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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: One of the DNSA anions shows a 25% rotational disorder in the benzene ring system.Weak C-H⋯O inter-actions between chain substructures give an overall three-dimensional structure.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.

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The hydrogen-bonded A–C and B–D chain structures in (II), extending along b. Non-associative H atoms have been omitted. For symmetry codes, see Table 2 ▶.
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fig4: The hydrogen-bonded A–C and B–D chain structures in (II), extending along b. Non-associative H atoms have been omitted. For symmetry codes, see Table 2 ▶.

Mentions: In the crystal of (II), the independent A and B 5-SSA anions form carb­oxy­lic acid O—H⋯Npyridine hydrogen bonds with the D and C NIC cations, respectively (Table 2 ▶) (see Fig. 2 ▶). These cation–anion subunits are then extended into independent chain structures through pyrrolidinium N—H⋯Osulfonate hydrogen bonds, which with anion C is three-centre (O51Bi and O53Bi) and with anion D, linear (O52Aii). These give independent zigzag chain substructures which extend along b. Although there are no formal hydrogen-bonding links between the two chains, there are π–π inter­actions between 5-SSA anion A and B benzene rings and C and D NIC cation pyridine rings, respectively [ring-centroid separations = 3.6422 (19) and 3.7117 (19) Å] (Fig. 4 ▶). The presence of a number of inter­molecular C—H⋯O hydrogen-bonding inter­actions to carboxyl, nitro and phenolic O-atom acceptors gives rise to an overall three-dimensional structure.


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 hydrogen-bonded A–C and B–D chain structures in (II), extending along b. Non-associative H atoms have been omitted. For symmetry codes, see Table 2 ▶.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig4: The hydrogen-bonded A–C and B–D chain structures in (II), extending along b. Non-associative H atoms have been omitted. For symmetry codes, see Table 2 ▶.
Mentions: In the crystal of (II), the independent A and B 5-SSA anions form carb­oxy­lic acid O—H⋯Npyridine hydrogen bonds with the D and C NIC cations, respectively (Table 2 ▶) (see Fig. 2 ▶). These cation–anion subunits are then extended into independent chain structures through pyrrolidinium N—H⋯Osulfonate hydrogen bonds, which with anion C is three-centre (O51Bi and O53Bi) and with anion D, linear (O52Aii). These give independent zigzag chain substructures which extend along b. Although there are no formal hydrogen-bonding links between the two chains, there are π–π inter­actions between 5-SSA anion A and B benzene rings and C and D NIC cation pyridine rings, respectively [ring-centroid separations = 3.6422 (19) and 3.7117 (19) Å] (Fig. 4 ▶). The presence of a number of inter­molecular C—H⋯O hydrogen-bonding inter­actions to carboxyl, nitro and phenolic O-atom acceptors gives rise to an overall three-dimensional structure.

Bottom Line: One of the DNSA anions shows a 25% rotational disorder in the benzene ring system.Weak C-H⋯O inter-actions between chain substructures give an overall three-dimensional structure.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