_S_obs 1.022 _refine_ls_shift/esd_max 0.025 _refine_ls_shift/esd_mean 0.003 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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Pd Pd 0.41164(2) 0.206131(13) 0.58503(3) 0.03815(10) Uani 1 d . . S S 0.51615(11) 0.17853(5) 0.46335(11) 0.0537(3) Uani 1 d . . Cl Cl 0.43286(11) 0.31017(5) 0.56410(12) 0.0592(3) Uani 1 d . . N1 N 0.3087(3) 0.20857(15) 0.6958(3) 0.0401(7) Uani 1 d . . N2 N 0.3857(3) 0.11779(14) 0.5960(3) 0.0369(6) Uani 1 d . . N3 N 0.4371(3) 0.07425(15) 0.5424(3) 0.0404(7) Uani 1 d . . N4 N 0.5585(4) 0.0626(2) 0.4280(4) 0.0588(11) Uani 1 d . . C1 C 0.2916(4) 0.0001(2) 0.7471(4) 0.0492(10) Uani 1 d . . C2 C 0.2422(5) -0.0578(2) 0.7383(5) 0.0575(11) Uani 1 d . . C3 C 0.1621(5) -0.0769(2) 0.6296(6) 0.0611(13) Uani 1 d . . C4 C 0.1326(4) -0.0388(2) 0.5290(5) 0.0588(12) Uani 1 d . . C5 C 0.1823(4) 0.0184(2) 0.5353(4) 0.0493(9) Uani 1 d . . C6 C 0.2625(3) 0.0383(2) 0.6453(3) 0.0367(7) Uani 1 d . . C7 C 0.3104(3) 0.1017(2) 0.6511(3) 0.0374(7) Uani 1 d . . C8 C 0.2683(3) 0.1520(2) 0.7115(3) 0.0397(8) Uani 1 d . . C9 C 0.1935(4) 0.1439(2) 0.7797(4) 0.0489(9) Uani 1 d . . C10 C 0.1598(5) 0.1949(3) 0.8328(5) 0.0612(13) Uani 1 d . . C11 C 0.2018(5) 0.2510(2) 0.8172(5) 0.0610(13) Uani 1 d . . C12 C 0.2759(4) 0.2565(2) 0.7476(4) 0.0513(10) Uani 1 d D . C13 C 0.5013(4) 0.0998(2) 0.4814(4) 0.0437(8) Uani 1 d . . H1N4 H 0.5545(46) 0.0209(27) 0.4367(48) 0.069(17) Uiso 1 d . . H2N4 H 0.5932(45) 0.0765(24) 0.3941(48) 0.055(15) Uiso 1 d . . H1 H 0.3445(43) 0.0143(23) 0.8220(45) 0.060(14) Uiso 1 d . . H2 H 0.2596(43) -0.0841(23) 0.8076(46) 0.058(14) Uiso 1 d . . H3 H 0.1286(50) -0.1122(27) 0.6235(51) 0.076(17) Uiso 1 d . . H4 H 0.0803(46) -0.0474(25) 0.4523(49) 0.067(15) Uiso 1 d . . H5 H 0.1659(37) 0.0424(20) 0.4715(40) 0.043(12) Uiso 1 d . . H9 H 0.1629(43) 0.1072(24) 0.7802(45) 0.057(14) Uiso 1 d . . H10 H 0.1131(48) 0.1887(24) 0.8831(51) 0.066(15) Uiso 1 d . . H11 H 0.1853(50) 0.2876(26) 0.8468(53) 0.076(18) Uiso 1 d . . H12 H 0.3020(43) 0.2956(15) 0.7322(47) 0.060 Uiso 1 d D . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Pd 0.0370(2) 0.0381(2) 0.0386(2) 0.00026(11) 0.01086(11) -0.00302(11) S 0.0595(6) 0.0501(6) 0.0637(7) 0.0063(5) 0.0370(6) -0.0037(5) Cl 0.0611(7) 0.0420(5) 0.0651(7) 0.0047(5) 0.0064(5) -0.0087(5) N1 0.038(2) 0.045(2) 0.0371(15) -0.0045(13) 0.0108(12) 0.0025(13) N2 0.0378(15) 0.040(2) 0.0347(14) -0.0040(12) 0.0134(12) 0.0001(12) N3 0.042(2) 0.044(2) 0.041(2) -0.0001(13) 0.0200(14) 0.0010(13) N4 0.068(3) 0.054(2) 0.075(3) -0.002(2) 0.052(2) -0.002(2) C1 0.061(3) 0.050(2) 0.036(2) -0.002(2) 0.015(2) -0.007(2) C2 