Weak intermolecular interactions in 11‐chloro‐2,3,4,5‐tetrahydro‐1H‐cyclohepta[b]quinoline

The title compound, C₁₄H₁₄ClN, is a chloro analogue of tacrine, an acetylcholinesterase inhibitor. The compound comprises a seven‐membered alicyclic ring whose CH donor groups are engaged in extensive intermolecular interactions. The important feature of this crystal structure is that, regardless of the presence of two typical hydrogen‐bonding acceptors, viz. chlorine and nitrogen, the corresponding C—H...Cl and C—H...N interactions take no significant role in crystal stabilization. The molecules form dimers through π–π interactions with an interplanar distance between interacting pyridine rings of 3.576 (1) Å. Within the dimers, the molecules are additionally interconnected by four C—H...π interactions. The dimers arrange into regular columns via further intermolecular C—H...π interactions.     

Cocrystallization of adamantane‐1,3‐dicarboxylic acid and 4,4′‐bipyridine

The cocrystallization of adamantane‐1,3‐dicarboxylic acid (adc) and 4,4′‐bipyridine (4,4′‐bpy) yields a unique 1:1 cocrystal, C₁₂H₁₆O₄·C₁₀H₈N₂, in the C2/c space group, with half of each molecule in the asymmetric unit. The mid‐point of the central C—C bond of the 4,4′‐bpy molecule rests on a center of inversion, while the adc molecule straddles a twofold rotation axis that passes through two of the adamantyl C atoms. The constituents of this cocrystal are joined by hydrogen bonds, the stronger of which are O—H...N hydrogen bonds [O...N = 2.6801 (17) Å] and the weaker of which are C—H...O hydrogen bonds [C...O = 3.367 (2) Å]. Alternate adc and 4,4′‐bpy molecules engage in these hydrogen bonds to form zigzag chains. In turn, these chains are linked through π–π interactions along the c axis to generate two‐dimensional layers. These layers are neatly packed into a stable crystalline three‐dimensional form via weak C—H...O hydrogen bonds [C...O = 3.2744 (19) Å] and van der Waals attractions.     

Di‐μ‐chlorido‐bis[chlorido(4′‐p‐tolyl‐2,2′:6′,2′′‐terpyridine‐κ3N,N′,N′′)nickel(II)]: a supramolecular system constructed by C—H...Cl interactions

The title complex, [Ni₂Cl₄(C₂₂H₁₇N₃)₂], was synthesized solvothermally. The molecule is a centrosymmetric dimer with the unique Ni^II centre in a distorted octahedral N₃Cl₃ coordination environment. The chloride bridges are highly asymmetric. In the 4′‐p‐tolyl‐2,2′:6′,2′′‐terpyridine ligand, the p‐tolyl group is perfectly coplanar with the attached pyridine ring, and this differs from the situation found in previously reported compounds; however, there are no π–π interactions between the ligands. The terminal Cl atom forms four intermolecular C—H...Cl hydrogen bonds with one methyl and three methine groups. The methyl group also forms intermolecular C—H...π interactions with a pyridine ring. These nonclassical hydrogen bonds extend the molecule into a three‐dimensional network.     

Three different fluoro‐ or chloro‐substituted 1′‐deoxy‐1′‐phenyl‐β‐D‐ribofuranoses

