A series of randomly nitrogen-substituted carbon clusters in graphitelike structures, containing up to 96 carbon atoms, is theoretically investigated through semiemipirical pseudopotential techniques. The evolution of conformation and electronic structure is obtained as a function of nitrogen content. Results from semiempirical geometry optimizations reveal that the clusters are planar for nitrogen concentrations up to [N]/[C]similar to 20%. Above this concentration, buckling develops in the clusters. One of the characteristics of these corrugated clusters is the presence of carbon dangling bonds. Chemical stabilization imposes that these structures evolve to either a three-dimensional, fully covalent carbon nitride network, or to molecular forms. Among the well-defined molecular structures that could develop in amorphous carbon nitride, we found nanotubules and a molecular cage of elemental compositions CN and C3N4, respectively. [S0163-1829(38)06943-4].58201391813924