From α‐carbamoyl‐α‐cyano­oxiranes to 3‐halogenopyruv­amides

The crystal structures of the first stable α‐diol from the α‐halogenopyruv­amide series, 3‐chloro‐2,2‐di­hydroxy‐3‐phenyl­propan­amide, C₉H₁₀­ClNO₃, and three products [3‐(4‐chloro­phenyl)‐2‐cyano‐2,3‐epoxy­propan­amide, C₁₀H₇­ClN₂O₂, 3‐bromo‐2‐cyano‐2‐hydroxy‐3‐p‐tolyl­propan­amide, C₁₁H₁₁Br­N₂O₂, 3‐bromo‐2‐oxo‐3‐p‐tolyl­propan­amide, C₁₀H₁₀­BrNO₂] obtained during the systematic synthesis of α‐halogenopyruv­amides are reported. The crystal structures are dominated by hydrogen bonds involving an amide group. The stability of the geminal diol could be ascribed to hydrogen bonds which involve both hydroxyl groups.     

5‐Fluoro‐1‐octanoyl­uracil

The crystal structure of 5‐fluoro‐1‐octanoyl­uracil [5‐fluoro‐1‐octanoyl­pyrimidine‐2,4(1H,3H)‐dione, C₁₂H₁₇FN₂O₃], a lipophilic prodrug of 5‐fluoro­uracil, is described. The 5‐fluoro­pyrimidine‐2,4(1H,3H)‐dione moiety is similar to the known structure of 1‐acetyl‐5‐fluoro­uracil. The 1‐octanoyl group and the 5‐fluoro­uracil moiety are essentially coplanar, with the octanoyl carbonyl group oriented towards the the ring C—H group and away from the nearer ring carbonyl group. The torsion angle C—N—C—O (from the ring CH group to the octanoyl carbonyl group) of 9.2 (2)° is similar to the corresponding torsion angles reported for 1‐acetyl‐5‐fluoro­uracil (17.3 and 1.6°) and 1,3‐di­acetyl‐5‐fluoro­uracil (8.8°).     

3,3a‐Dihydrocyclo­penta­[b]­chromen‐1(2H)‐ones from the reaction of salicylaldehyde and 2‐cyclo­penten‐1‐one

The two title chromene compounds, 3,3a‐dihydrocyclo­penta­[b]chromen‐1(2H)‐one, C₁₆H₁₂O₂, (I), and 2‐(2‐hydroxy­benzyl­idene)‐3,3a‐dihydrocyclo­penta­[b]chromen‐1(2H)‐one, C₁₉H₁₄O₃, (II), have been determined in the monoclinic space group P2₁/n. Compound (I) is mainly stabilized by C—H⋯π inter­actions. Compound (II) is linked into infinite one‐dimensional chains with a C(3) motif via inter­molecular O—H⋯O hydrogen bonds. The inter­molecular C—H⋯π and π–­π inter­actions also play key roles in stabilizing the crystal packing. Two intra­molecular C—H⋯O hydrogen bonds with S(5) motifs were detected in (II).     

Leurosine me­thio­dide–methanol–water (1/3/2)

The crystal structure of a methanol–water solvate ofleurosine me­thio­dide, (leurosine‐CH₃)⁺I^?·3CH₃OH·2H₂O (C₄₇H₅₉IN₄O₉·3CH₃OH·2H₂O), is described. The piperidine ring of the upper part of the mol­ecule adopts a sofa conformation. An intramolecular hydrogen bond between the tertiary N and the hydroxyl group of the vindoline moiety of the mol­ecule is present.     

1‐[4‐(Methyl­sulfonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole derivatives

Three related compounds containing a pyrazole moiety with vicinal phenyl rings featuring a methyl­sulfonyl substituent are described, namely 3‐methyl‐1‐[4‐(methyl­sulfonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole, C₁₇H₁₆N₂O₂S, ethyl 1‐[4‐(methyl­sul­fonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole‐3‐carboxyl­ate, C₁₉H₁₈N₂O₄S, and 1‐[4‐(methyl­sulfonyl)­phenyl]‐3‐[3‐(morpholino)­phenoxy­methyl]‐5‐phenyl‐1H‐pyrazole, C₂₇H₂₇N₃O₄S. The design of these compounds was based on celecoxib, a selective cyclo­oxy­genase‐2 (COX‐2) inhibitor, in order to study the influence of various substituents on COX‐2 and 5‐lipoxy­genase (5‐LOX) inhibition.     