Crystal structures are reported for three fluoro‐ or chloro‐substituted 1′‐deoxy‐1′‐phenyl‐β‐D‐ribofuranoses, namely 1′‐deoxy‐1′‐(2,4,5‐trifluorophenyl)‐β‐D‐ribofuranose, C₁₁H₁₁F₃O₄, (I), 1′‐deoxy‐1′‐(2,4,6‐trifluorophenyl)‐β‐D‐ribofuranose, C₁₁H₁₁F₃O₄, (II), and 1′‐(4‐chlorophenyl)‐1′‐deoxy‐β‐D‐ribofuranose, C₁₁H₁₃ClO₄, (III). The five‐membered furanose ring of the three compounds has a conformation between a C2′‐endo,C3′‐exo twist and a C2′‐endo envelope. The ribofuranose groups of (I) and (III) are connected by intermolecular O—H...O hydrogen bonds to six symmetry‐related molecules to form double layers, while the ribofuranose group of (II) is connected by O—H...O hydrogen bonds to four symmetry‐related molecules to form single layers. The O...O contact distance of the O—H...O hydrogen bonds ranges from 2.7172 (15) to 2.8895 (19) Å. Neighbouring double layers of (I) are connected by a very weak intermolecular C—F...π contact. The layers of (II) are connected by one C—H...O and two C—H...F contacts, while the double layers of (III) are connected by a C—H...Cl contact. The conformations of the molecules are compared with those of seven related molecules. The orientation of the benzene ring is coplanar with the H—C1′ bond or bisecting the H—C1′—C2′ angle, or intermediate between these positions. The orientation of the benzene ring is independent of the substitution pattern of the ring and depends mainly on crystal‐packing effects.     

Ethyl 1‐ethyl‐7‐fluoro‐4‐oxo‐1,4‐dihydroquinoline‐3‐carboxylate: X‐ray and DFT studies

The basic building unit in the structure of the title compound, C₁₄H₁₄FNO₃, is pairs of molecules arranged in an antiparallel fashion, enabling weak C—H...O interactions. Each molecule is additionally involved in π–π interactions with neighbouring molecules. The pairs of molecules formed by the C—H...O hydrogen bonds and π–π interactions form ribbon‐like chains running along the c axis. Theoretical calculations based on these pairs showed that, although the main intermolecular interaction is electrostatic, it is almost completely compensated by an exchange–repulsion contribution to the total energy. As a consequence, the dominating force is a dispersion interaction. The F atoms form weak C—F...H—C interactions with the H atoms of the neighbouring ethyl groups, with H...F separations in the range 2.59–2.80 Å.     

5‐Formylsalicylic acid and 5‐(benzimidazolium‐2‐yl)salicylate

Both title compounds are derivatives of salicylic acid. 5‐Formylsalicylic acid (systematic name: 5‐formyl‐2‐hydroxybenzoic acid), C₈H₆O₄, possesses three good hydrogen‐bond donors and/or acceptors coplanar with their attached benzene ring and abides very well by Etter's hydrogen‐bond rules. Intermolecular O—H...O and some weak C—H...O hydrogen bonds link the molecules into a planar sheet. Reaction of this acid and o‐phenylenediamine in refluxing ethanol produced in high yield the new zwitterionic compound 5‐(benzimidazolium‐2‐yl)salicylate [systematic name: 5‐(1H‐benzimidazol‐3‐ium‐2‐yl)‐2‐hydroxybenzoate], C₁₄H₁₀N₂O₃. Each imidazolium N—H group and its adjacent salicyl C—H group chelate one carboxylate O atom via hydrogen bonds, forming seven‐membered rings. As a result of steric hindrance, the planes of the molecules within these pairs of hydrogen‐bonded molecules are inclined to one another by ∼74°. There are also π–π stacking interactions between the parallel planes of the imidazole ring and the benzene ring of the salicyl component of the adjacent molecule on one side and the benzimidazolium component of the molecule on the other side.     

Monoclinic and orthorhombic polymorphs of 4,4′,6,6′‐tetrachloro‐2,2′‐(piperazine‐1,4‐diyldimethylene)diphenol

The title compound, C₁₈H₁₈Cl₄N₂O₂, crystallizes as monoclinic and orthorhombic polymorphs from CHCl₃–CH₃OH solution. In both polymorphic forms, the molecule lies on a crystallographic centre of inversion (at the piperazine ring centroid) and exhibits an intramolecular O—H...N hydrogen bond. In the monoclinic polymorph (space group P2₁/c), the molecules are linked by intermolecular C—H...Cl hydrogen bonds into a ribbon sheet built from R₈⁸(34) rings. In the orthorhombic polymorph (space group Pbcn), the molecules are linked by intermolecular C—H...O hydrogen bonds into a ribbon sheet of R₆⁶(34) rings. The sheets in the orthorhombic polymorph are crosslinked into a three‐dimensional framework by π–π stacking interactions.     

