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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 G, Wermuth UD - Acta Crystallogr Sect E Struct Rep Online (2014)

Bottom Line: 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.Also present are weak C-H⋯O hydrogen-bonding inter-actions between the chains, giving an overall three-dimensional structure.

View Article: PubMed Central - HTML - PubMed

Affiliation: Science and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia.

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 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 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 π-π 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.

No MeSH data available.


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The mol­ecular conformation and atom labelling for the two NIC cations (C and D) and the two DNSA anions (A and B) in the asymmetric unit of (I), with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines (see Table 1 ▶).
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fig1: The mol­ecular conformation and atom labelling for the two NIC cations (C and D) and the two DNSA anions (A and B) in the asymmetric unit of (I), with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines (see Table 1 ▶).

Mentions: In both the nicotinium salts of DNSA (I) and 5-SSA (II), proton-transfer to the pyrrolidine N-atom of nicotine has occurred as expected, generating an N11(R) chiral centre relative to the known C21(S) centre. Also, in both (I) and (II) (Figs. 1 ▶ and 2 ▶), the asymmetric units comprise two independent NIC+ cations (C and D) and either, for (I), two DNSA phenolate monoanions or two 5-SSA carboxyl­ate monoanions (A and B) (Figs. 1 ▶, 2 ▶). With (II), the two independent anion and cation pairs are pseudo-centrosymmetrically related but the presence of the inversion centre is obviated by the fact that both of the NIC cations have the same N11(R), C21(S) absolute configuration.


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

Smith G, Wermuth UD - Acta Crystallogr Sect E Struct Rep Online (2014)

The mol­ecular conformation and atom labelling for the two NIC cations (C and D) and the two DNSA anions (A and B) in the asymmetric unit of (I), with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines (see Table 1 ▶).
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4257264&req=5

fig1: The mol­ecular conformation and atom labelling for the two NIC cations (C and D) and the two DNSA anions (A and B) in the asymmetric unit of (I), with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines (see Table 1 ▶).
Mentions: In both the nicotinium salts of DNSA (I) and 5-SSA (II), proton-transfer to the pyrrolidine N-atom of nicotine has occurred as expected, generating an N11(R) chiral centre relative to the known C21(S) centre. Also, in both (I) and (II) (Figs. 1 ▶ and 2 ▶), the asymmetric units comprise two independent NIC+ cations (C and D) and either, for (I), two DNSA phenolate monoanions or two 5-SSA carboxyl­ate monoanions (A and B) (Figs. 1 ▶, 2 ▶). With (II), the two independent anion and cation pairs are pseudo-centrosymmetrically related but the presence of the inversion centre is obviated by the fact that both of the NIC cations have the same N11(R), C21(S) absolute configuration.

Bottom Line: 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.Also present are weak C-H⋯O hydrogen-bonding inter-actions between the chains, giving an overall three-dimensional structure.

View Article: PubMed Central - HTML - PubMed

Affiliation: Science and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia.

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 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 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 π-π 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.

No MeSH data available.


Related in: MedlinePlus