The crystal structures of fluoride and chloride complexes of tris[（2-benzimidazolyl）methyl]amine 1 were characterized by X-ray crystallography. 1 adopts （73 symmetrical geometry and cone-like conformation so as to allow its three NHs to associate with the anions through hydrogen bonds. Despite the different sizes of the anions, the two crystals are unexpectedly isostructural. The binding ability of the anions of 1 in solution was also studied by using of UV-vis spectroscopy.
3,3＇-Bis（5-（N-（4-hydroxylphenyl）imidomethyl）pyrrol-2-yl）pentane 1 has been synthesized and characterized. The crystal of its methanol complex, 1·（CH3OH）2, belongs to the orthorhombic system, space group Pccn with a = 18.094（2）, b = 11.6890（16）, c = 13.3629（19） , V = 2826.3（7） 3, Z = 8, C14.5H18N2O2, Mr = 252.31, Dc = 1.186 g/cm3, F（000） = 1080 and μ（MoKα） = 0.080 mm-1. The final R = 0.0662 and wR = 0.1801 for 1908 observed reflections with I 2σ（I）, and R = 0.0800 and wR = 0.1948 for all reflections. In the solid state, bridged by included methanol molecules, the molecules of compound 1 form interpenetrated grid structure through N–H···O and O–H···O hydrogen bonds.
A new 5,5＇-bisdiazo dipyrromethane, compound 2, has been synthesized and cha- racterized. The crystal of 2 is of monoclinic, space group P21/c with a = 16.3185（10）, b = 20.8225（13）, c = 18.5985（11） ）k, β = 114.5280（10）°, V = 5749.3（6） ）A^3, Z = 8, C25H26N602, Mr= 442.52, Dc= 1.022 g/cm, F（000） = 1872,/x（MoKa） = 0.068 mmI. The final R = 0.0469 and wR = 0.1143 for 10119 observed reflections with I 〉 2tr（/）, and R = 0.0677 and wR = 0.1231 for all reflections. The title compound prefers to form interlocked type dimer through quadruple N-H...N hydrogen bonds. The dimers self-assemble into a porous 3-D structure through O-H...O and C-H...N hydrogen bonds.