N‐{4‐Bromo‐2‐[(3‐bromo‐1‐phenylsulfonyl‐1H‐indol‐2‐yl)methyl]‐5‐methoxyphenyl}acetamide

In the title compound, C₂₄H₂₀Br₂N₂O₄S, the indole ring system is planar and the S atom has a distorted tetrahedral configuration. The sulfonyl‐bound phenyl ring is orthogonal to the indole ring system and the conformation of the phenyl­sulfonyl substituent with respect to the indole moiety is influenced by intramolecular C—H⃛O hydrogen bonds involving the two sulfonyl O atoms. The mean plane through the acetyl­amido group makes a dihedral angle of 57.0 (1)° with the phenyl ring of the benzyl moiety. In the crystal, glide‐related mol­ecules are linked together by N—H⃛O hydrogen bonds and C—H⃛π interactions to form molecular chains, which extend through the crystal. Inversion‐related chains are interlinked by C—H⃛π interactions to form molecular layers parallel to the bc plane. These layers are interconnected through π–π interactions involving the five‐ and six‐membered rings of the indole moiety.     

2‐Ethyl‐6‐methylpyridin‐3‐ol and its salt bis(2‐ethyl‐3‐hydroxy‐6‐methylpyridinium) succinate

The title compounds, C₈H₁₁NO, (I), and 2C₈H₁₂NO⁺·C₄H₄O₄²⁻, (II), both crystallize in the monoclinic space group P2₁/c. In the crystal structure of (I), intermolecular O—H...N hydrogen bonds combine the molecules into polymeric chains extending along the c axis. The chains are linked by C—H...π interactions between the methylene H atoms and the pyridine rings into polymeric layers parallel to the ac plane. In the crystal structure of (II), the succinate anion lies on an inversion centre. Its carboxylate groups interact with the 2‐ethyl‐3‐hydroxy‐6‐methylpyridinium cations via intermolecular N—H...O hydrogen bonds with the pyridine ring H atoms and O—H...O hydrogen bonds with the hydroxy H atoms to form polymeric chains, which extend along the [01] direction and comprise R₄⁴(18) hydrogen‐bonded ring motifs. These chains are linked to form a three‐dimensional network through nonclassical C—H...O hydrogen bonds between the pyridine ring H atoms and the hydroxy‐group O atoms of neighbouring cations. π–π interactions between the pyridine rings and C—H...π interactions between the methylene H atoms of the succinate anion and the pyridine rings are also present in this network.     

Contrasting the supramolecular structures in the isomeric pair 5‐bromo‐3‐nitrosalicylaldehyde phenylhydrazone and 3‐bromo‐5‐nitrosalicylaldehyde phenylhydrazone

Isomeric 5‐bromo‐3‐nitrosalicylaldehyde phenylhydrazone and 3‐bromo‐5‐nitrosalicylaldehyde phenylhydrazone, C₁₃H₁₀BrN₃O₃, both crystallize with two molecules in the asymmetric unit. In both isomers, an intramolecular O—H...N hydrogen bond links the hydroxy group and the imine N atom. In the 5‐bromo‐3‐nitro isomer, there are two independent N—H...O hydrogen‐bonded chains, each molecule in the asymmetric unit forming its own chain. These chains are then linked to form a three‐dimensional framework by a combination of weak C—H...O, C—H...Br, C—H...π and π–π stacking interactions. In the 3‐bromo‐5‐nitro isomer, N—H...O hydrogen bonds link the independent molecules alternately into a zigzag chain, which is reinforced by a weak C—H...O interaction. Individual chains are linked by a C—H...Br interaction and a three‐dimensional framework is generated by π–π stacking interactions.     

