Halogen Bond as Controlling the Crystal Structure of 4-Amino-3,5-Dihalogenobenzoic Acid and Its Effect on the Positional Ordering/Disordering of Acid Protons

Ueda, Keigo; Oguni, Masaharu; Asaji, Tetsuo

doi:10.1021/cg501479p

Cited by 13 publications

(8 citation statements)

References 35 publications

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“…Halogen bonds also play an important role in controlling molecular recognition in biological systems and determining molecular orientation within crystals. [5][6][7][8][9] The origin of the Lewis acid in halogen bonding is mainly attributed to a region of positive electrostatic potential (s-hole), [10][11][12][13][14][15] being the consequence of the diminished electron density on the extension of a covalent bond to the halogen atom. The applications of halogen bonds are dependent on their strength, which becomes stronger in the order F ( Cl < Br < I.…”

Section: Introductionmentioning

confidence: 99%

Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF₃⋯4-iodopyridine⋯N-base

Cheng

Yang

et al. 2017

RSC Adv.

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The ternary complexes of PhSiF 3 /4-iodopyridine/N-base (N-base ¼ HCN, NH 3 , NHNH 2 , and NH 2 CH 3), PhTF 3 /4-iodopyridine/NH 3 (T ¼ C and Ge), PhSiY 3 /4-iodopyridine/NH 3 (Y ¼ H and Cl), PhSiF 3 /4bromopyridine/NH 3 and the respective binary complexes have been investigated. 4-Halopyridine in these ternary complexes plays a dual role of both a Lewis acid with the s-hole on the halogen atom in the halogen bond and a Lewis base with the nitrogen atom in the tetrel bond. The interplay between both interactions in the ternary complexes has been analyzed in terms of the binding distance, binding energy, charge transfer, electron density and electrostatic potentials. A synergistic effect is found for the tetrel and halogen bonds in most of the ternary complexes, while a diminutive effect is present for the hydrogen and halogen bonds in PhCF 3 /4-iodopyridine/NH 3. The magnitude of cooperative energy depends on the strength of both interactions. Interestingly, PhSiCl 3 /4-iodopyridine has a stronger tetrel bond than PhSiH 3 /4-iodopyridine, inconsistent with the size of the s-hole on the Si atom. In addition, the tetrel bond exhibits a partially covalent interaction nature.

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Section: Introductionmentioning

confidence: 99%

Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF₃⋯4-iodopyridine⋯N-base

Cheng

Yang

et al. 2017

RSC Adv.

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“…Hydroxy acid (I) (Prout et al, 1988;Fig. 4) and amino acids (II) (Pant, 1965;Ueda et al, 2014) form interlocking ribbons in which adjacent carboxy dimers are connected by IÁ Á ÁI contacts, or amino-carboxy hydrogen-bonds, respectively. 4-Cyanobenzoic acid (III) forms a sheet structure in which carboxy dimers are connected lengthwise by R 2 2 (10) rings formed by CNÁ Á ÁH contacts, and laterally by R 3 3 (7) rings formed by weak C-HÁ Á ÁO bonds flanking each pair of carboxy groups (Higashi & Osaki, 1981).…”

