Supramolecular hydrogen‐bonded networks in adeninium phenylacetate phenylacetic acid monohydrate and adeninium 3‐carboxypropionate monohydrate

In the title compounds, C₅H₆N₅⁺·C₈H₇O₂⁻·C₈H₈O₂·H₂O, (I), and C₅H₆N₅⁺·C₄H₃O₄⁻·H₂O, (II), the adeninium cations form N—H...O hydrogen bonds with their anion counterparts and adeninium–adeninium self‐association base pairs with the R₂²(10) motif (Bernstein et al., 1995). A complete hydrogen‐bonding motif analysis is presented. Conventional hydrogen bonds lead to layer structures in (I) and to two‐dimensional infinite polymeric ribbons in (II). C—H...O interactions are found in both structures, while weak π–π stacking interactions are only observed in (I).     

Supramolecular hydrogen‐bonded networks in cytosinium succinate and cytosinium 4‐nitrobenzoate cytosine monohydrate

In cytosinium succinate (systematic name: 4‐amino‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium 3‐carboxypropanoate), C₄H₆N₃O⁺·C₄H₅O₄⁻, (I), the cytosinium cation forms one‐dimensional self‐assembling patterns by intermolecular N—H...O hydrogen bonding, while in cytosinium 4‐nitrobenzoate cytosine monohydrate [systematic name: 4‐amino‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium 4‐nitrobenzoate 4‐aminopyrimidin‐2(1H)‐one solvate monohydrate], C₄H₆N₃O⁺·C₇H₄NO₄⁻·C₄H₅N₃O·H₂O, (II), the cytosinium–cytosine base pair, held together by triple hydrogen bonds, leads to one‐dimensional polymeric ribbons via double N—H...O hydrogen bonds. This study illustrates clearly the different alignment of cytosine molecules in the crystal packing and their ability to form supramolecular hydrogen‐bonded networks with the anions.     

N—H...O and O—H...O hydrogen‐bonded supramolecular networks in 4‐chloroanilinium, 2‐hydroxyanilinium and 3‐hydroxyanilinium hydrogen phthalates

The title salts, 4‐chloroanilinium hydrogen phthalate (PCAHP), C₆H₇ClN⁺·C₈H₅O₄⁻, 2‐hydroxyanilinium hydrogen phthalate (2HAHP), C₆H₈NO⁺·C₈H₅O₄⁻, and 3‐hydroxyanilinium hydrogen phthalate (3HAHP), C₆H₈NO⁺·C₈H₅O₄⁻, all crystallize in the space group P2₁/c. The asymmetric unit of 2HAHP contains two independent ion pairs. The hydrogen phthalate ions of 2HAHP and 3HAHP show a short intramolecular O—H...O hydrogen bond, with O...O distances ranging from 2.3832 (15) to 2.3860 (14) Å. N—H...O and O—H...O hydrogen bonds, together with short C—H...O contacts in PCAHP and 3HAHP, generate extended hydrogen‐bond networks. PCAHP forms a two‐dimensional supramolecular sheet extending in the (100) plane, whereas 2HAHP has a supramolecular chain running parallel to the [100] direction and 3HAHP has a two‐dimensional network extending parallel to the (001) plane.     

Supramolecular hydrogen‐bonded networks in cytosinium nicotinate monohydrate and cytosinium isonicotinate cytosine dihydrate

The title compounds are proton‐transfer compounds of cytosine with nicotinic acid [systematic name: 4‐amino‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium nicotinate monohydrate (cytosinium nicotinate hydrate), C₄H₆N₃O⁺·C₆H₄NO₂⁻·H₂O, (I)] and isonicotinic acid [systematic name: 4‐amino‐2‐oxo‐2,3‐dihydropyrimidin‐1‐ium isonicotinate–4‐aminopyrimidin‐2(1H)‐one–water (1/1/2) (cytosinium isonicotinate cytosine dihydrate), C₄H₆N₃O⁺·C₆H₄NO₂⁻·C₄H₅N₃O·2H₂O, (II)]. In (I), the cation and anion are interlinked by N—H...O hydrogen bonding to form a one‐dimensional tape. These tapes are linked through water molecules to form discrete double sheets. In (II), the cytosinium–cytosine base pairs are connected by triple hydrogen bonds, leading to one‐dimensional polymeric ribbons. These ribbons are further interconnected via nicotinate–water and water–water hydrogen bonding, resulting in an overall three‐dimensional network.     