0.072(3) 0.049(2) 0.055(3) 0.008(2) 0.025(2) -0.008(2) C3 0.057(3) 0.047(3) 0.086(4) -0.006(2) 0.031(3) -0.013(2) C4 0.047(2) 0.060(3) 0.064(3) -0.014(2) 0.009(2) -0.007(2) C5 0.051(2) 0.054(3) 0.041(2) -0.001(2) 0.012(2) -0.003(2) C6 0.037(2) 0.041(2) 0.035(2) -0.0025(14) 0.0152(14) -0.0025(14) C7 0.038(2) 0.041(2) 0.034(2) -0.0045(14) 0.0126(14) -0.0032(14) C8 0.041(2) 0.044(2) 0.034(2) -0.0056(15) 0.0119(14) -0.001(2) C9 0.051(2) 0.054(3) 0.047(2) -0.003(2) 0.024(2) -0.002(2) C10 0.060(3) 0.073(3) 0.060(3) -0.011(2) 0.034(2) 0.008(2) C11 0.070(3) 0.053(3) 0.068(3) -0.015(2) 0.033(3) 0.012(2) C12 0.055(2) 0.045(2) 0.054(2) -0.007(2) 0.018(2) 0.004(2) C13 0.042(2) 0.044(2) 0.050(2) 0.000(2) 0.021(2) -0.002(2) _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 Pd N2 1.962(3) . y Pd N1 2.041(3) . y Pd S 2.2407(12) . y Pd Cl 2.3037(13) . y S C13 1.745(4) . y N1 C12 1.324(5) . ? N1 C8 1.359(5) . ? N2 C7 1.310(5) . y N2 N3 1.380(4) . y N3 C13 1.321(5) . y N4 C13 1.334(5) . y C1 C2 1.386(6) . ? C1 C6 1.387(5) . ? C2 C3 1.381(7) . ? C3 C4 1.375(8) . ? C4 C5 1.376(7) . ? C5 C6 1.397(5) . ? C6 C7 1.491(5) . ? C7 C8 1.471(5) . y C8 C9 1.382(5) . ? C9 C10 1.388(6) . ? C10 C11 1.357(8) . ? C11 C12 1.380(7) . ? 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 N2 Pd N1 81.06(13) . . y N2 Pd S 84.78(9) . . y N1 Pd S 165.83(10) . . y N2 Pd Cl 177.00(9) . . y N1 Pd Cl 98.57(10) . . y S Pd Cl 95.52(5) . . y C13 S Pd 95.21(13) . . y C12 N1 C8 119.1(4) . . ? C12 N1 Pd 128.9(3) . . ? C8 N1 Pd 111.9(2) . . y C7 N2 N3 120.6(3) . . ? C7 N2 Pd 116.3(3) . . y N3 N2 Pd 122.9(2) . . y C13 N3 N2 111.6(3) . . y C2 C1 C6 119.7(4) . . ? C3 C2 C1 120.2(5) . . ? C4 C3 C2 120.0(5) . . ? C3 C4 C5 120.6(5) . . ? C4 C5 C6 119.7(4) . . ? C1 C6 C5 119.7(4) . . ? C1 C6 C7 121.7(3) . . ? C5 C6 C7 118.5(3) . . ? N2 C7 C8 115.1(3) . . y N2 C7 C6 123.1(3) . . ? C8 C7 C6 121.7(3) . . ? N1 C8 C9 121.1(4) . . ? N1 C8 C7 115.0(3) . . y C9 C8 C7 123.9(4) . . ? C8 C9 C10 118.8(5) . . ? C11 C10 C9 119.3(5) . . ? C10 C11 C12 119.6(4) . . ? N1 C12 C11 122.1(4) . . ? N3 C13 N4 117.6(4) . . ? N3 C13 S 125.2(3) . . y N4 C13 S 117.1(3) . . ? _refine_diff_density_max 1.129 _refine_diff_density_min -1.151 _refine_diff_density_rms 0.114 #===END #-------------------------- data section of block --------------------------- data_2a _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C19 H14 Cl N3 Pd S' _chemical_formula_weight 458.24 _chemical_melting_point ? _chemical_compound_source ? 