The crystal structures and EPR spectra for two dinuclear, metallacyclic V IV complexes are reported. The coordinating ligands include a rare example of vanadium(IV) coordinated to the carbonyl oxygen of an amide moiety. In the solid state, the cavity of these complexes encircles two molecules of methylene chloride which interact only weakly with the metallacycle. EPR spectra are typical of mononuclear V IV ion indicating that the spins are not interacting. Crystal data: for 1, C 21H 20Cl 8N 4O 3V, M = 710.95, triclinic, space group P1, a = 10.543(2), b = 11.999(3), c = 13.654(2) Å, α = 64.170(14), β = 70.084(12), γ = 87.19(2)°, U = 1451.6(5) Å 3, Z = 2, D c = 1.627 g cm −3, T = 123(2) K, no. of unique reflections = 3797, no. of parameters = 355, R 1 = 0.0882, wR 2 = 0.1892 (all data). Crystal data for 2: C 40.5H 45Cl 13N 8O 6V, M = 71302.63, triclinic, space group P1, a = 11.933(5), b = 12.020(3), c = 12.047(4) Å, α = 63.24(2), β = 65.46(3), γ = 80.06(3)°, U = 1403.4(9) Å 3, Z = 2, D c = 1.54 g cm −3, T = 130 K, no. of unique reflections = 3663, no. of parameters = 224, R 1 = 0.1271, R w = 0.1384 ( F > 4.0 σ( F)).