Section: Figurementioning

confidence: 99%

A 2:1 co-crystal of 3,5-dibromo-4-cyanobenzoic acid and anthracene

Noland

Rieger

et al. 2017

Acta Crystallogr E Cryst Commun

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The title co-crystal, C 8 H 3 Br 2 NO 2 Á0.5C 14 H 10 , was self-assembled from a 2:1 mixture of the components in slowly evaporating dichloromethane. The molecules adopt a sheet structure parallel to (112) in which carboxy hydrogen-bonded dimers and anthracene molecules stagger in both dimensions. Within the sheets, six individual cyano acid molecules surround each anthracene molecule. Cyano acid molecules form one of the two possible R 2 2 (10) rings between neighboring cyano and bromo groups. Compared to the dichloro analog [Britton (2012). J. Chem. Crystallogr. 42,[851][852][853][854][855], the dihedral angle between the best-fit planes of acid and anthracene molecules has decreased from 7.1 to 0.9 (2) . Chemical contextDoyle Britton published roughly 30 crystallographic articles on solid-phase cyano-halo interactions from variously substituted halobenzonitriles and isocyanides. Britton postulated that 3,5-dichloro-4-cyanobenzoic acid might assemble into a honeycomb-like sheet structure (Fig. 1a) via a combination of carboxy hydrogen-bond dimerization and CNÁ Á ÁCl short contacts. In 2012, he found that the cyano acid molecules alone do not pack in this way, but slow evaporation of mixtures containing naphthalene or anthracene afforded 2:1 acid:hydrocarbon co-crystals roughly matching his proposed structure (Britton, 2012). However, no CNÁ Á ÁCl contacts were observed (Fig. 1b). Anthracene was the better fit, although it was too large to allow the ideal molecular arrangement. There is no obvious substitute for anthracene or naphthalene. Thus, we have prepared anthracene co-crystals with the dibromo analog in hopes that the larger Br bond and contact radii might close the CNÁ Á ÁX gaps observed with Cl. Structural commentaryThe benzene (C2-C5/C7/C8) and anthracene (C9-C15 and symmetry equivalents, Fig. 2) ring systems are nearly planar. The mean deviation of atoms from the planes of best fit are 0.0074 (17) Å and 0.0041 (14) Å , respectively, both of which are comparable to the corresponding values in the dichloro crystal. However, the dihedral angle between the carboxy group (O1-C1-O2) and the benzene ring is 3.2 (4) , compared with 7.2 in the dichloro analog. Supramolecular featuresThe dihedral angle between the benzene and anthracene planes is 0.9 (2) , which is much lower than 7.1 of the dichloro analog. As expected, R 2 2 (8) carboxy hydrogen-bonded dimers are observed (Table 1); these are located on an inversion center. R 2 2 (10) rings form about another inversion center based on C6 N1Á Á ÁBr2 contacts (Table 2); however, the corresponding N1Á Á ÁBr1 contacts are not observed (Fig. 3). Instead, 3.5534 (5) Å Br1Á Á ÁBr1 contacts form, slightly closer than the 3.70 Å non-bonded contact diameter of Br (Rowland & Taylor, 1996). In the title co-crystal, two corners of the anthracene molecule contact the cyano acid network (Fig. 3), whereas all four corners made contact in the Cl analog (Fig. 1b). Overall, substitution of Cl atoms with Br atoms has facilitated the formation of half of the envisioned CNÁ Á ...

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“…Thus, the hydrogen bis(pyridinium-2carboxylate) cation is similar to the Type A acid salts of carboxylic acids . The H atom is disordered, with a 0.50:0.50 ratio between the two positions towards the two carboxylate O atoms (Jones et al, 2013;Ueda et al, 2014). The dihedral angle between the planes of adjacent pyridinium rings is 60.8 (3) .…”

Section: Figurementioning

confidence: 99%

Reversible phase transition of 2-carboxypyridinium perchlorate–pyridinium-2-carboxylate (1/1)

et al. 2015

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The title salt, C6H6NO2(+)·ClO4(-)·C6H5NO2, was crystallized from an aqueous solution of equimolar quantities of perchloric acid and pyridine-2-carboxylic acid. Differential scanning calorimetry (DSC) measurements show that the compound undergoes a reversible phase transition at about 261.7 K, with a wide heat hysteresis of 21.9 K. The lower-temperature polymorph (denoted LT; T = 223 K) crystallizes in the space group C2/c, while the higher-temperature polymorph (denoted RT; T = 296 K) crystallizes in the space group P2/c. The relationship between these two phases can be described as: 2a(RT) = a(LT); 2b(RT) = b(LT); c(RT) = c(LT). The crystal structure contains an infinite zigzag hydrogen-bonded chain network of 2-carboxypyridinium cations. The most distinct difference between the higher (RT) and lower (LT) temperature phases is the change in dihedral angle between the planes of the carboxylic acid group and the pyridinium ring, which leads to the formation of different ten-membered hydrogen-bonded rings. In the RT phase, both the perchlorate anions and the hydrogen-bonded H atom within the carboxylic acid group are disordered. The disordered H atom is located on a twofold rotation axis. In the LT phase, the asymmetric unit is composed of two 2-carboxypyridinium cations, half an ordered perchlorate anion with ideal tetrahedral geometry and a disordered perchlorate anion. The phase transition is attributable to the order-disorder transition of half of the perchlorate anions.

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Halogen Bond as Controlling the Crystal Structure of 4-Amino-3,5-Dihalogenobenzoic Acid and Its Effect on the Positional Ordering/Disordering of Acid Protons

Cited by 13 publications

References 35 publications

Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF₃⋯4-iodopyridine⋯N-base

Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF₃⋯4-iodopyridine⋯N-base

A 2:1 co-crystal of 3,5-dibromo-4-cyanobenzoic acid and anthracene

Reversible phase transition of 2-carboxypyridinium perchlorate–pyridinium-2-carboxylate (1/1)

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Halogen Bond as Controlling the Crystal Structure of 4-Amino-3,5-Dihalogenobenzoic Acid and Its Effect on the Positional Ordering/Disordering of Acid Protons

Cited by 13 publications

References 35 publications

Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF3⋯4-iodopyridine⋯N-base

Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF3⋯4-iodopyridine⋯N-base

A 2:1 co-crystal of 3,5-dibromo-4-cyanobenzoic acid and anthracene

Reversible phase transition of 2-carboxypyridinium perchlorate–pyridinium-2-carboxylate (1/1)

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Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF₃⋯4-iodopyridine⋯N-base

Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF₃⋯4-iodopyridine⋯N-base