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' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Pd' 'Pd' -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'monoclinic' _symmetry_space_group_name_H-M 'P21/n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 12.235(3) _cell_length_b 9.413(2) _cell_length_c 15.670(4) _cell_angle_alpha 90.00 _cell_angle_beta 101.20(1) _cell_angle_gamma 90.00 _cell_volume 1770(1) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description 'prisms' _exptl_crystal_colour 'red' _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.719 _exptl_crystal_density_method ? _exptl_crystal_F_000 912 _exptl_absorpt_coefficient_mu 1.323 _exptl_absorpt_correction_type 'Walker&Stuart (1983)' _exptl_absorpt_correction_T_min 0.87 _exptl_absorpt_correction_T_max 1.06 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite' _diffrn_measurement_device 'Siemens AED diffractometer' _diffrn_measurement_method '\q/2\q scan' _diffrn_standards_number 1 _diffrn_standards_interval_count 100 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 3254 _diffrn_reflns_av_R_equivalents 0.0718 _diffrn_reflns_av_sigmaI/netI 0.1525 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 3.19 _diffrn_reflns_theta_max 25.17 _reflns_number_total 3140 _reflns_number_observed 1227 _reflns_observed_criterion >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SIR92 (Altomare et al., 1992)' _computing_structure_refinement 'SHELXL-92 (Sheldrick, 1993)' _computing_molecular_graphics 'ZORTEP (Zsolnai & Pritzkow, 1994)' _computing_publication_material 'PARST95 (Nardelli, 1995)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[s^2^(Fo^2^)+( 0.1117P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary none _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3140 _refine_ls_number_parameters 226 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.2002 _refine_ls_R_factor_obs 0.0685 _refine_ls_wR_factor_all 0.2534 _refine_ls_wR_factor_obs 0.1648 _refine_ls_goodness_of_fit_all 1.012 _refine_ls_goodness_of_fit_obs 1.125 _refine_ls_restrained_S_all 1.012 _refine_ls_restrained_S_obs 1.125 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Pd Pd 0.57181(10) 0.22538(12) 0.03775(8) 0.0538(5) Uani 1 d . . Cl Cl 0.7571(3) 0.2735(4) 0.0476(3) 0.0691(12) Uani 1 d . . S S 0.5939(3) 0.0717(4) 0.1493(3) 0.0603(11) Uani 1 d . . N1 N 0.5126(10) 0.3535(12) -0.0677(7) 0.052(3) Uani 1 d . . N2 N 0.4148(10) 0.1847(13) 0.0283(7) 0.054(3) Uani 1 d . . N3 N 0.3731(9) 0.0978(13) 0.0846(7) 0.054(3) Uani 1 d . . C1 C 0.1536(13) 0.3537(17) -0.0522(9) 0.059(4) Uani 1 d . . H1 H 0.1840(13) 0.4445(17) -0.0477(9) 0.071 Uiso 1 calc R . C2 C 0.0420(14) 0.3367(19) -0.0637(10) 0.066(4) Uani 1 d . . H2 H -0.0031(14) 