The salt–cocrystal spectrum in salicylic acid–adenine: the influence of crystal structure on proton-transfer balance

2019 ◽  
Vol 75 (4) ◽  
pp. 412-421 ◽  
Author(s):  
Sima Sedghiniya ◽  
Janet Soleimannejad ◽  
Jan Janczak
Keyword(s):  
Salicylic Acid ◽  
Proton Transfer ◽  
Crystal Engineering ◽  
X Ray Diffraction ◽  
Acid Base ◽  
Base Pairs ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Crystalline Environment ◽  
Opposite Extreme

At one extreme of the proton-transfer spectrum in cocrystals, proton transfer is absent, whilst at the opposite extreme, in salts, the proton-transfer process is complete. However, for acid–base pairs with a small ΔpK a (pK a of base − pK a of acid), prediction of the extent of proton transfer is not possible as there is a continuum between the salt and cocrystal ends. In this context, we attempt to illustrate that in these systems, in addition to ΔpK a, the crystalline environment could change the extent of proton transfer. To this end, two compounds of salicylic acid (SaH) and adenine (Ad) have been prepared. Despite the same small ΔpK a value (≈1.2), different ionization states are found. Both crystals, namely adeninium salicylate monohydrate, C5H6N5 +·C7H5O3 −·H2O, I, and adeninium salicylate–adenine–salicylic acid–water (1/2/1/2), C5H6N5 +·C7H5O3 −·2C5H5N5·C7H6O3·2H2O, II, have been characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis (C, H and N) techniques. In addition, the intermolecular hydrogen-bonding interactions of compounds I and II have been investigated and quantified in detail on the basis of Hirshfeld surface analysis and fingerprint plots. Throughout the study, we use crystal engineering, which is based on modifications of the intermolecular interactions, thus offering a more comprehensive screening of the salt–cocrystal continuum in comparison with pure pK a analysis.

scholarly journals Study on novel structure of tris-(4,4′-dimethyl-2,2′-dipyridyl) Nickel salicylic acid boric acid, Ni(C12H12N2)3●(C7H5O3)2●(H3BO3)

2021 ◽  
Vol 252 ◽  
pp. 02069
Author(s):  
Xiaoyan Ren ◽  
Haixing Liu ◽  
Yanfang Huo
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Salicylic Acid ◽  
Hydrothermal Reaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Novel Structure ◽  
Novel Complex

A novel complex Ni(C12H12N2)3●(C7H5O3)2●(H3BO3) has been synthesized from a hydrothermal reaction and the crystal structure has been determined by means of single-crystal X-ray diffraction. Triclinic, P-1. a= 12.5380(13) Å, b = 13.0100(15) Å, c = 15.1490(18) Å, α= 102.760(3)°, β= 94.480(2)°, γ= 94.540(2)°. V=2390.9(5) Å3. Z=2. R1 =0.0661, wR2 = 0.2128, T=293(2) K. The Ni atom is coordinated by six N atoms from three 4,4′-dimethyl-2,2′-dipyridyl molecular. The molecular structure stabilized by the O-H…O hydrogen-bonding interactions.

scholarly journals Crystal engineering: co-crystals of cinnamic acid derivatives with a pyridyl derivative co-crystallizer

2016 ◽  
Vol 72 (1) ◽  
pp. 87-95 ◽  
Author(s):  
Daniel A. Lorenzo ◽  
Sebastian J. K. Forrest ◽  
Hazel A. Sparkes
Keyword(s):  
Hydrogen Bonding ◽  
Diffraction Analysis ◽  
Cinnamic Acid ◽  
Crystal Engineering ◽  
X Ray Diffraction ◽  
Cinnamic Acid Derivative ◽  
Cinnamic Acid Derivatives ◽  
X Ray ◽  
Single Crystal Structures ◽  
Hydrogen Bonding Interactions

A number of hydrogen-bonded co-crystals, consisting of a cinnamic acid derivative and a pyridyl co-crystallizer, have been synthesized and their properties investigated by X-ray diffraction. Samples were prepared by recrystallization or solvent drop grinding oftrans-cinnamic acid (1), 4-methylcinnamic acid (2), 4-methoxy cinnamic acid (3) or 3,4-methoxy cinnamic acid (4), with 4,4-dipyridyl (A),iso-nicotinamide (B) or nicotinamide (C). The X-ray single-crystal structures of seven novel co-crystals, obtained through recrystallization, are examined and the hydrogen-bonding interactions discussed. Consistent hydrogen-bonding motifs were observed for samples prepared when using 4,4-dipyridyl (A) oriso-nicotinamide (B) as the co-crystallizing agent. Powder X-ray diffraction analysis of the samples prepared by solvent drop grinding suggests the formation of ten co-crystals.

scholarly journals Synthesis, Crystal Structure, and Hirshfeld Surface Analysis of Ciprofloxacin-Salicylic Acid Molecular Salt

