The reaction of (NH4)(2)Ce(NO3)(6) and CaCl2 with dipicH(2) resulted in the title compound (1). 1 crystallizes in the triclinic system, space group P (1) over bar, with a = 11.234(2) Angstrom, b = 12.719(4) Angstrom, c = 16.142(4) Angstrom, alpha = 95.63(2)degrees, beta = 103.73(2)degrees, gamma = 113.83(2)degrees, and Z = 2. The structure consists of Ce(dipic)(3)(2-) and Ca(dipicH(2))(OH2)(3)(2+) ions linked by carboxylate groups forming an infinite linear chain having alternating tricapped trigonal prismatic and square antiprismatic polyhedra.