0.4163(19) -0.0642(10) 0.079 Uiso 1 calc R . C3 C -0.0052(12) 0.2076(19) -0.0744(10) 0.060(4) Uani 1 d . . H3 H -0.0824(12) 0.1996(19) -0.0841(10) 0.072 Uiso 1 calc R . C4 C 0.0586(12) 0.0873(17) -0.0712(9) 0.056(4) Uani 1 d . . H4 H 0.0255(12) -0.0019(17) -0.0789(9) 0.068 Uiso 1 calc R . C5 C 0.1727(12) 0.1012(15) -0.0564(10) 0.058(4) Uani 1 d . . H5 H 0.2161(12) 0.0196(15) -0.0526(10) 0.070 Uiso 1 calc R . C6 C 0.2253(10) 0.2321(15) -0.0471(8) 0.042(3) Uani 1 d . . C7 C 0.3422(11) 0.2538(15) -0.0335(8) 0.046(4) Uani 1 d . . C8 C 0.3963(12) 0.3414(15) -0.0889(10) 0.054(4) Uani 1 d . . C9 C 0.3404(13) 0.4113(17) -0.1633(10) 0.065(5) Uani 1 d . . H9 H 0.2640(13) 0.3986(17) -0.1814(10) 0.078 Uiso 1 calc R . C10 C 0.3974(16) 0.4995(16) -0.2108(12) 0.079(5) Uani 1 d . . H10 H 0.3600(16) 0.5528(16) -0.2574(12) 0.095 Uiso 1 calc R . C11 C 0.5085(16) 0.5044(19) -0.1866(13) 0.085(6) Uani 1 d . . H11 H 0.5487(16) 0.5604(19) -0.2186(13) 0.102 Uiso 1 calc R . C12 C 0.5655(13) 0.4297(16) -0.1162(11) 0.061(4) Uani 1 d . . H12 H 0.6429(13) 0.4337(16) -0.1030(11) 0.073 Uiso 1 calc R . C13 C 0.4526(10) 0.0383(14) 0.1416(8) 0.039(3) Uani 1 d . . C14 C 0.4175(11) -0.0589(14) 0.2024(9) 0.045(3) Uani 1 d . . C15 C 0.4906(13) -0.1162(16) 0.2745(10) 0.063(4) Uani 1 d . . H15 H 0.5656(13) -0.0921(16) 0.2827(10) 0.076 Uiso 1 calc R . C16 C 0.4570(15) -0.2057(18) 0.3335(10) 0.071(5) Uani 1 d . . H16 H 0.5071(15) -0.2325(18) 0.3834(10) 0.085 Uiso 1 calc R . C17 C 0.3519(14) -0.2548(17) 0.3196(10) 0.065(5) Uani 1 d . . H17 H 0.3298(14) -0.3194(17) 0.3578(10) 0.078 Uiso 1 calc R . C18 C 0.2778(14) -0.2076(17) 0.2479(10) 0.068(5) Uani 1 d . . H18 H 0.2050(14) -0.2414(17) 0.2379(10) 0.081 Uiso 1 calc R . C19 C 0.3074(12) -0.1141(18) 0.1916(10) 0.063(4) Uani 1 d . . H19 H 0.2542(12) -0.0846(18) 0.1442(10) 0.075 Uiso 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 Pd 0.0499(7) 0.0559(8) 0.0551(8) -0.0022(7) 0.0092(5) -0.0028(6) Cl 0.053(2) 0.054(2) 0.100(3) 0.000(2) 0.012(2) -0.007(2) S 0.049(2) 0.065(3) 0.064(3) 0.012(2) 0.002(2) -0.003(2) N1 0.065(8) 0.055(8) 0.033(7) -0.007(6) 0.007(6) -0.018(7) N2 0.061(8) 0.068(8) 0.030(6) -0.002(6) 0.003(6) -0.013(7) N3 0.054(8) 0.062(8) 0.041(7) 0.020(6) -0.001(6) -0.005(6) C1 0.066(11) 0.069(11) 0.043(9) -0.001(8) 0.010(8) -0.005(9) C2 0.065(12) 0.067(11) 0.068(11) 0.003(9) 0.020(9) 0.011(10) C3 0.041(8) 0.082(13) 0.063(10) -0.003(9) 0.022(8) -0.016(9) C4 0.045(9) 0.058(10) 0.064(10) -0.005(8) 0.004(8) -0.019(8) C5 0.057(10) 0.039(9) 0.080(12) -0.003(8) 0.019(9) 0.003(7) C6 0.031(7) 0.059(9) 0.034(7) 0.007(7) 0.003(6) -0.005(7) C7 0.049(8) 0.061(10) 0.026(7) -0.002(7) 