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Crystal structures and hydrogen bonding in the proton-transfer salts of nicotine with 3,5-di-nitro-salicylic acid and 5-sulfosalicylic acid.

ABSTRACT: The structures of the 1:1 anhydrous salts of nicotine (NIC) with 3,5-di-nitro-salicylic acid (DNSA) and 5-sulfosalicylic acid (5-SSA), namely (1R,2S)-1-methyl-2-(pyridin-3-yl)-1H-pyrrolidin-1-ium 2-carb-oxy-4,6-di-nitro-phenolate, C10H15N2 (+)·C7H3N2O7 (-), (I), and (1R,2S)-1-methyl-2-(pyridin-3-yl)-1H-pyrrolidin-1-ium 3-carb-oxy-4-hy-droxy-benzene-sulfonate, 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 ?-?-associated stacks which are parallel to the NIC cation chains along a [ring-centroid separation = 3.857?(2)?Å]. Weak C-H?O inter-actions 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 carb-oxy-lic acid O-H?Npyridine hydrogen bonds. These chains, which extend along b, are pseudocentrosymmetrically related and give ?-? inter-actions 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 inter-actions between the chains, giving an overall three-dimensional structure.

SUBMITTER: Smith G

PROVIDER: S-EPMC4257264 | biostudies-literature | 2014 Nov

REPOSITORIES: biostudies-literature

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Crystal structures and hydrogen bonding in the proton-transfer salts of nicotine with 3,5-di-nitro-salicylic acid and 5-sulfosalicylic acid.

Smith Graham G Wermuth Urs D UD

Acta crystallographica. Section E, Structure reports online 20141029 Pt 11

The structures of the 1:1 anhydrous salts of nicotine (NIC) with 3,5-di-nitro-salicylic acid (DNSA) and 5-sulfosalicylic acid (5-SSA), namely (1R,2S)-1-methyl-2-(pyridin-3-yl)-1H-pyrrolidin-1-ium 2-carb-oxy-4,6-di-nitro-phenolate, C10H15N2 (+)·C7H3N2O7 (-), (I), and (1R,2S)-1-methyl-2-(pyridin-3-yl)-1H-pyrrolidin-1-ium 3-carb-oxy-4-hy-droxy-benzene-sulfonate, C10H15N2 (+)·C7H5O6S(-), (II), are reported. The asymmetric units of both (I) and (II) comprise two independent nicotinium cations (C and ...[more]

PMID: 25484766

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Project description:The crystal structures of two ammonium salts of 2-amino-4-nitro-benzoic acid are described, namely di-methyl-aza-nium 2-amino-4-nitro-benzoate, C2H8N+·C7H5N2O4-, (I), and di-butyl-aza-nium 2-amino-4-nitro-benzoate, C8H20N+·C7H5N2O4-, (II). The asymmetric unit of (I) comprises a single cation and a single anion. In the anion, small twists are noted for the carboxyl-ate and nitro groups from the ring to which they are connected, as indicated by the dihedral angles of 11.45 (13) and 3.71 (15)°, respectively; the dihedral angle between the substituents is 7.9 (2)°. The asymmetric unit of (II) comprises two independent pairs of cations and anions. In the cations, different conformations are noted in the side chains in that three chains have an all-trans [(+)-anti-periplanar] conformation, while one has a distinctive kink resulting in a (+)-synclinal conformation. The anions, again, exhibit twists with the dihedral angles between the carboxyl-ate and nitro groups and the ring being 12.73 (6) and 4.30 (10)°, respectively, for the first anion and 8.1 (4) and 12.6 (3)°, respectively, for the second. The difference between anions in (I) and (II) is that in the anions of (II), the terminal groups are conrotatory, forming dihedral angles of 17.02 (8) and 19.0 (5)°, respectively. In each independent anion of (I) and (II), an intra-molecular amino-N-H⋯O(carboxyl-ate) hydrogen bond is formed. In the crystal of (I), anions are linked into a jagged supra-molecular chain by charge-assisted amine-N-H⋯O(carboxyl-ate) hydrogen bonds and these are connected into layers via charge-assisted ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds. The resulting layers stack along the a axis, being connected by nitro-N-O⋯π(arene) and methyl-C-H⋯O(nitro) inter-actions. In the crystal of (II), the anions are connected into four-ion aggregates by charge-assisted amino-N-H⋯O(carboxyl-ate) hydrogen bonding. The formation of ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds, involving all ammonium-N-H and carboxyl-ate O atoms leads to a three-dimensional architecture; additional C-H⋯O(nitro) inter-actions contribute to the packing. The Hirshfeld surface analysis confirms the importance of the hydrogen bonding in both crystal structures. Indeed, O⋯H/H⋯O inter-actions contribute nearly 50% to the entire Hirshfeld surface in (I).

Dataset Information

Crystal structures and hydrogen bonding in the proton-transfer salts of nicotine with 3,5-di-nitro-salicylic acid and 5-sulfosalicylic acid.

Publications

Crystal structures and hydrogen bonding in the proton-transfer salts of nicotine with 3,5-di-nitro-salicylic acid and 5-sulfosalicylic acid.

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