Abstract

Ionic palladium complexes with mononuclear anions [Ph₃PCH₂C(O)Me][PdCl₃(Dmso-S)] (I) and [Ph₄Sb(Dmso-O)][PdBr₃(Dmso-S)] (II) are synthesized from tetraorganylphosphonium or tetraorganylstibonium halide and palladium dihalide in the presence of hydrochloric or hydrobromic acid. The structures of complexes I and II are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 1907718 (I) and 1979208 (II)). The complexes contain tetrahedral tetraorganylphosphonium or tetraorganylstibonium cations and square anions [PdHal₃(Dmso-S)]⁻. According to the XRD data, the phosphorus and antimony atoms in the cations have a slightly distorted tetrahedral coordination with the CPC (105.76(7)°−110.31(7)°) and CSbC (100.03(16)°−117.62(15)°) bond angles slightly differed from the theoretical value and close P−C (1.7903(15)−1.8037(16) Å) and Sb−C (2.061(5)−2.100(4) Å) bond lengths. The P−C_Alk bonds are longer (1.8037(16) Å) than the P−C_Ph bonds. In the square planar anions [PdHal₃(Dmso-S)]⁻, the Pd−Cl and Pd−Br bond lengths vary in ranges of 2.2918(7)−2.3012(8) and 2.371(3)−2.403(2) Å, respectively, and the S−Pd distances (2.2492(6) and 2.237(2) Å) are less than the sum of covalent radii of palladium and sulfur atoms (2.44 Å). The cis-ClPdCl (89.88(3)°) and cis-BrPdBr (88.93(4)°, 89.59(4)°) angles do not almost differ from the theoretical value (90°). The trans-ClPdCl and trans-SPdCl angles are comparable and equal to 178.15(2)° and 178.714(19)°. The corresponding values for complex II are 174.22(3)° and 177.53(4)°. The deviations of the palladium atom from the Cl₃S and Br₃S planes are insignificant (0.019 and 0.033 Å). The structural organization in the crystals of the complexes is formed by interionic contacts S=O···H–C (2.56−2.72 Å (I) and 2.44−2.62 Å (II)), Pd–Cl···H–C (2.83−2.93 Å), and Br···H (2.86−3.04 Å).