A Ca(II) coordination polymer [CaII(5-AIP)(DMA)]n] (5-AIP=5-aminoisophthalic, DMA=dimethylacetamide) has been prepared by hydrothermal method using directional solvents like DMA. Single crystal X-ray analysis confirms the coordination of 5-AIP to the hepta coordinate metal centre along with DMA molecules. It crystallizes in orthorhombic space group Pna21 and has a polymeric structure containing CaII centers which adopt hepta coordinate pentagonal bipyramidal geometry. [CaII(5-AIP)(DMA)]n] has been successfully employed as catalyst in bicarbonate mediated epoxidation of various olefins.