2014 ◽  
Vol 2014 ◽  
pp. 1-5 ◽  
Author(s):  
Ravikumar Nagalapalli ◽  
Shankar Yaga Bheem
Keyword(s):  
Salicylic Acid ◽  
Acid Group ◽  
X Ray Diffraction ◽  
Carboxylic Acid Group ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Hirshfeld Surfaces ◽  
Ft Ir ◽  
Molecular Salt ◽  
Ft Ir Spectroscopy

In the present study, ciprofloxacin-salicylic acid molecular salt has been synthesized and preliminarily characterized by FT-IR spectroscopy. The single crystal X-ray diffraction (SCXRD) reveals the proton transfer from carboxylic acid group of salicylic acid to piperazine moiety in ciprofloxacin confirming the formation of new molecular salt. The molecular packing of the molecular salt is mainly supported by N+–H⋯O−, O–H⋯O, C–H⋯F, C–H⋯π, and π-π interactions. The 3D Hirshfeld surfaces and the associated 2D fingerprint plots were investigated for intermolecular hydrogen bonding interactions.

Supramolecular heterosynthon assemblies of ortho-phenylenediamine with substituted aromatic carboxylic acids

2018 ◽  
Vol 74 (1) ◽  
pp. 32-41 ◽  
Author(s):  
Risha Mishra ◽  
Raghavaiah Pallepogu
Keyword(s):  
X Ray Diffraction ◽  
Acid Base ◽  
Neutral Species ◽  
X Ray ◽  
Nitrobenzoic Acid ◽  
Hydrogen Bonding Interactions ◽  
Crystallization Experiments ◽  
Supramolecular Networks ◽  
Aromatic Anions ◽  
Ground Material

Co-crystallization experiments conducted between ortho-phenylenediamine (OPDA) and five substituted aromatic acids (phthalic acid, salicylic acid, 4-hydroxybenzoic acid, 4-nitrobenzoic acid and 3,5-dinitrobenzoic acid) reveal the formation of supramolecular networks constructed from acid–base heterosynthons of ortho-phenylenediammonium cations with respective aromatic anions. All of these coformers are generally regarded as safe (GRAS) molecules. The five reported crystal structures are sustained predominantly by intermolecular N+−H...O−, N—H...O− and N—H...O hydrogen-bonding interactions; in addition intramolecular O—H...O and intermolecular O—H...O, O—H...O− and C—H...O interactions contribute to the formation of various networks. Five 1:1 salts [NH2C6H4NH3]+·[COOHC6H4COO]− (1); [NH2C6H4NH3]+·[OHC6H4COO]− (2); [{NH2C6H4NH2}2·{OHC6H4COOH}2·{NH2C6H4NH3}+ 2·{OHC6H4COO}− 2] (OPDPHB) (3); [NH2C6H4NH3]+·[NO2C6H4COO]− (4) and [NH2C6H4NH3]+·[(NO2)2C6H4COO]− (5) were isolated as single crystals by the slow evaporation method and were characterized using spectroscopic and X-ray crystallographic techniques. X-ray diffraction studies confirmed the formation of salts. The pK a difference between the amine and respective acid favours the transfer of a proton from the acid to the amine, which leads to the formation of the anion and the cation. The interactions between these ions resulted in a stable heterosynthon in each case. The asymmetric units of salts (1), (2), (4) and (5) contain one anion and one cation each, but salt (3) consists of two anions, two cations and two neutral species in its asymmetric unit. A polymorph of salt (3) was also isolated from the crystallization of the ground material from liquid-assisted grinding [{NH2C6H4NH2}·{NH2C6H4NH3}+·{OHC6H4COO}−] (OPDPHB 3P). The polymorph crystallized in the monoclinic non-centrosymmetric space group P21. The liquid-assisted grinding experiments using a 1:1 ratio also revealed the formation of the expected salts, except salt (3), where this product matches with polymorph (OPDPHB 3P).

A New Organic-Inorganic Hybrid Based on L-Arginine and Polyoxoanion

2015 ◽  
Vol 1105 ◽  
pp. 335-338
Author(s):  
Qiong Wu ◽  
Jing Lu ◽  
Xiao Lin Ji ◽  
Tao Yu Zou ◽  
Zhen Fang Qiao ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Sodium Cation ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Inorganic Hybrid ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Photocatalytic Activities ◽  
Metal Organic ◽  
Supramolecular Networks

Modifying polyoxometalates with organic and/or metal-organic moieties is a widely adopted method for broading the range of properties. In this work a new polyoxometalate constructed from Anderson-type polyoxoanions and L-arginine (Arg =L-arginine) molecules Na [CrMo6(OH)6O18]}(H2Arg)2·8H2O(1) has been synthesized via conventional method and characterized by routine techniques. Single-crystal X-Ray diffraction analysis shows that compound 1 is constructed by chiralL-arginine grafted Anderson-type clusters, sodium cation and water molecules which are further stabilized by hydrogen bonding interactions constitute 3D supramolecular networks. In addition, both antitumor behavior and photocatalytic activities of compound 1 were investigated.

