# Copyright The Royal Society of Chemistry, 1999 # CCDC Number: 182/1134 data_global # 1. Deposition details _publ_contact_author ; Julio Real Departament de Qu\'imica Universitat Aut\'onoma de Barcelona 08193 Bellaterra Spain ; _publ_contact_author_phone '34 93 5812894' _publ_contact_author_fax '34 93 5813101' _publ_contact_author_email real@cc.uab.es _publ_requested_journal 'Chemical Communications' #============================================================= # 2. Title and author list _publ_section_title ; Low symmetry metal complexes: chloro cysteineethylester-N,S triphenylphosphine palladium(II), a new regioselective hydrocarboxylation catalyst for 2-phenylpropanoic acid, and its crystal structure. ; loop_ _publ_author_name _publ_author_address 'Real, Julio' ; Departament de Qu\'imica Universitat Aut\'onoma de Barcelona 08193 Bellaterra Spain ; 'Pag\`es, Montserrat' ; Departament de Qu\'imica Universitat Aut\'onoma de Barcelona 08193 Bellaterra Spain ; 'Polo, Alfonso' ; Departament de Qu\'imica Universitat de Girona Facultad de Ci\`encies Campus de Montilivi 17071 Girona Spain ; 'Alvarez-Larena, Angel' ; Servei de Difracci\'o de Raigs-X Universitat Aut\'onoma de Barcelona 08193 Bellaterra Spain ; 'Piniella, J. Francesc' ; Unitat de Cristal.lografia i Mineralogia Universitat Aut\'onoma de Barcelona 08193 Bellaterra Spain ; #============================================================= data_compound2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; Chloro(cysteineethylester-N,S)triphenylphosphinepalladium(II) ; _chemical_formula_sum 'C23 H25 Cl N O2 P Pd S' _chemical_formula_weight 552.32 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' 'O' 'O' 0.0106 0.0060 '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' 'Cl' 'Cl' 0.1484 0.1585 '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' '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 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 7.929(5) _cell_length_b 10.330(2) _cell_length_c 28.769(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2356.4(16) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 11.52 _cell_measurement_theta_max 13.91 _exptl_crystal_description prism _exptl_crystal_colour orange _exptl_crystal_size_max 0.54 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.557 _exptl_crystal_F_000 1120 _exptl_absorpt_coefficient_mu 1.077 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.955 _exptl_absorpt_correction_T_max 1.000 _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_type 'Enraf-Nonius CAD4' _diffrn_measurement_method 'omega/2theta scan' _diffrn_standards_number 3 _diffrn_standards_interval_time 120 _diffrn_standards_decay_% 0 _diffrn_reflns_number 