3‐(1‐Pyridinio)propane­sulfonate and 3‐(benzyl­dimethyl­ammonio)propane­sulfonate monohydrate

3‐(1‐Pyridinio)propane­sulfonate, C₈H₁₁NO₃S, and 3‐(benzyl­dimethyl­ammonio)propane­sulfonate monohydrate, C₁₂H₁₉NO₃S·H₂O, used as additives during protein refolding and crystallization, both crystallize in the monoclinic system in the P2₁/c space group, with one mol­ecule (or one set of mol­ecules) per asymmetric unit. The solvent water mol­ecule present in the second crystal structure results in the formation of a dimer through hydrogen bonds. The conformation of the propane­sulfonate moiety is similar in both structures.     

2‐Pyridone–tartronic acid (1/1), 3‐hydroxy­pyridinium hydrogen tartronate and 4‐hydroxy­pyridinium hydrogen tartronate

Tartronic acid forms a hydrogen‐bonded complex, C₅H₅NO·C₃H₄O₅, (I), with 2‐pyridone, while it forms acid salts, namely 3‐hydroxy­pyridinium hydrogen tartronate, (II), and 4‐hy­droxy­pyridinium hydrogen tartronate, (III), both C₅H₆NO⁺·C₃H₃O₅⁻, with 3‐hydroxy­pyridine and 4‐hydroxy­pyridine, respectively. In (I), the pyridone mol­ecules and the acid mol­ecules form R(8) and R(10) hydrogen‐bonded rings, respectively, around the inversion centres. In (II) and (III), the cations and anions are linked by N—H⋯O and O—H⋯O hydrogen bonds to form a hydrogen‐bonded chain. In each of (I), (II) and (III), an intermolecular hydrogen bond is formed between a carboxyl group and the hydroxyl group attached to the central C atom, and in (I), the hydroxyl group participates in an intramolecular hydrogen bond with a carbonyl group. No intermolecular hydrogen bond is formed between the carboxyl groups in (I), or between the carboxyl and carboxyl­ate groups in (II) and (III).     

The 1:1 cocrystals of the proton‐transfer compound dilituric acid–phenyl­biguanide monohydrate

A proton‐transfer compound, 1‐phenyl­biguanidium 5‐nitro‐2,6‐dioxo‐1,2,3,6‐tetra­hydro­pyrimidin‐4‐olate monohydrate, C₈H₁₂N₅⁺·C₄H₂N₃O₅⁻·H₂O, has been synthesized by a reaction between dilituric acid (5‐nitro‐2,4,6‐trihydroxy­pyrimi­dine, Dilit) and phenyl­biguanide (N‐phenyl­imido­carbonimidic diamide, Big). This compound cocrystallized as a 1:1 adduct, and the asymmetric unit consists of two dilituric amino–oxo planar tautomeric anions (Dilit⁻), two monoprotonated phenyl­biguanidium cations (BigH⁺) and two water mol­ecules of crystallization (Z′ = 2). Protonation occurs at the N atom attached to the phenyl ring of Big as a result of the proton‐transfer process from the acidic hydr­oxy group of Dilit. In the crystal structure, the hydrated 1:1 adduct is stabilized by 25 two‐ and three‐center hydrogen bonds.     

1-Amino-2-nitraminoethane

The mol­ecule of title compound, C₂H₇N₃O₂, has a zwitterionic structure. All non-H atoms, apart from the terminal N atom of the NH₃ group, lie in the same plane, with a maximum deviation of 0.056 (1) Å for the amine N atom of the nitr­amine group, whereas the deviation of the terminal N atom of the NH₃ group from the same plane is 1.222 (2) Å. Intermolecular hydrogen bonds within the crystal form a three-dimensional network.     

Di‐μ‐hydro­xo‐bis­(diiso­propyl­gallium)–1,4,8,11‐tetra­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane (1/1)

The hydro­lysis product [Ga₂(C₃H₇)₄(OH)₂]·C₁₄H₃₂N₄, derived from the tetrakis­(triiso­propyl­gallium)–1,4,8,11‐tetra­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane (1/1) adduct, consists of a centrosymmetric [ⁱPr₂Ga(μ‐OH)]₂ unit hydrogen bonded through the hydroxyl group to a nitro­gen on an adjacent centrosymmetric 1,4,8,11‐tetra­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane molecule, resulting in the generation of a molecular chain through the crystal.     

