Xray Studies on Crystalline Complexes Involving Amino Acids and Peptides XXXIV. Novel Mode of Aggregation, Interaction Patterns and Chiral Effects in the Maleic Acid Complexes of DL- and L- Arginine

Abstract

Amino acid - carboxylic acid complexes provide useful information in relation to molecular interactions in present day biological systems and to prebiotic self-organisation. The crystal structures of the complexes of maleic acid with DL- arginine (orthorhombic; Pca2₁; a=15.9829, b=5.4127, c=16.1885; R=0.0522 for 956 reflections) and L- arginine (triclinic; P1; a=5.2641, b=8.0388, c=9.7860, α=106.197, β=97.275, γ=101.64; R=0.039 for 1749 reflections) have been determined. The complexes are made up of positively charged zwitterionic arginine molecules and negatively charged semi-maleate ions which contain an intramolecular symmetric O—H—O hydrogen bond. In both the structures, the amino acid molecules aggregate into layers. In each layer, S2 head-to-tail sequences are interconnected through specific intermolecular interactions between α-carboxylate and guanidyl groups, an arrangement observed for the first time in crystal structures involving arginine. The carboxylate-guanidyl interactions are of different types in the two complexes and consequently aggregation patterns in them exhibit substantial differences. Interactions between the amino acid layers involve the semi-maleate ions in both the complexes. In addition, water-bridges also exist in the L complex. The full potential of the guanidyl group for specific interactions is realized in both the structures. The L complex contains an array of water-mediated salt bridges. The structures demonstrate that the effect of chirality on molecular aggregation can span a wide range.