Two new supramolecular compounds,2C 10 H 9 N 2 + ·C 8 HF 4 O 4 2-·C 8 H 2 F 4 O 4 /(H 2 tfbdc)· (tfbdc)·(Hbipy) 2 (1) and C 4 H 6 N 2 2+ ·C 8 HF 4 O 4 2-/(tfbdc)·(H 2 pz) (2),were synthesized and characterized by elemental analysis,IR spectra,and single-crystal X-ray diffraction.Compound 1 crystallizes in the triclinic system,space group P1,with a=8.3453(12),b=10.1798(15),c=10.6626(16),α=87.591(2),β=74.047(2),γ=69.006(2)°,V=834.53(12) 3,D c=1.614 g/cm 3,F(000)=400,u=1.45 cm-1,Z=2,the final R=0.0353 and wR=0.1005 for 5882 observed reflections with I > 2σ(I);and compound 2 crystallizes in the monoclinic system,space group P2 1 /c,with a=10.471(4),b=5.4419(19),c=12.249(4),β=114.909(6)°,V=633(4)3,D c=1.669 g/cm 3,F(000)=320,u=1.63 cm-1,Z=2,the final R=0.0794 and wR=0.2923 for 3213 observed reflections with I > 2σ(I).Both compounds 1 and 2 crystallize as charge-transfer organic salts with the dianionic or neutral acid components lying at the inversion centers.Hbipy + cations and anionic acid in compound 1 are linked to form a chain by means of C-H···O hydrogen bonds.Adjacent chains are further extended into a two-dimensional layer network via N-H···O and O-H···N hydrogen bonds.In compound 2,the acid and base subunits are arranged alternately to generate a linear tape motif via N-H O hydrogen bonds;these tapes are further combined into a three-dimensional array with CdSO 4 topology via C-H O intermolecular hydrogen bonds.