Hydrogen‐bonded sheet structures in methyl 4‐(4‐chloroanilino)‐3‐nitrobenzoate and methyl 1‐benzyl‐2‐(4‐chlorophenyl)‐1H‐benzimidazole‐5‐carboxylate

In methyl 4‐(4‐chloroanilino)‐3‐nitrobenzoate, C₁₄H₁₁ClN₂O₄, (I), there is an intramolecular N—H...O hydrogen bond and the intramolecular distances provide evidence for electronic polarization of the o‐quinonoid type. The molecules are linked into sheets built from N—H...O, C—H...O and C—H...π(arene) hydrogen bonds, together with an aromatic π–π stacking interaction. The molecules of methyl 1‐benzyl‐2‐(4‐chlorophenyl)‐1H‐benzimidazole‐5‐carboxylate, C₂₂H₁₇ClN₂O₂, (II), are also linked into sheets, this time by a combination of C—H...π(arene) hydrogen bonds and aromatic π–π stacking interactions.     

9,9′‐Biacridine N,N′‐dioxide: a novel potential bridging ligand bearing the bulky acridine N‐oxide skeleton

The title compound, C₂₆H₁₆N₂O₂, is a potential linear bridging O‐donor ligand comprising bulky acridine N‐oxide ring systems. Weak intermolecular C—H...O hydrogen‐bonding interactions link adjacent molecules to form extended chains. The structure also contains intermolecular C—H...π interactions.     

Assembling an isomer grid: the isomorphous 4‐, 3‐ and 2‐fluoro‐N′‐(4‐pyridyl)benzamides

The three title isomers, 4‐, (I), 3‐, (II), and 2‐fluoro‐N′‐(4‐pyridyl)benzamide, (III), all C₁₂H₉FN₂O, crystallize in the P2₁/c space group (No. 14) with similar unit‐cell parameters and are isomorphous and isostructural at the primary hydrogen‐bonding level. An intramolecular C—H...O=C interaction is present in all three isomers [C...O = 2.8681 (17)–2.884 (2) Å and C—H...O117–118°], with an additional N—H...F [N...F = 2.7544 (15) Å] interaction in (III). Intermolecular amide–pyridine N—H...N hydrogen bonds link molecules into one‐dimensional zigzag chains [graph set C(6)] along the [010] direction as the primary hydrogen bond [N...N = 3.022 (2), 3.049 (2) and 3.0213 (17) Å]. These are augmented in (I) by C—H...π(arene) and cyclic C—F...π(arene) contacts about inversion centres, in (II) by C—F...F—C interactions [C...F = 3.037 (2) Å] and weaker C—H...π(arene)/C—H...F contacts, and in (III) by C—H...π(arene) and C=O...O=C interactions, linking the alternating chains into two‐dimensional sheets. Typical amide N—H...O=C hydrogen bonds [as C(4) chains] are not present [N...O = 3.438 (2) Å in (I), 3.562 (2) Å in (II) and 3.7854 (16) Å in (III)]; the C=O group is effectively shielded and only participates in weaker interactions/contacts. This series is unusual as the three isomers are isomorphous (having similar unit‐cell parameters, packing and alignment), but they differ in their interactions and contacts at the secondary level.     

