The reaction of dipicolinicacid (2,6-pyridinedicarboxylic acid) with FeCl3 results in the unusual title ion-pair compound, [Fe(C7H3NO4)(H2O)(3)][Fe(C7H3NO4)(2)].6H(2)O. Each Fe atom has an octahedral geometry. The dipicolinate ligands are nearly planar, with the two in the anion being perpendicular to each other and displaying a dihedral angle of 93.74(6)degrees, The Fe-O(carboxylate) bond distances are comparable and range from 2.008 (2) to 2.028 (2) Angstrom, while the Fe-N distances are 2.059 (2), 2.054 (2) and 2.054 (2) Angstrom. The Fe-O(water) distances are 1,971 (2), 1.987 (2) and 2.004 (2) Angstrom. The cation, anion and water molecules are involved in an extensive three-dimensional hydrogen-bonding network, with O ... O distances ranging from 2.36(2) to 2.953 (3) Angstrom and angles ranging from 129 to 177 degrees.