The isotypic hydrogen phosphate and arsenate dihydrates M2HXO4·2H2O (M = Rb,Cs; X = P,As)

The four isotypic alkaline metal monohydrogen arsenate(V) and phosphate(V) dihydrates M₂HXO₄·2H₂O (M = Rb, Cs; X = P, As) [namely dicaesium monohydrogen arsenate(V) dihydrate, Cs₂HAsO₄·2H₂O, dicaesium monohydrogen phosphate(V) dihydrate, Cs₂HPO₄·2H₂O, dirubidium monohydrogen arsenate(V) dihydrate, Rb₂HAsO₄·2H₂O, and dirubidium monohydrogen phosphate(V) dihydrate, Rb₂HPO₄·2H₂O] were synthesized by reaction of an aqueous H₃XO₄ solution with one equivalent of aqueous M₂CO₃. Their crystal structures are made up of undulating chains extending along [001] of tetrahedral [XO₃(OH)]⁻ anions connected via strong O—H...O hydrogen bonds. These chains are in turn connected into a three‐dimensional network via medium‐strength hydrogen bonding involving the water molecules. Two crystallographically different M⁺ cations are located in channels running along [001] or in the free space of the [XO₃(OH)]⁻ chains, respectively. They are coordinated by eight and twelve O atoms forming irregular polyhedra. The structures possess pseudosymmetry. Due to the ordering of the protons in the [XO₃(OH)]⁻ chains in the actual structures, the symmetry is reduced from C2/c to P2₁/c. Nevertheless, the deviation from C2/c symmetry is minute.     

Cinnamic acid hydrogen bonds to isoniazid and N′‐(propan‐2‐ylidene)isonicotinohydrazide,an in situ reaction product of isoniazid and acetone

A new polymorph of the cinnamic acid–isoniazid cocrystal has been prepared by slow evaporation, namely cinnamic acid–pyridine‐4‐carbohydrazide (1/1), C₉H₈O₂·C₆H₇N₃O. The crystal structure is characterized by a hydrogen‐bonded tetrameric arrangement of two molecules of isoniazid and two of cinnamic acid. Possible modification of the hydrogen bonding was investigated by changing the hydrazide group of isoniazid via an in situ reaction with acetone and cocrystallization with cinnamic acid. In the structure of cinnamic acid–N′‐(propan‐2‐ylidene)isonicotinohydrazide (1/1), C₉H₈O₂·C₉H₁₁N₃O, carboxylic acid–pyridine O—H...N and hydrazide–hydrazide N—H...O hydrogen bonds are formed.     

4‐(3‐Azaniumylpropyl)morpholin‐4‐ium chloride hydrogen oxalate: an unusual example of a dication with different counter‐anions

The mixed organic–inorganic title salt, C₇H₁₈N₂O²⁺·C₂HO₄⁻·Cl⁻, forms an assembly of ionic components which are stabilized through a series of hydrogen bonds and charge‐assisted intermolecular interactions. The title assembly crystallizes in the monoclinic C2/c space group with Z = 8. The asymmetric unit consists of a 4‐(3‐azaniumylpropyl)morpholin‐4‐ium dication, a hydrogen oxalate counter‐anion and an inorganic chloride counter‐anion. The organic cations and anions are connected through a network of N—H...O, O—H...O and C—H...O hydrogen bonds, forming several intermolecular rings that can be described by the graph‐set notations R₃³(13), R₂¹(5), R₁²(5), R₂¹(6), R₂³(6), R₂²(8) and R₃³(9). The 4‐(3‐azaniumylpropyl)morpholin‐4‐ium dications are interconnected through N—H...O hydrogen bonds, forming C(9) chains that run diagonally along the ab face. Furthermore, the hydrogen oxalate anions are interconnected via O—H...O hydrogen bonds, forming head‐to‐tail C(5) chains along the crystallographic b axis. The two types of chains are linked through additional N—H...O and O—H...O hydrogen bonds, and the hydrogen oxalate chains are sandwiched by the 4‐(3‐azaniumylpropyl)morpholin‐4‐ium chains, forming organic layers that are separated by the chloride anions. Finally, the layered three‐dimensional structure is stabilized via intermolecular N—H...Cl and C—H...Cl interactions.     