2,2′‐Anhydro‐1‐(3′,5′‐di‐O‐acetyl‐β‐D‐arabinofuranosyl)uracil,a cyclouridine nucleoside with a C4′‐endo furanosyl conformation

2,2′‐Anhydro‐1‐(3′,5′‐di‐O‐acetyl‐β‐D‐arabinofuranosyl)uracil, C₁₃H₁₄N₂O₇, was obtained by refluxing 2′,3′‐O‐(methoxymethylene)uridine in acetic anhydride. The structure exhibits a nearly perfect C4′‐endo (⁴E) conformation. The best four‐atom plane of the five‐membered furanose ring is O—C—C—C, involving the C atoms of the fused five‐membered oxazolidine ring, and the torsion angle is only −0.4 (2)°. The oxazolidine ring is essentially coplanar with the six‐membered uracil ring [r.m.s. deviation = 0.012 (5) Å and dihedral angle = −3.2 (3)°]. The conformation at the exocyclic C—C bond is gauche–trans which is stabilized by various C—H...π and C—O...π interactions.     

3,3′‐Dinitro‐2,2′‐dithiodipyridine

In the title compound, C₁₀H₆N₄O₄S₂, (I), the molecule has a centre of inversion. The structure is a positional isomer of 5,5′‐dinitro‐2,2′‐dithiodipyridine [Brito, Mundaca, Cárdenas, López‐Rodríguez & Vargas (2007). Acta Cryst. E 63 , o3351–o3352], (II). The 3‐nitropyridine fragment of (I) shows excellent agreement with the bonding geometries of (II). The most obvious differences between them are in the S—S bond length [2.1167 (12) Å in (I) and 2.0719 (11) Å in (II)], and in the C—C_ipso—N_ring [119.8 (2)° in (I) and 123.9 (3)° in (II)] and S—C—C [122.62 (18)° in (I) and 116.0 (2)° in (II)] angles. The crystal structure of (I) has an intramolecular C—H...O interaction, with an H...O distance of 2.40 (3) Å, whereas this kind of interaction is not evident in (II). The molecules of (I) are linked into centrosymmetric R⁴₄(30) motifs by a C—H...O interaction. There are no aromatic π–π stacking and no C—H...π(arene) interactions. Compound (I) can be used as a nucleophilic tecton in self‐assembly reactions with metal centres of varying lability.     

4‐Methoxy‐1‐naphthol: chains formed by O—H...O hydrogen bonds and π–π stacking interactions

The structure of 4‐methoxy‐1‐naphthol, C₁₁H₁₀O₂, (I), contains an intermolecular O—H...O hydrogen bond which links the molecules into a simple C(2) chain running parallel to the shortest crystallographic b axis. This chain is reinforced by intermolecular π–π stacking interactions. Comparisons are drawn between the crystal structure of (I) and those of several of its simple analogues, including 1‐naphthol and some monosubstituted derivatives, and that of its isomer 7‐methoxy‐2‐naphthol. This comparison shows a close similarity in the packing of the molecules of its simple analogues that form π‐stacks along the shortest crystallographic axes. A substantial spatial overlap is observed between adjacent molecules in such stacks. In this group of monosubstituted naphthols, the overlap depends mainly on the position of the substituents carried by the naphthalene moiety, and the extent of the overlap depends on the substituent type. By contrast with (I), in the crystal structure of the isomeric 7‐methoxy‐2‐naphthol there are no O—H...O hydrogen bonds or π–π stacking interactions, and sheets are formed by O—H...π and C—H...π interactions.     

Intra‐ and intermolecular Se...X (X = Se,O) interactions in selenium‐containing heterocycles: 3‐benzoylimino‐5‐(morpholin‐4‐yl)‐1,2,4‐diselenazole

