Supramolecular Architectures in 5,5′-Substituted Hydantoins: Crystal Structures and Hirshfeld Surface Analyses

Abstract

A series of three 5,5′-substituted hydantoin derivatives (1−3) were synthesized, and their crystal structures were solved using single-crystal synchrotron/powder-crystal X-ray diffraction data with a detailed analysis of Hirshfeld surfaces and fingerprint plots facilitating a comparison of intermolecular interactions in building different supramolecular architectures. A comparison of supramolecular assembly in the compounds with that in similar 5,5′-substituted hydantoins in the Cambridge Structural Database (CSD) has been presented. The crystal packing in compounds 1−3 containing complementary hydrogen bonding groups, i.e. the amino NH donors and carbonyl O acceptors, exhibits three types of supramolecular synthons. In the dipropyl substituted hydantoin (1), intermolecular N−H···O hydrogen bonds with only one carbonyl O atom acting as a double acceptor generate a one-dimensional C11(4)C11(4)[R22(8)] network propagating along the [100] direction, while in 3, a 5-spiro fused hydantoin, the cyclic R22(8) motifs self-organize through pairs of N−H···O hydrogen bonds to form a C22(9)[R22(8)][R22(8)] framework running along the [1−10] direction. The molecular assembly in 2, with a dibutyl substitution at the hydantoin C-5 position, produces R44(17) synthons, which are edge-fused to form two-dimensional molecular sheets in the (100) plane. The formation of a supramolecular architecture built with an R44(17) synthon is unprecedented among the substituted hydantoin structures in the CSD.