Double anomeric effects and a hydrogen‐bonded supramolecular motif in N,N′‐bis(3‐nitrophenyl)methanediamine

In the title compound, C₁₃H₁₂N₄O₄, the molecule lies on a crystallographic twofold axis. Molecules are linked into complex sheets parallel to (100) via one N—H...O and two C—H...O hydrogen bonds. Within the molecule, the 3‐nitroanilino fragment is essentially planar, and the C—N—C—N—C fragment assumes a nearly perpendicular/perpendicular conformation, with C—N—C—N torsion angles of 81.18 (18)°, which is controlled by a pair of adjacent anomeric interactions. The findings constitute the first demonstration of two anomeric effects existing in one N—C—N unit.     

Hydrogen‐bonded sheets in benzylmethylammonium hydrogen maleate

In the title compound, C₈H₁₂N⁺·C₄H₃O₄⁻, there is a short and almost linear but asymmetric O—H...O hydrogen bond in the anion. The ions are linked into C₂²(6) chains by two short and nearly linear N—H...O hydrogen bonds and the chains are further weakly linked into sheets by a single C—H...O hydrogen bond.     

Supramolecular hydrogen‐bonded networks in adeninediium hemioxalate chloride and adeninium semioxalate hemi(oxalic acid) monohydrate

In 9H‐adenine‐1,7‐diium hemioxalate chloride, C₅H₇N₅²⁺·0.5C₂O₄²⁻·Cl⁻, (I), adenine is doubly protonated, while in 7H‐adenin‐1‐ium semioxalate hemi(oxalic acid) monohydrate, C₅H₆N₅⁺·C₂HO₄⁻·0.5C₂H₂O₄·H₂O, (II), adenine and one oxalate anion are both monoprotonated. In (I), the adeninium cation forms R₂²(8) and R₁²(5) hydrogen‐bonding motifs with the centrosymmetric oxalate anion, while in (II), the cation forms R₂¹(6) and R₁²(5) motifs with the centrosymmetric oxalic acid molecule and R₁²(5)and R₂²(9) motifs with the monoprotonated oxalate anion. Linear hydrogen‐bonded trimers are observed in (I) and (II). In both structures, the hydrogen bonds lead to the formation of two‐dimensional supramolecular hydrogen‐bonded sheets in the crystal packing. The significance of this study lies in the analysis of the interactions occurring via hydrogen bonds and the diversity seen in the supramolecular hydrogen‐bonded networks as a result of such interactions.     

N—H...O,O—H...O hydrogen‐bonded supramolecular sheet formation in the bis(2‐aminoanilinium) fumarate, 3‐methylanilinium hydrogen fumarate and 4‐chloroanilinium hydrogen fumarate salts

In bis(2‐aminoanilinum) fumarate, 2C₆H₉N₂⁺·C₄H₂O₄²⁻, (I), the asymmetric unit consists of two aminoanilinium cations and one fumarate dianion, whereas in 3‐methylanilinium hydrogen fumarate, C₇H₁₀N⁺·C₄H₃O₄⁻, (II), and 4‐chloroanilinium hydrogen fumarate, C₆H₇ClN⁺·C₄H₃O₄⁻, (III), the asymmetric unit contains two symmetry‐independent hydrogen fumate anions and anilinium cations with a slight difference in their geometric parameters; the two salts are isostructural. In (II) and (III), the carboxylic acid H atoms of the anions are disordered across both ends of the anion, with equal site occupancies of 0.50. Both the 4‐chloroanilinium cations of (III) are disordered over two orientations with major occupancies fixed at 0.60 in each case. The hydrogen fumarate anions of (II) and (III) form one‐dimensional anionic chains linked through O—H...O hydrogen bonds. Salts (II) and (III) form two‐dimensional supramolecular sheets built from R₄⁴(16), R₄⁴(18), R₅⁵(25) and C₂²(14) motifs extending parallel to the (010) plane, whereas in (I), an (010) sheet is formed built from two R₄³(13) motifs, two R₂²(9) motifs and an R₄⁴(18) motif.     

