Complexes Ru(DMF)(6)(n+) (n = 2, 3; DMF=N,N-dimethylformamide) are prepared by a direct and simple synthesis from commercially available RuCl3 .xH2O and characterized by UV-vis, NMR, and cyclic voltammetry. Crystal and molecular structures are presented for [Ru(DMF)(6)](CF3SO3)(3) (I) and [Ru(DMF)(6)](CF3SO3)(2) (II). I is monoclinic, of space group P2(1)/c, with a = 18.28(1) Angstrom, b = 18.62(1) Angstrom, c = 13.29(1) Angstrom, beta = 100.8(1)degrees, V = 4443(5) degrees(3), Z = 4, d(calc) = 1.495 g cm(-3), and d(obs) = 1.49 (25 degrees C) g cm(-3). R = 0.061 (R(w) = 0.061) for 4506 independent observed reflections with I > 3 sigma(I). II is triclinic, of space group P (1) over bar, with a = 8.799(2) Angstrom, b = 9.557(2) Angstrom, c = 11.627(2) Angstrom, alpha = 76.11(2)degrees, beta = 84.73(2)degrees, gamma = 85.12(2)degrees, V = 943.1(3)Angstrom(3), Z = 1, d(calc) = 1.475 g cm(-3), and d(obs) = 1.477 (25 degrees C) g cm(-3). R = 0.061 (R(w) = 0.058) for 5189 independent observed reflections with I > 3 sigma(I). Metal to ligand coordination is through the oxygen atom with average Ru-O distances of 2.02(1) Angstrom (I) and 2.088(9) Angstrom in the octahedral units. The reduction potential for I measured by cyclic voltammetry is 0.28 V vs NHE.