Molecular salts of 2,6-dihydroxybenzoic acid (2,6-DHB) with N-heterocycles: Crystal structures, spectral properties and Hirshfeld surface analysis

Abstract In the present study, two molecular complexes of 2,6-DHB with pharmaceutically active nutraceuticals i.e. nicotinic acid (NA) and nicotinamide (NIC) have been synthesized and preliminarily characterized by powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC) and FT-IR spectroscopy. Finally the crystal structures were solved by single crystal X-ray diffraction and the structures were analyzed in terms of supramolecular interactions. The salt 1 crystallizes in the monoclinic space group Cc , with a = 10.1503(1) A, b = 12.3821(1) A, c = 9.5291(1) A, β = 94.343(1)°, V = 1194.20(2) A 3 , Z = 4. The salt 2 crystallizes in monoclinic space group P 2 1 / n , with a = 7.0098 (1) A, b = 12.5495 (1) A, c = 13.4048 (1) A, β = 92.746 (1)°, V = 1177.86 (2) A 3 , Z = 4. The molecular packing of both salts are stabilized by N + –H⋯O − , O–H⋯O − , N–H⋯O and O–H⋯O hydrogen bonding interactions. DFT calculations substantiate the features of crystal structures. The Hirshfeld surfaces and the associated 2D fingerprint plots were investigated which revealed that more than two-third of close contacts were associated with relatively weak H⋯H, C⋯H and H⋯C interactions. The use of 3-D Hirshfeld surfaces in combination with 2-D fingerprint plots revealed that these weak interactions play major role in molecular crystal packing.