[2,5‐Bis(2,2′‐bipyridyl‐6‐yl)‐3,4‐diazahexa‐2,4‐diene]dichloridomanganese(II): from a mononuclear compound to a three‐dimensional supramolecular framework through C—H...Cl hydrogen bonds and π–π stacking interactions

The title compound, [MnCl₂(C₂₄H₂₀N₆)], has been synthesized and characterized based on the multifunctional ligand 2,5‐bis(2,2′‐bipyridyl‐6‐yl)‐3,4‐diazahexa‐2,4‐diene (L). The Mn^II centre is five‐coordinate with an approximately square‐pyramidal geometry. The L ligand acts as a tridendate chelating ligand. The mononuclear molecules are bridged into a one‐dimensional chain by two C—H...Cl hydrogen bonds. These chains are assembled into a two‐dimensional layer through π–π stacking interactions between adjacent uncoordinated bipyridyl groups. Furthermore, a three‐dimensional supramolecular framework is attained through π–π stacking interactions between adjacent coordinated bipyridyl groups.     

Polymorphic forms of lupane triterpenoid betulonic aldehyde (betulonal)

The lupane triterpenoid betulonic aldehyde [also known as betulonal; systematic name: lup‐20(29)‐en‐28‐al‐3‐one, C₃₀H₄₆O₂] is a product of betulin oxidation. Crystals were obtained from hexane [form (I)] and dimethyl sulfoxide [form (II)] solutions. Forms (I) and (II) are both orthorhombic. The molecular geometric parameters in the two forms are similar, but the structures are different with respect to the crystal packing. Polymorph (I) contains two independent molecules in the asymmetric unit, while polymorph (II) contains only one molecule, which has a disordered aldehyde group [the disorder ratio is 0.769 (4):0.231 (4)]. In each molecule, the six‐membered rings have chair conformations, whereas the cyclopentane ring in each molecule adopts an envelope conformation. All the rings in the lupane nucleus are trans‐fused. The extended structures of both polymorphs are stabilized by weak intermolecular C—H...O and van der Waals interactions. Weak intramolecular C—H...O interactions are also observed.     

2‐Ethylsulfanyl‐7‐(furan‐2‐yl)‐4‐(thiophen‐2‐yl)pyrazolo[1,5‐a][1,3,5]triazine: π‐stacked chains of hydrogen‐bonded R22(10) dimers

In the title compound, C₁₅H₁₂N₄OS₂, the bond distances in the fused heterocyclic system show evidence for aromatic‐type delocalization in the pyrazole ring with some bond fixation in the triazine ring. The thiophenyl substituent is slightly disordered over two sets of atomic sites having occupancies of 0.934 (4) and 0.066 (4). The non‐H atoms in the entire molecule are nearly coplanar, with the planes of the furanyl substituent and the major orientation of the thiophenyl substituent making dihedral angles of 5.72 (17) and 1.8 (3)°, respectively, with that of the fused ring system. Molecules are linked into centrosymmetric R₂²(10) dimers by C—H...O hydrogen bonds and these dimers are further linked into chains by a single π–π stacking interaction. Comparisons are made with some related 4,7‐diaryl‐2‐(ethylsulfanyl)pyrazolo[1,5‐a][1,3,5]triazines which contain variously substituted aryl groups in place of the furanyl and thiophenyl substituents in the title compound.     

An unusual conformation of gabapentin (Gpn) in Pyr‐Gpn‐NH‐NH‐Pyr stabilized by weak interactions

The crystal structure of N‐[(1‐{2‐oxo‐2‐[2‐(pyrazin‐2‐ylcarbonyl)hydrazin‐1‐yl]ethyl}cyclohexyl)methyl]pyrazine‐2‐carboxamide monohydrate (Pyr‐Gpn‐NN‐NH‐Pyr·H₂O), C₁₉H₂₃N₇O₃·H₂O, reveals an unusual trans–gauche (tg⁻) conformation for the gabapentin (Gpn) residue around the C^γ—C^β (θ₁) and C^β—C^α (θ₂) bonds. The molecular conformation is stabilized by intramolecular N—H...N hydrogen bonds and weak C—H...O interactions. The packing of the molecules in the crystal lattice shows a network of strong N—H...O and O—H...O hydrogen bonds together with weak C—H...O and π–π inteactions.     