2069 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0202 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 34 _diffrn_reflns_theta_min 1.42 _diffrn_reflns_theta_max 24.95 _reflns_number_total 2069 _reflns_number_gt 1910 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CAD4 (Enraf-Nonius)' _computing_cell_refinement 'CAD4 (Enraf-Nonius)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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 w=1/[\s^2^(Fo^2^)+(0.0225P)^2^+2.5111P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.01(4) _refine_ls_number_reflns 2069 _refine_ls_number_parameters 277 _refine_ls_number_restraints 21 _refine_ls_R_factor_all 0.0302 _refine_ls_R_factor_gt 0.0229 _refine_ls_wR_factor_ref 0.0631 _refine_ls_wR_factor_gt 0.0595 _refine_ls_goodness_of_fit_ref 1.130 _refine_ls_restrained_S_all 1.129 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Pd Pd 0.01321(5) 0.86839(4) 0.169860(13) 0.03235(11) Uani 1 d . . . S S 0.0130(2) 0.72771(13) 0.11002(5) 0.0432(3) Uani 1 d . . . Cl Cl 0.0468(2) 1.00248(17) 0.23516(5) 0.0575(5) Uani 1 d . . . P P -0.13301(18) 1.01832(13) 0.12968(5) 0.0327(3) Uani 1 d . . . C11 C 0.0051(7) 1.1335(5) 0.10151(16) 0.0384(11) Uani 1 d D . . C12 C -0.0432(8) 1.2017(6) 0.0625(2) 0.0525(17) Uani 1 d D . . H12 H -0.1503 1.1883 0.0503 0.063 Uiso 1 calc R . . C13 C 0.0631(9) 1.2891(7) 0.0412(3) 0.066(2) Uani 1 d D . . H13 H 0.0272 1.3338 0.0150 0.079 Uiso 1 calc R . . C14 C 0.2220(9) 1.3102(7) 0.0588(3) 0.068(2) Uani 1 d D . . H14 H 0.2948 1.3680 0.0443 0.082 Uiso 1 calc R . . C15 C 0.2719(8) 1.2443(7) 0.0982(3) 0.063(2) Uani 1 d D . . H15 H 0.3792 1.2583 0.1102 0.076 Uiso 1 calc R . . C16 C 0.1639(7) 1.1571(6) 0.1202(2) 0.0513(16) Uani 1 d D . . H16 H 0.1979 1.1149 0.1472 0.062 Uiso 1 calc R . . C21 C -0.2722(6) 1.1143(5) 0.1665(2) 0.0369(12) Uani 1 d D . . C22 C -0.3902(7) 1.0504(6) 0.1942(2) 0.0475(15) Uani 1 d D . . H22 H -0.3899 0.9605 0.1957 0.057 Uiso 1 calc R . . C23 C -0.5068(8) 1.1196(6) 0.21929(19) 0.0596(16) Uani 1 d D . . H23 H -0.5866 1.0760 0.2371 0.071 Uiso 1 calc R . . C24 C -0.5070(9) 1.2530(6) 0.2184(2) 0.0641(19) Uani 1 d D . . H24 H -0.5885 1.2994 0.2346 0.077 Uiso 1 calc R . . C25 C -0.3857(9) 1.3164(7) 0.1933(2) 0.0620(19) Uani 1 d D . . H25 H -0.3810 1.4063 0.1943 0.074 Uiso 1 calc R . . C26 C -0.2689(8) 1.2488(5) 0.1664(2) 0.0477(14) Uani 1 d D . . H26 H -0.1898 1.2932 0.1486 0.057 Uiso 1 calc R . . C31 C -0.2697(7) 0.9647(5) 0.08303(18) 0.0356(12) Uani 1 d D . . C32 C -0.4447(7) 0.9685(6) 0.0854(2) 0.0473(15) Uani 1 d D . . H32 H -0.4959 1.0013 0.1120 0.057 Uiso 1 calc R . . C33 C -0.5444(8) 0.9250(7) 0.0494(2) 0.0541(17) Uani 1 d D . . H33 H -0.6612 0.9271 