Chiral discrimination in hydrogen‐bonded complexes of 2‐methylol oxirane with hydrogen peroxide

A systematic quantum chemical study reveals the effects of chirality on the intermolecular interactions between two chiral molecules bound by hydrogen bonds. The methods used are second‐order Møller–Plesset perturbation theory (MP2) with the 6‐311++g(d,p) basis set. Complexes via the O? H···O hydrogen bond formed between the chiral 2‐methylol oxirane (S) and chiral HOOH (P and M) molecules have been investigated, which lead to four diastereomeric complexes. The nomenclature of the complexes used in this article is enantiomeric configuration sign corresponding to English letters. Such as: sm, sp. The relative positions of the methylol group and the hydrogen peroxide are designated as syn (same side) and anti (opposite side). The largest chirodiastaltic energy was ΔE_chir = ?1.329 kcal mol^?1 [9% of the counterpoise correct average binding energy D_e(corr)] between the sm‐syn and sp‐anti in favor of sm‐syn. The largest diastereofacial energy was ?1.428 kcal mol^?1 between sm‐syn and sm‐anti in favor of sm‐syn. To take into account solvents effect, the polarizable continuum model (PCM) method has been used to evaluate the chirodiastaltic energies, and diastereofacial energies of the 2‐methylol oxirane···HOOH complexes. The chiral 2,3‐dimethylol oxirane (S, S) is C₂ symmetry which offers two identical faces. Hence, the chirodiastaltic energy is identical to the diastereomeric energy, and is ΔE_chir = 0.563 kcal mol^?1 or 5.3% of the D_e(corr) in favor of s,s‐p. The optimized structures, interaction energies, and chirodiastaltic energies for various isomers were estimated. The harmonic frequencies, IR intensities, rotational constants, and dipole moments were also reported. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Epoxy‐based networks combining chemical and supramolecular hydrogen‐bonding crosslinks

We combine the supramolecular chemistry of heterocyclic ureas with the chemistry of epoxides to synthesize new crosslinked materials incorporating both chemical and supramolecular hydrogen‐bonded links. A two‐step facile and solvent‐free procedure is used to obtain chemically and thermally stable networks from widely available ingredients: epoxy resins and fatty acids. The density of both chemical and physical crosslinks is controlled by the stoichiometry of the reactants and the use of a proper catalyst to limit side reactions. Depending on the stoichiometry, a wide range of thermomechanical properties can be attained. The method can be used to produce elastomeric objects of complex shapes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1133–1141, 2010     

Two‐dimensional hydrogen‐bonded networks in two novel glycoluril derivatives

Two new glycoluril derivatives, namely diethyl 6‐ethyl‐1,4‐dioxo‐1,2,2a,3,4,6,7,7b‐octahydro‐5H‐2,3,4a,6,7a‐pentaazacyclopenta[cd]indene‐2a,7b‐dicarboxylate, C₁₄H₂₁N₅O₆, (I), and 6‐ethyl‐2a,7b‐diphenyl‐1,2,2a,3,4,6,7,7b‐octahydro‐5H‐2,3,4a,6,7a‐pentaazacyclopenta[cd]indene‐1,4‐dione, C₂₀H₂₁N₅O₂, (II), both bearing two free syn‐urea NH groups and two ureidyl C=O groups, assemble the same one‐dimensional chains in the solid state running parallel to the [010] direction via N—H...O hydrogen bonds. Furthermore, the chains of (I) are linked together into two‐dimensional networks via C—H...O hydrogen bonds.     

Two N,N′‐diaryl‐2,2,2‐trichloroethane‐1,1‐diamines: hydrogen‐bonded supramolecular structures in one and two dimensions

The molecules of 2,2,2‐trichloro‐N,N′‐diphenylethane‐1,1‐diamine, C₁₄H₁₃Cl₃N₂, are linked into (040) sheets by a combination of C—H...Cl and C—H...π(arene) hydrogen bonds. In 2,2,2‐trichloro‐N,N′‐bis(4‐methylphenyl)ethane‐1,1‐diamine, C₁₆H₁₇Cl₃N₂, the molecules are linked into C(7) chains by two independent C—H...Cl hydrogen bonds and one Cl...Cl contact.     