Electronic structure,novel synthesis,and O—H...O and C—H...O interactions in two 6‐oxopiperidine‐2‐carboxylic acid derivatives

Molecules of (S)‐6‐oxo‐1‐(thiophen‐2‐ylmethyl)piperidine‐2‐carboxylic acid, C₁₁H₁₃NO₃S, crystallize as single enantiomers in the space group P2₁ and the thiophene ring is disordered over two positions, while (S)‐6‐oxo‐1‐(thiophen‐3‐ylmethyl)piperidine‐2‐carboxylic acid, C₁₁H₁₃NO₃S, crystallizes as a single enantiomer in the space group P2₁2₁2₁. Their absolute configurations were confirmed by anomalous dispersion effects in diffraction measurements on the crystals. The molecules of each compound are linked by a combination of strong O—H...O hydrogen bonds and weak C—H...O interactions, resulting in two‐ and three‐dimensional networks, respectively, in the crystal structures.     

Four related benzazepine derivatives in a reaction pathway leading to a benzazepine carboxylic acid: hydrogen‐bonded assembly in zero,one, two and three dimensions

(2R*,4S*)‐Methyl 2,3,4,5‐tetrahydro‐1,4‐epoxy‐1H‐benz[b]azepine‐2‐carboxylate, C₁₂H₁₃NO₃, (I), and its reduction product (2R*,4S*)‐methyl 4‐hydroxy‐2,3,4,5‐tetrahydro‐1H‐benz[b]azepine‐2‐carboxylate, C₁₂H₁₅NO₃, (II), both crystallize as single enantiomers in the space group P2₁2₁2₁, while the hydrolysis product (2RS,4SR)‐4‐hydroxy‐2,3,4,5‐tetrahydro‐1H‐benz[b]azepine‐2‐carboxylic acid, C₁₁H₁₃NO₃, (III), and the lactone (2RS,5SR)‐8‐(trifluoromethoxy)‐5,6‐dihydro‐1H‐2,5‐methanobenz[e][1,4]oxazocin‐3(2H)‐one, C₁₂H₁₀F₃NO₃, (IV), both crystallize as racemic mixtures in the space group P2₁/c. The molecules of compound (IV) are linked into centrosymmetric R₂²(10) dimers by N—H...O hydrogen bonds, and those of compound (I) are linked into chains by C—H...π(arene) hydrogen bonds. A combination of O—H...O and O—H...N hydrogen bonds links the molecules of compound (III) into sheets containing equal numbers of R₄⁴(14) and R₄⁴(26) rings, and a combination of C—H...π(arene) hydrogen bonds and three‐centre O—H...(N,O) hydrogen bonds links the molecules of compound (II) into a three‐dimensional framework structure. Comparisons are made with some related compounds.     

Formation of lithium,sodium and potassium complexes with 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol (taci)

Single crystals of (1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)lithium(I) diiodide dihydrate, [Li(C₆H₁₆N₃O₃)(C₆H₁₅N₃O₃)]I₂·2H₂O or [Li(Htaci)(taci)]I₂·2H₂O (taci is 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol), (I), bis(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)sodium(I) iodide, [Na(C₆H₁₅N₃O₃)₂]I or [Na(taci)₂]I, (II), and bis(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)potassium(I) iodide, [K(C₆H₁₅N₃O₃)₂]I or [K(taci)₂]I, (III), were grown by diffusion of MeOH into aqueous solutions of the complexes. The structures of the Na and K complexes are isotypic. In all three complexes, the taci ligands adopt a chair conformation with axial hydroxy groups, and the metal cations exhibit exclusive O‐atom coordination. The six O atoms of the resulting MO₆ unit define a centrosymmetric trigonal antiprism with approximate D_3d symmetry. The interligand O...O distances increase significantly in the order Li < Na < K. The structure of (I) exhibits a complex three‐dimensional network of R—NH₂—H...NH₂—R, R—O—H...NH₂—R and R—O—H...O(H)—H...NH₂—R hydrogen bonds. The structures of the Na and K complexes consist of a stack of layers, in which each taci ligand is bonded to three neighbours via pairwise O—H...NH₂ interactions between vicinal HO—CH—CH—NH₂ groups.