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 C1 1(4)C1 1(4)[R2 2(8)] network propagating along the [100] direction, while in 3, a 5-spiro fused hydantoin, the cyclic R2 2(8) motifs self-organize through pairs of N−H···O hydrogen bonds to form a C2 2(9)[R2 2(8)][R2 2(8)] framework running along the [1−10] direction. The molecular assembly in 2, with a dibutyl substitution at the hydantoin C-5 position, produces R4 4(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 R4 4(17) synthon is unprecedented among the substituted hydantoin structures in the CSD.

Supramolecular structure of 5-methyl-5-phenyl hydantoin and hydrogen-bonding patterns in 5,5′-substituted hydantoins

“…The N1-C2-O2 bond angle 130.0 (2)°is greater than the N3-C2-O2 angle 123.2 (2)°. This difference is also observed in all 136 hydantoins derivative entries including the hydantoin molecule [40], and can be attributed to the fact the N3 atom shares its lone pair between the O2 and O4 atoms, while the N1 atom is involved in a π-resonance with the C2-O2 carbonyl group only [41]. The molecular structure and crystal packing of (I) are stabilized by N-H···O hydrogen bonds.…”

Selective picomolar level fluorometric sensing of the Cr(vi)-oxoanion in a water medium by a novel metal–organic complex

“…Molecular Hirshfeld surfaces [42][43][44][45][46][47][48] in the crystal structure of MOC are determined based on the electron distribution calculated as the sum of spherical atom electron densities. 49,50 For a specified crystal structure and set of spherical atomic electron densities, the Hirshfeld surface is unique.…”

Structural and Hirshfeld Surface Analyses of a Novel Hetero-Tetranuclear CuII-NaI Bis(Salamo)-Based Coordination Compound

“…As for the large amount of white region in dnorm surfaces, it is suggested that there is a weaker and farther contact between molecules, rather than hydrogen bonding. Figure 7 showed that the two-dimensional (2D) plots that were generated [87] …”

“…As for the large amount of white region in d norm surfaces, it is suggested that there is a weaker and farther contact between molecules, rather than hydrogen bonding. Figure 7 showed that the two-dimensional (2D) plots that were generated [87] correspond to the O···H, C···H and H···H interactions from the Hirshfeld surface of the coordination compound 1. With the help of these analysis results, different interactions can be separated from each other that would commonly overlap in full fingerprint plots.…”