The reactions of SbCl3 and HgCl2 with 2-(3-pyridyl)benzimidazole (PyBIm) in solution acidified with HC1 have been investigated. The PyBIm ligands are protonated into 2-(3-pyridinio)benzimidazolium (H2PyBIm) cations and the corresponding metal ions are bonded with chloride atoms into coordination anions, forming two new coordination compounds, namely,(H2PyBIm)(SbCl5) 1 and (H2PyBIm)2(Hg2Cl8) 2. Both compounds were characterized by X-ray crystallography. Crystal data for 1: triclinic, space group P1 with a = 5.7030(7), b = 9.0625(11), c =16.5929(18)(A), α = 91.808(7), β = 93.234(6), γ = 99.216(7)°, C12H11N3SbCl5, Mr = 496.24, V =844.44(17) (A)3, Z = 2, Dc = 1.952 g/cm3, μ(MoKα) = 2.419 mm-1, F(000) = 480, the final R = 0.0496and wR = 0.1382 for 3433 observed reflections (I > 2σ(I)). Crystal data for 2: monoclinic, space group P21/c with a = 7.8061(5), b = 15.8127(9), c = 12.2435(9) (A), β = 91.955(4)°, C24H22N6Hg2Cl8,Mr = 1079.26, V= 1510.40(17) (A)3, Z=2,Dc = 2.373 g/cm3, μ(MoKα) = 10.889 mm-1, F(000) =1008, the final R = 0.0293 and wR = 0.0562 for 2854 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that the antimony(Ⅲ) is five-coordinated, exhibiting a slightly distorted square-pyramidal coordination geometry; while in 2, a dimeric [Hg2Cl8]4- anion consists of two trigonal bipyramids sharing two common edges. The organic cations and coordination anions are bonding interactions in compounds 1 and 2, respectively; both are further aggregated into 3D frameworks by strong π-π contacts. [Hg2 l8]4- an