Hydrogen Bonding in the 2,2'-Bipyridinium Salt of 1,2,4,5-Benzenetetracarboxylic Acid (Pyromellitic Acid)

Mrvoš-Sermek, Draginja; Popović, Zora; Matković‐Čalogović, Dubravka

doi:10.1107/s0108270196003940

Cited by 19 publications

(22 citation statements)

References 9 publications

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“…With formation of a salt, nitrogen acquires a positive charge through proton transfer (donation of hydrogen) from the acid component: CN → CNH + . The nitrogen XPS thus reveals that one of the nitrogen atoms of bipyridine has been protonated (CNH + ), shifting its photoemission to higher energy (Table 1), in agreement with the single crystal X-ray diffraction (XRD) structure, 35 Table 1), revealing that a proton has been transferred from 5-sulfosalicylic acid to one of the 4,4′-bipyridine nitrogen atoms, forming a 1:1 salt. This is confirmed by the subsequently obtained single crystal XRD, with 4BPY/sulfo involving NH + , SO 3 − [BPY + , sulfo − ] (Figure 3 and Supporting Information).…”

Section: ■ Introductionsupporting

confidence: 54%

“…In the 2BPY/BTA salt, single crystal XRD 35 shows the donated hydrogen (from COOH) to be closer to nitrogen than that donated by SO 3 H in the 4BPY/ sulfo salt (Table 1). This can be viewed as a more complete proton transfer from the acid and leads to decreased electron density (higher effective positive charge) at the protonated nitrogen CNH + for 2BPY as it interacts more strongly with the hydrogen atom.…”

Section: ■ Discussionmentioning

confidence: 94%

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Proton Transfer, Hydrogen Bonding, and Disorder: Nitrogen Near-Edge X-ray Absorption Fine Structure and X-ray Photoelectron Spectroscopy of Bipyridine–Acid Salts and Co-crystals

Stevens

Newton

Jaye

et al. 2015

Crystal Growth & Design

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The sensitivity of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to Brønsted donation and the protonation state of nitrogen in the solid state is investigated through a series of multicomponent bipyridine− acid systems alongside X-ray photoelectron spectroscopy (XPS) data. A large shift to high energy occurs for the 1s → 1π* resonance in the nitrogen K-edge NEXAFS with proton transfer from the acid to the bipyridine base molecule and allows assignment as a salt (CNH + ), with the peak ratio providing the stoichiometry of the types of nitrogen species present. A corresponding binding energy shift for CNH + is observed in the nitrogen XPS, clearly identifying protonation and formation of a salt. The similar magnitude shifts observed with both techniques relative to the unprotonated nitrogen of co-crystals (CN) suggest that the chemical state (initial-state) effects dominate. Results from both techniques reveal the sensitivity to identify proton transfer, hydrogen bond disorder, and even the potential to distinguish variations in hydrogen bond length to nitrogen. ■ INTRODUCTIONProton (hydrogen) transfer can be thought of as one of the simplest chemical reactions, ranging from complete transfer from an acidic to a basic moiety (protonation through Brønsted donation) to varying degrees of sharing through hydrogen bonding. Whether Brønsted proton transfer occurs has a profound effect on the location of protons in crystal structures and influences chemical and physical properties. These interactions can be employed to target properties of solid forms (crystal engineering), with particular relevance to the pharmaceutical industry where acid/base guest molecules can be combined with active ingredients to tailor properties such as solubility and bioavailability through formation of salts and cocrystals. 1−4 Other relevant fields are organic ferroelectrics, 5 energetic materials, 6 and the design of materials with targeted optical properties such as color 7 and luminescence. 8,9 Even among hydrogen bonds, the level of interaction with the donor and acceptor atoms can vary significantly, from relatively weak to strong with quasi-covalent character, 10 and there is also the possibility of disordered hydrogen bonds. 11 While X-ray diffraction (XRD) and solid-state nuclear magnetic resonance spectroscopy (ssNMR) are often techniques of choice for structural characterization, 2,11−14 they are not always unambiguous with regard to proton locations (although further clarity can often be obtained by neutron diffraction). 11,13−16 The importance of accurate characterization of salts vs co-crystals based on this relatively small difference in proton location should not be underestimated, particularly with the wider implications for intellectual property and regulatory control in the pharmaceutical industry. 4,17 X-ray photoelectron spectroscopy (XPS) has recently been shown to unequivocally identify whether intermolecular proton transfer occurs in a range of two-component systems and distinguish protonation (salt...

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Section: ■ Introductionsupporting

confidence: 54%

Section: ■ Discussionmentioning

confidence: 94%

Proton Transfer, Hydrogen Bonding, and Disorder: Nitrogen Near-Edge X-ray Absorption Fine Structure and X-ray Photoelectron Spectroscopy of Bipyridine–Acid Salts and Co-crystals

Stevens

Newton

Jaye

et al. 2015

Crystal Growth & Design

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“…The crystal structures of (H 2 BTC)(Hphen) 2 (H 4 BTC) (where phen is 1,10-phenanthroline) [5], (H 3 BTC)(Hbipy) × 3H 2 O(where bipy is 2,2'-bipyridine) [6] and (H 2 BTC)(Hbipy) 2 (H 4 BTC) [7] have also been reported previously. The asymmetric unit of the title crystal structure contains two bis(2-ammonioethyl)amine cations, two halfs of benzene-1,2,4,5-tetracarboxylate anions and six water molecules.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of bis[bis(2-ammonioethyl)amine] benzene-1,2,4,5- tetracarboxylate hexahydrate, [C4H15N3]2[C10H2O8] · 6H2O

Pasban¹,

Esmhosseini²,

Ahmadi³

et al. 2012

Zeitschrift Für Kristallographie - New Crystal Structures

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“…These morphologies are clearly too big to be polyimide crystallites. As PMA is a well- known tecton for supramolecular solid-state assemblies, such as co-crystals and salts, 18,19 we speculate that several different compounds of this type form hydrothermally at 140 C. Consequently, we did not further pursue low T R . For T R ¼ 200 C, we only investigated shorter t R , since full condensation and high crystallinity had already been obtained at t R ¼ 24 h (Fig.…”

Section: Hydrothermal Synthesis Of Pi6mentioning

confidence: 99%

Green one-pot synthesis and processing of polyimide–silica hybrid materials

et al. 2017

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Hydrogen Bonding in the 2,2'-Bipyridinium Salt of 1,2,4,5-Benzenetetracarboxylic Acid (Pyromellitic Acid)

Cited by 19 publications

References 9 publications

Proton Transfer, Hydrogen Bonding, and Disorder: Nitrogen Near-Edge X-ray Absorption Fine Structure and X-ray Photoelectron Spectroscopy of Bipyridine–Acid Salts and Co-crystals

Proton Transfer, Hydrogen Bonding, and Disorder: Nitrogen Near-Edge X-ray Absorption Fine Structure and X-ray Photoelectron Spectroscopy of Bipyridine–Acid Salts and Co-crystals

Crystal structure of bis[bis(2-ammonioethyl)amine] benzene-1,2,4,5- tetracarboxylate hexahydrate, [C4H15N3]2[C10H2O8] · 6H2O

Green one-pot synthesis and processing of polyimide–silica hybrid materials

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