The title methanol solvate, C(24)H(22)N(4)O(5).CH(3)OH, forms an extended three-dimensional hydrogen-bonded structure, assisted by the presence of several good donor and acceptor sites. It shows none of the crystal packing features typically expected of piperazinediones, such as amide-to-amide R(2)(2)(8) hydrogen bonding. In this structure the methanol solvent appears to play only a space-filling role; it is not involved in any hydrogen bonding and instead is disordered over several sites. This study reports, to the best of our knowledge, the first crystal structure of an indane-containing piperazinedione compound which exhibits a three-dimensional hydrogen-bonded structure formed by classical (N-H...O and N-H...N) hydrogen-bonding interactions.