An orthogonal arrangement of imino nitroxide ligands in Cu-I and Ag-I complexes results in propagation of an intramolecular ferromagnetic interaction between the coordinated imino nitroxides through these diamagnetic ions. Reaction of [Cu-I(CH3CN)(4)](PF6) and Ag-I(PF6) with imino nitroxides in ethanol solution gave [Cu-I(immepy)(2)-(PF6) (1) and [Ag-I(impy)(2)](PF6) (2), respectively (immepy 2-(2-(6-methylpyridyl))-4,4,5,5-tetramethyl-4,5-dihydro-1H imidazolyl-l-oxy and impy 2-(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxy). Complex 1 crystallizes in the orthorhombic space group Pba2, which has a unit cell with a 11.251(2) Angstrom, b = 14.745(3) Angstrom, c = 9.747(2) Angstrom, V = 1617.0(5) Angstrom(3), and Z = 2. Refinement with 991 reflections observed [I-0 > 3 sigma(I-0)] gave R = 0.044 (R-w = 0.053). In 1, imino nitroxides coordinate to the Cu-I ions in a tetrahedral fashion, the dihedral angle between coordinating imino nitroxides being 88.7 degrees. Magnetic susceptibility measurement for 1 shows typical triplet-singlet behavior with strong ferromagnetic interactions (J = 55.1(6) cm(-1) with g = 2.0; H = -JS(1).S-2) The UV-visible absorption spectrum of 1 shows strong bands at 454 and 766 nm assignable to charge-transfer bands from the Cu ion to the ligand NLUMO and SOMO, respectively. The pi-back-donation to the SOMO induces the spin on the Cu ion and results in the strong ferromagnetic interaction. Complex 2 crystallizes in the orthorhombic space group P2(1)cn which has a unit cell with a = 10.535(6) Angstrom, b = 31.295(3) Angstrom, c 8.921(4) Angstrom, V = 2941(1) Angstrom(3), and Z = 4. Refinement with 1882 reflections [I-0 > 3 sigma(I-0)] gave R = 0.058 (R-w = 0.074). Ln 2, the four coordination sites of the Ag-I ion were completed with two imino nitroxides and the dihedral angle between the imino nitroxides is 79.2 degrees. The EPR spectrum of a frozen ethanol solution of 2 shows a typical triplet signal with zero field splitting (D = 0.043 cm(-1) and E = 0.014 cm(-1)). Curie plots for the rim = 2 signal below 80 K gave a positive Weiss constant (theta = 4 K), suggesting an intramolecular ferromagnetic interaction in 2.