Crystalline C-N films composed of α- and β-C3N4, as well as other C-N phases, have been synthesized via bias-assisted hot-filament chemical vapor deposition using a gas mixture of nitrogen and methane. Scanning electron microscopy(SEM), energy dispersive X-ray (EDX) analysis, X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the films. Lattice constants of the α- and β-C3N4 phases obtained coincide very well with the theoretical values. In addition to these phases, two new C-N phases in the films have been identified by TEM and XRD; one having a tetragonal structure with a = 5.65 Å, c = 2.75Å, and the second having a monoclinic structure with a = 5.065 Å, b= 11.5 Å, c = 2.801 Å and β = 96°. Their stoichiometric values and atomic arrangements have not yet been identified. Furthermore, variation in growth parameters, for example methane concentration, bias voltage, etc., can yield preferred growth of different C-N phases.