Crystal structures and hydrogen bonding in the proton-transfer salts of nicotine with 3,5-dinitrosalicylic acid and 5-sulfosalicylic acid

Abstract

The structures of the 1:1 anhydrous salts of nicotine (NIC) with 3,5-dinitrosalicylic acid (DNSA) and 5-sulfosalicylic acid (5-SSA), namely (1R,2S)-1-methyl-2-(pyridin-3-yl)-1H-pyrrolidin-1-ium 2-carboxy-4,6-dinitrophenolate, C10H15N2+·C7H3N2O7−, (I), and (1R,2S)-1-methyl-2-(pyridin-3-yl)-1H-pyrrolidin-1-ium 3-carboxy-4-hydroxybenzenesulfonate, C10H15N2+·C7H5O6S−, (II), are reported. The asymmetric units of both (I) and (II) comprise two independent nicotinium cations (C and D) and either two DNSA or two 5-SSA anions (A and B), respectively. One of the DNSA anions shows a 25% rotational disorder in the benzene ring system. In the crystal of (I), inter-unit pyrrolidinium N—H...Npyridine hydrogen bonds generate zigzag NIC cation chains which extend along a, while the DNSA anions are not involved in any formal inter-species hydrogen bonding but instead form π–π-associated stacks which are parallel to the NIC cation chains along a [ring-centroid separation = 3.857 (2) Å]. Weak C—H...O interactions between chain substructures give an overall three-dimensional structure. In the crystal of (II), A and B anions form independent zigzag chains with C and D cations, respectively, through carboxylic acid O—H...Npyridine hydrogen bonds. These chains, which extend along b, are pseudocentrosymmetrically related and give π–π interactions between the benzene rings of anions A and B and the pyridine rings of the NIC cations C and D, respectively [ring centroid separations = 3.6422 (19) and 3.7117 (19) Å]. Also present are weak C—H...O hydrogen-bonding interactions between the chains, giving an overall three-dimensional structure.

Keywords

• crystal structure
• nicotine
• proton-transfer salts
• 3,5-dinitrosalicylic acid
• 5-sulfosalicylic acid
• hydrogen-bonding
• π–π interactions