Die Kristallstrukturen der Palladium(II)-Komplexe [Pd(CH3CN)4](BF4)2, [PdCl(μ2 -PPh2)(HPPh2)]2 · CH2Cl2 und [PdCl(HPPh2) {H(OPPh2)2}] / The Crystal Structures of the Palladium(II) Complexes [Pd(CH3CN)4](BF4)2, [PdCl(μ2-PPh2)(HPPh2)] · CH2Cl2, and [PdCl(HPPh2){H(OPPh2)2}]

Abstract

The crystal structures of the title compounds were solved by X-ray methods. [Pd(CH3CN)4](BF4)2: Space group Pbca, Z = 4,812 observed unique reflections, R = 0.057, wR = 0.033. Lattice dimensions at -80 °C: α = 1027.5(5), b = 1242.8(6), c = 1280.3(6) pm. The compound consists of planar [Pd(CH3CN)4]2+ ions with Pd-N bond lengths of 195.6 pm and BF4 - anions. [PdCl(μ2-PPh2(HPPh2)]2 • CH2Cl2 crystallizes in two polymorphic forms in the same space group type but with different cell parameters, which depends on the conditions of the synthesis. α-form: Space group P21/c, Z = 4, 4680 observed unique reflections, R = 0.041, wR = 0.033. Lattice dimensions at -80 °C: a = 937.2(2), b = 1750.3(6), c = 1593.9(5) pm, β = 106.32(2)°. β-form: Space group Ρ21/n, Ζ = 4, 2519 observed unique reflections, R = 0.105, wR = 0.067. Lattice dimensions at -80 °C: a = 1118.0(4), b = 1222.4(3), c = 1849.9(4) pm, β = 90.72(2)°. Both polymorphs contain centrosymmetric molecules [PdCl μ2- PPh2)(HPPh2)]2 with Pd-P bond lengths of 226.6 pm for the bridging PPh2 groups and Pd-P bond lengths of 232.2 pm for the terminal HPPh2 ligands. [PdCl(HPPh2){H(OPPh2)2}]: Space group Pbca, Z = 8,3673 observed unique reflections, R = 0.038, wR = 0.032. Lattice dimensions at -80 °C: a = 1736.6(3), b = 1874.4(4), c = 1983.1(4) pm. The palladium atom has planar coordination consisting of the chlorine atom, the phosphorus atom of the HPPh2 ligand (Pd-P bond length 235.5 pm), and by the two phosphorus atoms of the H(OPPh2)2 chelate (Pd-P bond lengths 225.9 and 231.0 pm).