In the selenium‐containing heterocyclic title compound {systematic name: N‐[5‐(morpholin‐4‐yl)‐3H‐1,2,4‐diselenazol‐3‐ylidene]benzamide}, C₁₃H₁₃N₃O₂Se₂, the five‐membered 1,2,4‐diselenazole ring and the amide group form a planar unit, but the phenyl ring plane is twisted by 22.12 (19)° relative to this plane. The five consecutive N—C bond lengths are all of similar lengths [1.316 (6)–1.358 (6) Å], indicating substantial delocalization along these bonds. The Se...O distance of 2.302 (3) Å, combined with a longer than usual amide C=O bond of 2.252 (5) Å, suggest a significant interaction between the amide O atom and its adjacent Se atom. An analysis of related structures containing an Se—Se...X unit (X = Se, S, O) shows a strong correlation between the Se—Se bond length and the strength of the Se...X interaction. When X = O, the strength of the Se...O interaction also correlates with the carbonyl C=O bond length. Weak intermolecular Se...Se, Se...O, C—H...O, C—H...π and π–π interactions each serve to link the molecules into ribbons or chains, with the C—H...O motif being a double helix, while the combination of all interactions generates the overall three‐dimensional supramolecular framework.     

4‐(Pyrrol‐1‐yl)‐1,2,4‐triazole

The asymmetric unit of the title compound, C₆H₆N₄, comprises one and a half molecules with a C₂ axis through the second molecule. Each molecule consists of two planar five‐membered rings connected by a triazole–pyrrole N—N bond with the triazole ring close to being at right angles to the pyrrole ring. The molecules are linked by C—H...N hydrogen bonds and weaker offset face‐to‐face π–π interactions.     

2,3,12,13‐Tetrabromo‐5,10,15,20‐tetrakis(4‐butoxyphenyl)porphyrin 1,2‐dichloroethane solvate

Nonmesogenic 2,3,12,13‐tetrabromo‐5,10,15,20‐tetrakis(4‐butoxyphenyl)porphyrin crystallizes as the title 1,2‐dichloroethane solvate, C₆₀H₅₈Br₄N₄O₄·C₂H₄Cl₂. The porphyrin ring shows a nonplanar conformation, with an average mean plane displacement of the β‐pyrrole C atoms from the 24‐atom (C₂₀N₄) core of ±0.50 (3) Å. The 1,2‐dichloroethane solvent is incorporated between the porphyrin units and induces the formation of one‐dimensional chains via interhalogen Cl...Br and butyl–aryl C—H...π interactions. These chains are oriented along the unit‐cell a axis, with the macrocyclic ring planes lying almost parallel to the (010) plane. The chains are arranged in an offset fashion by aligning the butoxy chains approximately above or below the faces of the adjacent porphyrin core, resulting in decreased interporphyrin π–π interactions, and they are held together by weak intermolecular (C—Br...π, C—H...π and C—H...Br) interactions. The nonplanar geometry of the macrocyclic ring is probably due to the weak interporphyrin interactions induced by the solvent molecule and the peripheral butoxy groups. The nonplanarity of the mesogens could influence the mesogenic behaviour differently relative to planar porphyrin mesogens.     

4,6‐Dimethyl‐2‐[(4‐phenylpiperidin‐1‐yl)methyl]isothiazolo[5,4‐b]pyridin‐3(2H)‐one and 4,6‐dimethyl‐2‐[(4‐phenyl‐1,2,3,6‐tetrahydropyridin‐1‐yl)methyl]isothiazolo[5,4‐b]pyridin‐3(2H)‐one

In the crystal structures of the title compounds, C₂₀H₂₃N₃OS, (II), and C₂₀H₂₁N₃OS, (III), significant differences occur in the conformation of, respectively, the phenylpiperidine and phenyltetrahydropyridine substituents at the 2‐position of the isothiazolopyridine system. The piperidine ring adopts a chair conformation, while the tetrahydropyridine ring assumes a half‐chair form. The phenylpiperidine and phenyltetrahydropyridine fragments exhibit different conformations resulting from the steric and conjugation effects in the phenyl ring, respectively. Theoretical calculations show that both conformations are energetically stable and correspond to a minimum of energy for the analyzed systems. The molecular packing in (II) is influenced by π–π interactions of the isothiazolopyridine systems, with a shortest centroid‐to‐centroid separation of 3.5843 (11) Å between pyridine rings. In the crystal structure of (III), the molecules are linked by C—H...O hydrogen bonds and C—H...π interactions.