The 2:1 complex of maleic acid and 1,4‐diazabicyclo[2.2.2]octane: hydrogen‐bonded sheets linked by C–H⋯O hydrogen bonds

In the title complex, 1,4‐diazo­niabi­cyclo­[2.2.2]­octane bis­(hy­drogen maleate), C₆H₁₄N₂²⁺·2C₄H₃O₄^?, the C₄H₃O₄^? and C₆H₁₄N₂²⁺ ions, derived from maleic acid and 1,4‐di­aza­bi­cyclo­[2.2.2]­octane, respectively, are disordered across a mirror plane in space group Cmc2₁, and they are linked by two nearly linear N—H?O hydrogen bonds, with N?O distances of 2.662 (3) and 2.614 (4) Å, and N—H?O angles of 173°. The crystal structure consists of sheets with reticulations of 3.3792 (4) Å in stratum and 7.3892 (8) Å in width. The sheets are linked by C—H?O hydrogen bonds.     

1:2 Complexes of chloranilic acid with pyrazole and imidazole,and the aceto­nitrile solvate of a 1:1 complex with imidazole

2,5‐Di­chloro‐3,6‐di­hydroxy‐1,4‐benzo­quinone (chloranilic acid) forms X—H?Y (X, Y = N or O) and C—H?Cl hydrogen bonds with pyrazole and imidazole to afford bis­(pyrazolium) di­chloro­anilate and bis­(imidazolium) di­chloro­anilate, (I) and (II), both 2C₃H₅N₂⁺·C₆Cl₂O₄^2?, and imidazolium chloro­anilate aceto­nitrile solvate, C₃H₅N₂⁺·­C₆HCl₂O₄^?·C₂H₃N, (III). Their crystal structures demonstrate three novel supramolecular architectures based on supramolecular synthons to build a ladder, (I), a two‐dimensional network, (II), and a flat ribbon, (III).     

Triphenylphosphine oxide–3‐chlorobenzoic acid (1/1)

In the title compound, C₁₈H₁₅OP·C₇H₅ClO₂, the tri­phenyl­phosphine oxide molecule forms a single directed hydrogen bond with the 3‐chloro­benzoic acid molecule, with an O⃛O=P distance of 2.607 (2) Å. The C—Cl and C=O bonds adopt a cisoid conformation in the 3‐chloro­benzoic acid molecule.     

Weak antiferromagnetic inter­actions in hydro­nium diaqua‐1κO,2κO‐trichloro‐1κCl,2κ2Cl‐μ‐dimethyl­glycinato‐1κO:2κ2O′,N‐dimethyl­glycinato‐1κ2N,O‐dicuprate(II)

The crystal structure of the title compound, (H₃O)[Cu₂(C₄H₈NO₂)₂Cl₃(H₂O)₂], contains two Cu^II ions bridged by the carboxyl­ate group of a dimethyl­glycinate ion in an anti–anti configuration. The Cu^II atoms both have an approximately square‐pyramidal conformation geometry and are 5.977 (2) Å apart. The two dimethyl­glycinate ligands have similar conformations, although they play different roles in the structure. A weak antiferromagnetic inter­action between the two copper ions could be inferred from the magnetic susceptibility measurements.     

The hydrogen‐bonded adduct 7,16‐diazonia‐18‐crown‐6–4‐aminobenzenesulfonate–water (1/2/2)

In the title hydrated adduct, 1,4,10,13‐tetraoxa‐7,16‐diazo­nia­cyclo­octa­decane bis(4‐amino­benzene­sulfonate) dihydrate, C₁₂H₂₈N₂O₄²⁺·2C₆H₆NO₃S⁻·2H₂O, formed between 7,16‐di­aza‐18‐crown‐6 and the dihydrate of 4‐amino­benzene­sulfonic acid, the macrocyclic cations lie across centres of inversion in the orthorhombic space group Pbca. The anions alone form zigzag chains, and the cations and anions together form sheets that are linked via water mol­ecules and anions to form a three‐dimensional grid.     