0.0521 0.065 Uiso 1 calc R . . C34 C -0.4698(7) 0.8782(6) 0.00954(19) 0.0517(15) Uani 1 d D . . H34 H -0.5367 0.8489 -0.0148 0.062 Uiso 1 calc R . . C35 C -0.2959(7) 0.8747(6) 0.0056(2) 0.0491(15) Uani 1 d D . . H35 H -0.2457 0.8442 -0.0215 0.059 Uiso 1 calc R . . C36 C -0.1980(7) 0.9169(6) 0.04207(19) 0.0426(14) Uani 1 d D . . H36 H -0.0812 0.9134 0.0394 0.051 Uiso 1 calc R . . C1 C 0.3798(8) 0.6614(6) 0.1554(2) 0.0430(15) Uani 1 d . . . C2 C 0.2136(6) 0.6195(6) 0.1761(2) 0.0394(13) Uani 1 d . . . H2 H 0.2345 0.5441 0.1960 0.047 Uiso 1 calc R . . C3 C 0.0814(7) 0.5844(5) 0.1420(2) 0.0412(14) Uani 1 d . . . H3A H -0.0141 0.5465 0.1581 0.049 Uiso 1 calc R . . H3B H 0.1254 0.5206 0.1204 0.049 Uiso 1 calc R . . C4 C 0.5984(8) 0.6053(8) 0.1037(3) 0.063(2) Uani 1 d . . . H4A H 0.6826 0.6043 0.1282 0.076 Uiso 1 calc R . . H4B H 0.6001 0.6899 0.0890 0.076 Uiso 1 calc R . . C5 C 0.6352(9) 0.5039(8) 0.0692(3) 0.070(2) Uani 1 d . . . H5A H 0.7441 0.5193 0.0557 0.105 Uiso 1 calc R . . H5B H 0.5509 0.5055 0.0453 0.105 Uiso 1 calc R . . H5C H 0.6347 0.4208 0.0842 0.105 Uiso 1 calc R . . O1 O 0.4563(5) 0.7543(5) 0.16809(19) 0.0629(12) Uani 1 d . . . O2 O 0.4313(5) 0.5793(4) 0.12313(18) 0.0509(12) Uani 1 d . . . N N 0.1492(6) 0.7260(5) 0.20584(16) 0.0385(11) Uani 1 d D . . H0A H 0.242(5) 0.769(6) 0.2151(17) 0.058 Uiso 1 d D . . H0B H 0.088(6) 0.701(6) 0.2306(12) 0.058 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 0.03364(19) 0.03272(19) 0.03068(18) -0.00040(16) -0.00019(18) 0.00075(19) S 0.0481(8) 0.0437(7) 0.0378(7) -0.0091(6) -0.0074(8) 0.0056(8) Cl 0.0653(11) 0.0625(9) 0.0446(8) -0.0184(7) -0.0087(8) 0.0174(8) P 0.0325(7) 0.0330(7) 0.0326(7) -0.0003(6) -0.0021(6) -0.0008(6) C11 0.038(3) 0.039(3) 0.038(3) -0.002(2) 0.005(3) 0.000(4) C12 0.049(4) 0.053(4) 0.055(4) 0.014(3) -0.015(3) -0.008(3) C13 0.086(6) 0.055(4) 0.056(4) 0.014(3) -0.009(4) -0.014(4) C14 0.064(5) 0.050(4) 0.090(6) 0.006(4) 0.017(4) -0.016(4) C15 0.042(4) 0.060(4) 0.086(6) 0.017(4) 0.002(4) -0.015(3) C16 0.046(3) 0.052(4) 0.055(4) 0.013(3) -0.001(3) -0.004(3) C21 0.038(3) 0.041(3) 0.032(3) -0.006(3) -0.007(2) 0.002(2) C22 0.050(4) 0.050(4) 0.043(4) -0.006(3) 0.006(3) -0.007(3) C23 0.043(3) 0.094(5) 0.041(3) -0.004(3) 0.002(3) 0.003(5) C24 0.057(4) 0.089(5) 0.046(4) -0.017(3) -0.003(4) 0.029(5) C25 0.079(5) 0.051(4) 0.056(4) -0.004(3) -0.001(4) 0.019(4) C26 0.056(3) 0.043(3) 0.045(4) -0.003(3) -0.002(3) 0.004(3) C31 0.036(3) 0.034(3) 0.037(3) 0.003(2) -0.003(2) -0.004(2) C32 0.044(4) 0.050(4) 0.048(4) -0.003(3) -0.003(3) 0.000(3) C33 0.041(4) 0.068(4) 0.054(4) -0.005(3) -0.009(3) -0.004(3) C34 0.061(4) 0.050(3) 0.044(3) -0.004(3) -0.020(3) -0.005(4) C35 0.062(4) 0.046(3) 0.039(3) -0.002(3) -0.001(3) 