Abstract: Under the solvothermal system，  5-(hydroxymethyl) isophthalic acid and nitrogen heterocyclic ligand 4，4′-di(1H-imidazol-1-yl)-1，1′-biphenyl(4，4′-DIB) reacted with Mn(Ⅱ) ions to obtain complex Mn[(HIPA)(4，4′-DIB)](1). Crystallographic analysis indicates that complex 1 crystallizes in the monoclinic   P2₁/c space group. In the complex 1,  HIPA^2- ligands connect dinuclear Mn₂(CO₂)₄ units to form a two-dimensional (2D)  structure，  and then the adjacent layers are further connected together by 4，4′-DIB to obtain a three-dimensional (3D) pillar-layered framework with six connected pcu net. When auxiliary ligand 4，4′-DIB is replaced by (E)-1，2-di(pyridin-4-yl)ethene (DPEE)，  another complex Mn[(HIPA)(DPEE)]·xGuest (2) is obtained in the same reaction system. Complex 2 crystallizes in monoclinic P2₁/c space group with Mn₂(CO₂)₄ units. The structure of complex 2  is a 2D structure with sql net,  Mn₂(CO₂)₄ unit is stereoscopic in complex 1，  and planar structure in complex  2.  The different configurations of Mn₂(CO₂)₄ lead to different structural characteristics of complexes 1 and 2.

Key words: coordination polymer； , 5-(hydroxymethyl)isophthalic acid； Mn₂(CO₂)₄unit； , pillar-layered structure； , effect of ligand