A New POM-Based Supramolecular Compound: Synthesis, Structure and Adsorptive Property of [Cu(phen)2]3[W6O19]

2014 ◽  
Vol 919-921 ◽  
pp. 2013-2016 ◽  
Author(s):  
Ya Bing Liu ◽  
Hong Jie Wang ◽  
Hong Kai Zhao
Keyword(s):  
Three Dimensional ◽  
Building Blocks ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Hybrid Compound ◽  
Adsorptive Property ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Compound Synthesis ◽  
Metal Organic

A POM - based organice - inorganic hybrid compound with the chemical formula of[Cu (phen)2]3[W6O19] (phen = 1,10-phenanthroline) (1) has been hydrothermally synthesized andstructurally characterized by the elemental analysis, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space groupC2/c witha=18.319(4) Å,b= 17.311(4) Å,c= 22.248(4) Å,β= 112.40(3) o,V= 6523(2) Å3,Z= 4, R1= 0.0448, andwR2=0.1218. Compound 1 consists of the [W6O19]3-building blocks and [Cu (phen)2]+metal organic cationic moieties, which are packed together via the extensive hydrogen-bonding interactions to form a three-dimensional supramolecular framework. The adsorption of methylene blue (MB) under UV irradiation with 1 as the heterogeneous adsorbent has been investigated, showing a good adsorptive property of 1 for MB degradation.

Study on a Novel Structure of Zn Phenanthroline Malic Acid Hydrate, [Zn (C12H8N2)(C4H4O5)(H2O)](H2O)

2013 ◽  
Vol 739 ◽  
pp. 26-29
Author(s):  
Hai Xing Liu ◽  
Jing Zhong Xiao ◽  
Huan Mei Guo ◽  
Qing Hua Zhang ◽  
Zhang Xue Yu ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Malic Acid ◽  
Hydrothermal Reaction ◽  
Crystal Packing ◽  
X Ray Diffraction ◽  
Acid Anion ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Novel Structure ◽  
Acid Hydrate

A novel Zn complex [Zn (C12H8N2)(C4H4O5)(H2O)](H2O) has been synthesized from a hydrothermal reaction and the crystal structure has been determined by means of single-crystal X-ray diffraction. The Zn atom is six-coordinated by two phenanthroline N atoms, three O atoms from malic acid anion and one O atom from water. The crystal packing is stabilized by O-H...O hydrogen bonding interactions.

An Intramolecular Boron Nitrogen Lewis Acid Base Pair on a Rigid Naphthyl Backbone

2012 ◽  
Vol 67 (6) ◽  
pp. 589-593 ◽  
Author(s):  
Daniel Winkelhaus ◽  
Beate Neumann ◽  
Norbert W. Mitzel
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Lewis Acid ◽  
Elemental Analysis ◽  
Base Pair ◽  
Ring System ◽  
X Ray Diffraction ◽  
Acid Base ◽  
X Ray ◽  
Boron Nitrogen

The reaction of (C6F5)2BCl with 8-lithio-N,N-dimethyl-1-naphthylamine (1) afforded the fivemembered ring system 8-bis(pentafluorophenyl)boryl-N,N-dimethyl-1-naphthylamine (2) with an intramolecular dative B-N bond. The compound was characterised by elemental analysis, NMR spectroscopy and single-crystal X-ray diffraction.

scholarly journals Selective Crystallization of Four Bis(phthalocyaninato)neodymium(III) Polymorphs

2020 ◽  
Author(s):  
Maegan Dailey ◽  
Claire Besson
Keyword(s):  
Crystal Packing ◽  
Detailed Comparison ◽  
Protonated Form ◽  
Slow Evaporation ◽  
X Ray Diffraction ◽  
Acid Base ◽  
Initial Oxidation ◽  
X Ray ◽  
Secondary Interactions ◽  
Selective Crystallization

Four polymorphs of bis(phthalocyaninato)neodymium(III) were reproducibly and selectively crystallized by the slow evaporation of saturated solutions. The obtained phase depended on the initial oxidation state of the NdPc<sub>2</sub> molecule and the choice of solvent. Single-crystal X-ray diffraction studies were used to correct previous mis-identifications and provide missing coordinates for the γ-phase as well as a detailed comparison of molecular structure and crystal packing in all NdPc<sub>2</sub> polymorphs. The primary feature in all phases is columnar stacking based on parallel π π interactions, with a variety of slip angles within those stacks as well as secondary interactions between them. Chemical redox and acid-base titrations, performed on re-dissolved crystals demonstrate that NdPc<sub>2</sub><sup>+</sup> and NdPc<sub>2</sub><sup>-</sup> are easily obtained through weak oxidizing and reducing agents, respectively. Additionally, we show that the protonated form of the NdPc<sub>2</sub><sup>-</sup> complex has a nearly identical UV-Vis spectra to that of neutral NdPc<sub>2</sub>, explaining some of the confusion over chemical composition in previously published literature.<br>

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