Two new compounds containing iodine substituted donor (DIETS = diiodoethylenedithiodithiadiselenafulvalene) and paramagnetic [Cr(CN)(6)](3-) anion, namely, (DIETS)8(Cl)(2)[Cr(CN)6](2/3).2H(2)O (1) and (DIETS)3(Et4N)[Cr(CN)6].3H(2)O (2) are reported. The structures of both compounds contain two different inorganic layers. In 1, one layer contains Cr(CN)(6)(3-) anions and water molecules and the second layer contains Cl- anions. In 2, the one layer contains Cr(CN)(6)(3-) anions, Et4N+ cations and water molecules while the other one does not contain Et4N+ cations. The -I...NC- contacts (2.725Angstrom in 1, 3.05Angstrom in 2) observed between DIETS and Cr(CN)(6) units are extremely short by comparison with the van der Walls separation of 3.65Angstrom. Both compounds are semiconductive, with sigma(300K)= 1 and 0.2 S.cm(-1) and E-a= 65 and 175meV for I and 2 respectively. Despite these short anion...Donor contacts no magnetic interactions were observed between the localized spins and the conducting electrons.