Synthesis and structure of palladium complexes [Ph3PCH2C(O)Me][PdCl3(dmso-S)] and [Ph4Sb(dmso-O)][PdBr3(dmso-S)]

Interaction of tetraorganylphosphonium, -stibonium halides with palladium dihalide in water in the presence of hydrochloric or hydrobromic acid, followed by recrystallization from dimethyl sulfoxide, has been used to synthesize palladium(II) ionic complexes with mononuclear anions [Ph3PCH2C(O)Me][PdCl3(dmso-S)] and [Ph4Sb(dmso-O)][PdBr3(dmso-S)]. The complexes include tetrahedral cations of tetraorganylphosphonium, -stibonium and square anions [PdHal3(dmso-S)]-. According to the X-ray analysis data obtained on an automatic diffractometer D8 Quest Bruker (MoKa-radiation, λ = 0.71073 Å, graphite monochromator) at 293 K, of crystals 1 [C23H26O2PCl3PdS, M 610.22, monoclinic syngony, symmetry group Р21/с; cell parameters: a 14.204(4)Å, b 9.827(3) Å, c 19.722(6) Å, α = γ = 90.00 degrees, β = 110.850(12) degrees; V = 2572.6(13) Å3; the crystal size is 0.22×0.2×0.14 mm; intervals of reflection indexes are -27 ≤ h ≤ 27, -19 ≤ k ≤ 19, -33 ≤ l ≤ 38; total reflections 146030; independent reflections 20362; Rint 0.0504; GOOF 1.016; R1 = 0.0473, wR2 = 0.0937; residual electron density 0.61/-1.44 e/Å3] and 2 [C14H16OSBr1,5Pd0,5S0,5, M 466.27, monoclinic syngony, symmetry group Р212121; cell parameters: a 9.308(10) Å, b 15.707(16) Å, c 21.65(3) Å, α = γ = 90.00 degrees, β = 90.90 degrees; V = 3165(6) Å3; the crystal size is 0.46×0.29×0.25 mm; intervals of reflection indexes are -11 ≤ h ≤ 12, -21 ≤ k ≤ 21, -29 ≤ l ≤ 29; total reflections 52839; independent reflections 8521; Rint 0.0479; GOOF 1.027; R1 = 0.0311, wR2 = 0.0593; residual electron density 0.84/-0.95 e/Å3] the phosphorus and antimony atoms in cations have a slightly distorted tetrahedral coordination with bond angles: CPC 105.76(7)-110.31(7) degrees and CSbC 100.03(16)-117.62(15) degrees, differ little from the theoretical value, and by close bond lengths: P-C [1.7903(15)-1.8037(16) Å] and Sb-C [2.061(5)-2.100(4) Å]. The P-CAlk bond is longer [1.8037(16) Å] than the P-CPh. In the [PdHal3(dmso-S)]- square planar anions the Pd-Cl and Pd-Br bond lengths vary in the ranges 2.2918(7)-2.3012(8) and 2.371(3)-2.403(2) Å, respectively, while the S-Pd distances [2.2492(6) and 2.237(2) Å] are less than the sum of the covalent radii of palladium and sulfur atoms (2.44 Å). The ClPdCl cis-angles [89.88(3) degrees] and BrPdBr ones [88.93(4) degrees, 89.59(4) degrees] practically do not differ from the theoretical value (90 degrees); the values of the ClPdCl and SPdCl trans-angles are comparable to each other and amount to 178.15(2) degrees and 178.714(19) degrees. Similar values for complex 2 are 174.22(3) degrees and 177.53(4) degrees. The deviation of the palladium atom from the Cl3S and Br3S planes is insignificant (0.019 and 0.033 Å). The structural organization of crystals 1 and 2 is controlled by intermolecular bonds S=O∙∙∙H-C 2.56-2.72 Å (1) and 2.44-2.62 Å (2); Pd-Cl∙∙∙H-C (2.83-2.93 Å) and Pd-Br∙∙∙H-C (2.86-3.04 Å). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1907718 (1), 1979208 (2); deposit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).