Energy decomposition analysis of cation–π, metal ion–lone pair,hydrogen bonded,charge‐assisted hydrogen bonded,and π–π interactions

This study probes the nature of noncovalent interactions, such as cation–π, metal ion–lone pair (M–LP), hydrogen bonding (HB), charge‐assisted hydrogen bonding (CAHB), and π–π interactions, using energy decomposition schemes—density functional theory (DFT)–symmetry‐adapted perturbation theory and reduced variational space. Among cation–π complexes, the polarization and electrostatic components are the major contributors to the interaction energy (IE) for metal ion–π complexes, while for onium ion–π complexes ( , , , and ) the dispersion component is prominent. For M–LP complexes, the electrostatic component contributes more to the IE except the dicationic metal ion complexes with H₂S and PH₃ where the polarization component dominates. Although electrostatic component dominates for the HB and CAHB complexes, dispersion is predominant in π–π complexes.Copyright © 2015 Wiley Periodicals, Inc.     

Inter‐ring and endo anomeric effects,and hydrogen‐bonded supramolecular motifs in two 2,4,6,8‐tetraazabicyclo[3.3.0]octane derivatives

In 2,4,6,8‐tetrakis(4‐chlorophenyl)‐2,4,6,8‐tetraazabicyclo[3.3.0]octane, C₂₈H₂₂Cl₄N₄, the imidazolidine rings adopt envelope conformations, which are favoured by two equal endo anomeric effects. The molecule lies on a crystallographic twofold axis and molecules are linked into a three‐dimensional framework via two C—H...Cl hydrogen bonds. In 2,4,6,8‐tetrakis(4‐methoxyphenyl)‐2,4,6,8‐tetraazabicyclo[3.3.0]octane, C₃₂H₃₄N₄O₄, one of the methyl groups is disordered over two sets of sites and the same methyl group participates in an intermolecular C—H...O hydrogen bond, which in turn causes a considerable deviation from the preferred conformation. There are two unequal inter‐ring anomeric effects in the N—C—N groups. Molecules are linked into corrugated sheets by one C—H...π hydrogen bond and two independent C—H...O hydrogen bonds involving methoxy groups.     

2‐Amino‐5‐nitro‐4,6‐dipiperidinopyrimidinium hydrogen­sulfate monohydrate: hydrogen‐bonded sheets containing highly distorted cations

In the title compound, C₁₄H₂₃N₆O₂⁺·HSO₄⁻·H₂O, the pyrimidinium ring of the cation adopts a twist‐boat conformation, induced by steric clashes between adjacent ring substituents; the anions and the water mol­ecules are linked by three O—H⃛O hydrogen bonds [H⃛O = 1.70–1.78 Å, O⃛O = 2.548 (2)–2.761 (2) Å and O—H⃛O = 161–168°] into chains of edge‐fused R(12) rings, which are linked into sheets by the cations, via three N—H⃛O hydrogen bonds [H⃛O = 1.96–2.17 Å, N⃛O = 2.820 (2)–2.935 (2) Å and N—H⃛O = 145–173°].     

4‐Aminopyridinium hydrogen maleate

The title compound, C₅H₇N₂⁺·C₄H₃O₄⁻, crystallizes in space group P2₁ with one ion pair in the asymmetric unit. The hydrogen maleate anion possesses nearly planar geometry and displays an extremely short intramolecular O—H...O hydrogen bond, with an O...O distance of 2.4198 (19) Å. Classical N—H...O hydrogen bonds, together with short C—H...O contacts, generate an extensive hydrogen‐bonding network.     

Supra­molecular hydrogen‐bonding networks in bis­(adeninium) phthalate phthalic acid 1.45‐hydrate

In the title compound, 2C₅H₆N₅⁺·C₈H₄O₄²⁻·C₈H₆O₄·1.45H₂O, the asymmetric unit comprises two adeninium cations, two half phthalate anions with crystallographic C₂ symmetry, one neutral phthalic acid mol­ecule, and one fully occupied and one partially occupied site (0.45) for water mol­ecules. The adeninium cations form N—H⋯O hydrogen bonds with the phthalate anions. The cations also form infinite one‐dimensional polymeric ribbons via N—H⋯N inter­actions. In the crystal packing, hydrogen‐bonded columns of cations, anions and phthalate anions extend parallel to the c axis. The water mol­ecules crosslink adjacent columns into hydrogen‐bonded layers.     