0.004(3) C36 0.041(3) 0.048(3) 0.039(3) 0.001(3) -0.003(2) 0.001(3) C1 0.039(3) 0.042(3) 0.048(4) 0.007(3) -0.005(3) 0.001(3) C2 0.039(3) 0.034(3) 0.046(3) 0.006(3) -0.002(2) 0.001(2) C3 0.036(3) 0.035(3) 0.052(4) -0.005(3) 0.007(3) -0.005(2) C4 0.038(3) 0.065(5) 0.086(6) 0.006(4) 0.018(3) -0.003(3) C5 0.053(4) 0.073(5) 0.084(6) -0.005(4) 0.030(4) 0.000(4) O1 0.057(3) 0.061(3) 0.070(3) -0.008(3) 0.007(3) -0.023(2) O2 0.033(2) 0.047(3) 0.073(3) -0.004(2) 0.010(2) -0.0036(17) N 0.046(3) 0.039(3) 0.031(3) 0.003(2) 0.003(2) 0.001(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 N 2.097(5) . ? Pd S 2.2530(14) . ? Pd P 2.2537(15) . ? Pd Cl 2.3493(16) . ? S C3 1.826(6) . ? P C11 1.809(5) . ? P C31 1.812(6) . ? P C21 1.823(6) . ? C11 C12 1.378(6) . ? C11 C16 1.390(7) . ? C12 C13 1.379(7) . ? C13 C14 1.375(8) . ? C14 C15 1.379(7) . ? C15 C16 1.395(7) . ? C21 C26 1.390(7) . ? C21 C22 1.395(7) . ? C22 C23 1.374(7) . ? C23 C24 1.378(7) . ? C24 C25 1.368(8) . ? C25 C26 1.395(7) . ? C31 C32 1.390(7) . ? C31 C36 1.399(6) . ? C32 C33 1.377(7) . ? C33 C34 1.379(7) . ? C34 C35 1.384(7) . ? C35 C36 1.377(6) . ? C1 O1 1.192(7) . ? C1 O2 1.323(8) . ? C1 C2 1.509(8) . ? C2 C3 1.482(8) . ? C2 N 1.483(7) . ? C4 O2 1.463(7) . ? C4 C5 1.473(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 N Pd S 85.71(14) . . ? N Pd P 178.62(14) . . ? S Pd P 92.92(6) . . ? N Pd Cl 87.74(14) . . ? S Pd Cl 172.52(6) . . ? P Pd Cl 93.63(6) . . ? C3 S Pd 97.9(2) . . ? C11 P C31 103.4(2) . . ? C11 P C21 105.6(2) . . ? C31 P C21 103.5(2) . . ? C11 P Pd 111.75(18) . . ? C31 P Pd 118.55(18) . . ? C21 P Pd 112.79(19) . . ? C12 C11 C16 118.5(5) . . ? C12 C11 P 122.2(4) . . ? C16 C11 P 119.4(4) . . ? C11 C12 C13 121.8(6) . . ? C14 C13 C12 120.0(6) . . ? C13 C14 C15 119.1(6) . . ? C14 C15 C16 121.0(6) . . ? C11 C16 C15 119.6(6) . . ? C26 C21 C22 119.1(5) . . ? C26 C21 P 122.1(4) . . ? C22 C21 P 118.8(4) . . ? C23 C22 C21 120.4(6) . . ? C22 C23 C24 120.7(6) . . ? C25 C24 C23 119.2(6) . . ? C24 C25 C26 121.3(6) . . ? C21 C26 C25 119.1(6) . . ? C32 C31 C36 117.2(5) . . ? C32 C31 P 123.6(4) . . ? C36 C31 P 119.2(4) . . ? C33 C32 C31 121.8(6) . . ? C32 C33 C34 119.6(6) . . ? C33 C34 C35 120.3(5) . . ? C36 C35 C34 119.4(6) . . ? C35 C36 C31 121.7(5) . . ? O1 C1 O2 125.0(6) . . ? O1 C1 C2 123.7(6) . . ? O2 C1 C2 111.3(5) . . ? C3 C2 N 108.7(4) . . ? C3 C2 C1 115.3(5) . . ? N C2 C1 108.4(5) . . ? C2 C3 S 110.2(4) . . ? O2 C4 C5 107.8(6) . . ? C1 O2 C4 115.5(5) . . ? C2 N Pd 114.4(4) . . ? _diffrn_measured_fraction_theta_max 0.864 _diffrn_reflns_theta_full 24.95 _diffrn_measured_fraction_theta_full 0.864 _refine_diff_density_max 0.581 _refine_diff_density_min -0.459 _refine_diff_density_rms 0.072