0.002(6) 0.000(7) C8 0.053(10) 0.045(9) 0.060(10) -0.012(8) -0.001(8) 0.002(7) C9 0.057(10) 0.076(12) 0.058(11) 0.024(9) 0.002(8) -0.007(9) C10 0.092(14) 0.039(9) 0.107(15) 0.027(10) 0.021(12) 0.019(9) C11 0.074(13) 0.079(13) 0.106(16) 0.027(12) 0.026(12) 0.009(11) C12 0.058(10) 0.058(10) 0.072(11) -0.007(9) 0.022(9) 0.002(8) C13 0.038(7) 0.047(8) 0.030(7) -0.013(6) -0.001(6) 0.005(6) C14 0.037(8) 0.039(8) 0.051(9) -0.001(7) -0.014(7) 0.002(6) C15 0.068(11) 0.057(10) 0.064(11) -0.002(9) 0.012(9) -0.010(8) C16 0.088(13) 0.080(12) 0.042(9) 0.020(9) 0.006(9) 0.010(11) C17 0.068(11) 0.075(12) 0.050(9) 0.024(9) 0.006(8) -0.005(9) C18 0.080(12) 0.068(11) 0.062(10) 0.027(9) 0.031(9) 0.003(9) C19 0.055(10) 0.087(12) 0.047(9) 0.020(9) 0.010(8) 0.003(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 Pd N2 1.937(12) . y Pd N1 2.060(12) . y Pd S 2.245(4) . y Pd Cl 2.287(4) . y S C13 1.738(13) . y N1 C12 1.30(2) . ? N1 C8 1.40(2) . y N2 C7 1.35(2) . y N2 N3 1.372(15) . y N3 C13 1.312(15) . y C1 C2 1.35(2) . ? C1 C6 1.43(2) . ? C2 C3 1.34(2) . ? C3 C4 1.37(2) . ? C4 C5 1.38(2) . ? C5 C6 1.38(2) . ? C6 C7 1.42(2) . ? C7 C8 1.45(2) . y C8 C9 1.40(2) . ? C9 C10 1.39(2) . ? C10 C11 1.34(2) . ? C11 C12 1.38(2) . ? C13 C14 1.45(2) . ? C14 C15 1.40(2) . ? C14 C19 1.42(2) . ? C15 C16 1.37(2) . ? C16 C17 1.34(2) . ? C17 C18 1.37(2) . ? C18 C19 1.34(2) . ? 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 N2 Pd N1 82.3(5) . . y N2 Pd S 84.3(4) . . y N1 Pd S 166.5(3) . . y N2 Pd Cl 179.5(3) . . y N1 Pd Cl 97.3(4) . . y S Pd Cl 96.1(2) . . y C13 S Pd 95.4(5) . . y C12 N1 C8 120.2(13) . . ? C12 N1 Pd 130.7(11) . . ? C8 N1 Pd 108.9(9) . . y C7 N2 N3 118.4(12) . . ? C7 N2 Pd 117.7(9) . . y N3 N2 Pd 123.8(9) . . y C13 N3 N2 111.9(11) . . y C2 C1 C6 120.3(15) . . ? C3 C2 C1 121.5(15) . . ? C2 C3 C4 121.0(13) . . ? C3 C4 C5 118.6(14) . . ? C4 C5 C6 122.6(14) . . ? C5 C6 C7 125.3(13) . . ? C5 C6 C1 115.9(12) . . ? C7 C6 C1 118.8(13) . . ? N2 C7 C6 122.8(12) . . ? N2 C7 C8 113.1(12) . . y C6 C7 C8 123.9(12) . . ? C9 C8 N1 118.0(14) . . ? C9 C8 C7 124.2(13) . . ? N1 C8 C7 117.8(13) . . y C10 C9 C8 120.9(15) . . ? C11 C10 C9 117.2(16) . . ? C10 C11 C12 122.5(17) . . ? N1 C12 C11 121.0(16) . . ? N3 C13 C14 116.3(11) . . ? N3 C13 S 124.5(11) . . y C14 C13 S 119.2(9) . . ? C15 C14 C19 113.3(13) . . ? C15 C14 C13 123.3(12) . . ? C19 C14 C13 123.3(12) . . ? C16 C15 C14 123.4(15) . . ? C17 C16 C15 120.3(15) . . ? C16 C17 C18 118.7(15) . . ? C19 C18 C17 122.0(16) . . ? C18 C19 C14 122.0(15) . . ? _refine_diff_density_max 1.333 _refine_diff_density_min -1.150 _refine_diff_density_rms 0.180 #===END