Seven 5‐benzylamino‐3‐tert‐butyl‐1‐phenyl‐1H‐pyrazoles: unexpected isomorphisms,and hydrogen‐bonded supramolecular structures in zero,one and two dimensions

5‐Benzylamino‐3‐tert‐butyl‐1‐phenyl‐1H‐pyrazole, C₂₀H₂₃N₃, (I), and its 5‐[4‐(trifluoromethyl)benzyl]‐, C₂₁H₂₂F₃N₃, (III), and 5‐(4‐bromobenzyl)‐, C₂₀H₂₂BrN₃, (V), analogues, are isomorphous in the space group C2/c, but not strictly isostructural; molecules of (I) form hydrogen‐bonded chains, while those of (III) and (V) form hydrogen‐bonded sheets, albeit with slightly different architectures. Molecules of 3‐tert‐butyl‐5‐(4‐methylbenzylamino)‐1‐phenyl‐1H‐pyrazole, C₂₁H₂₅N₃, (II), are linked into hydrogen‐bonded dimers by a combination of N—H...π(arene) and C—H...π(arene) hydrogen bonds, while those of 3‐tert‐butyl‐5‐(4‐chlorobenzylamino)‐1‐phenyl‐1H‐pyrazole, C₂₀H₂₂ClN₃, (IV), form hydrogen‐bonded chains of rings which are themselves linked into sheets by an aromatic π–π stacking interaction. Simple hydrogen‐bonded chains built from a single N—H...O hydrogen bond are formed in 3‐tert‐butyl‐5‐(4‐nitrobenzylamino)‐1‐phenyl‐1H‐pyrazole, C₂₀H₂₂N₄O₂, (VI), while in 3‐tert‐butyl‐5‐(3,4,5‐trimethoxybenzylamino)‐1‐phenyl‐1H‐pyrazole, C₂₃H₂₉N₃O₃, (VII), which crystallizes with Z′ = 2 in the space group P, pairs of molecules are linked into two independent centrosymmetric dimers, one generated by a three‐centre N—H...(O)₂ hydrogen bond and the other by a two‐centre N—H...O hydrogen bond.     

The hydrogen‐bonded complex bis(tert‐butylammonium) 2,6‐dichlorophenolate 2,4‐dichlorophenol–2,4‐dichlorophenolate tetrahydrofuran disolvate containing a chiral R53(10) hydrogen‐bonded ring as a supramolecular synthon

A fixed hydrogen‐bonding motif with a high probability of occurring when appropriate functional groups are involved is described as a `supramolecular hydrogen‐bonding synthon'. The identification of these synthons may enable the prediction of accurate crystal structures. The rare chiral hydrogen‐bonding motif R₅³(10) was observed previously in a cocrystal of 2,4,6‐trichlorophenol, 2,4‐dichlorophenol and dicyclohexylamine. In the title solvated salt, 2C₄H₁₂N⁺·C₆H₃Cl₂O⁻·(C₆H₃Cl₂O⁻·C₆H₄Cl₂O)·2C₄H₈O, five components, namely two tert‐butylammonium cations, one 2,4‐dichlorophenol molecule, one 2,4‐dichlorophenolate anion and one 2,6‐dichlorophenolate anion, are bound by N—H…O and O—H…O hydrogen bonds to form a hydrogen‐bonded ring, with the graph‐set motif R₅³(10), which is further associated with two pendant tetrahydrofuran molecules by N—H…O hydrogen bonds. The hydrogen‐bonded ring has internal symmetry, with a twofold axis running through the centre of the 2,6‐dichlorophenolate anion, and is isostructural with a previous and related structure formed from 2,4‐dichlorophenol, dicyclohexylamine and 2,4,6‐trichlorophenol. In the title crystal, helical columns are built by the alignment and twisting of the chiral hydrogen‐bonded rings, along and across the c axis, and successive pairs of rings are associated with each other through C—H…π interactions. Neighbouring helical columns are inversely related and, therefore, no chirality is sustained, in contrast to the previous case.