A 1:1 adduct of hexa­methylene­tetramine and 4‐hydroxy‐3‐methoxy­benz­aldehyde

In the title complex, C₆H₁₂N₄·C₈H₈O₃, the hexa­methyl­ene­tetramine mol­ecule accepts a single intermolecular O—H?N hydrogen bond from the hydroxy group of the 4‐hydroxy‐3‐methoxy­benz­aldehyde moiety. The non‐centrosymmetric crystal structure is built from alternating molecular sheets of 4‐hydroxy‐3‐methoxy­benz­aldehyde and hexa­methyl­ene­tetramine mol­ecules, and is stabilized by intermolecular O—H?N, C—H?O and C—H?π interactions.     

Diaqua­bis[5‐(pyrazin‐2‐yl‐κN1)‐1H‐tetra­zolato‐κN1]manganese(II) and diaqua­bis[5‐(pyrazin‐2‐yl‐κN1)‐1H‐tetra­zolato‐κN1]zinc(II)

The two new title complexes, [Mn(C₅H₃N₆)₂(H₂O)₂] and [Zn(C₅H₃N₆)₂(H₂O)₂], are isomorphous. In both compounds, the metal atom is located on an inversion center and is coordinated by four N atoms from two 5‐(pyrazin‐2‐yl)‐1H‐tetra­zolate anions in the basal plane and by two O atoms of water ligands in the apical positions to form a distorted octa­hedral geometry. Inter­molecular hydrogen‐bond inter­actions between the uncoordinated N atoms of the tetra­zolate anions and the H atoms of the water mol­ecules lead to the formation of a three‐dimensional network.     

Moxifloxacinium chloride–water–methanol (2/1/1), a novel anti­bacterial agent

Moxifloxacin, a novel fluoro­quinolone with a broad spectrum of anti­bacterial activity, is available as the solvated monohydro­chloride salt 7‐[(S,S)‐2‐aza‐8‐azoniabicyclo­[4.3.0]non‐8‐yl]‐1‐cyclo­propyl‐6‐fluoro‐8‐meth­oxy‐4‐oxo‐1,4‐dihydroquinoline‐3‐carboxylic acid chloride–water–methanol (2/1/1), C₂₁H₂₅FN₃O₄⁺·Cl⁻·0.5H₂O·0.5CH₃OH. The asymmetric unit contains two cations, two chloride ions, a mol­ecule of water and one methanol mol­ecule. The two cations adopt conformations that differ by an almost 180° rotation with respect to the piperidinopyrrolidine side chain. The cyclo­propyl ring and the meth­oxy group are not coplanar with the quinoline ring system. The carboxylic acid function, the protonated terminal piperidyl N atom, the water mol­ecule, the chloride ion and the methanol mol­ecule participate in O—H⋯O, O—H⋯Cl, N—H⋯O and N—H⋯Cl hydrogen bonding, linking the mol­ecules into extended two‐dimensional networks.     

Four bis(1‐chloro‐2,2,4,4‐tetramethyl‐3‐oxocyclobutan‐1‐yl)oligosulfanes

The four oligosulfanes, bis(1‐chloro‐2,2,4,4‐tetra­methyl‐3‐oxo­cyclo­butan‐1‐yl)­disulfane, C₁₆H₂₄Cl₂O₂S₂, (III), 1,3‐bis(1‐chloro‐2,2,4,4‐tetra­methyl‐3‐oxo­cyclo­butan‐1‐yl)­trisulfane, C₁₆H₂₄Cl₂O₂S₃, (V), 1,4‐bis(1‐chloro‐2,2,4,4‐tetra­methyl‐3‐oxo­cyclo­butan‐1‐yl)­tetrasulfane, C₁₆H₂₄Cl₂O₂S₄, (VII), and 1,6‐bis(1‐chloro‐2,2,4,4‐tetra­methyl‐3‐oxo­cyclo­butan‐1‐yl)­hexasul­fane, C₁₆H₂₄Cl₂O₂S₆, (VIII), all have similar geometric parameters, with the C—C bond lengths involving the chloro‐substituted cyclo­butanyl C atom being elongated to about 1.59 Å. There are two mol­ecules in the asymmetric units of the tri‐ and tetrasulfanes, and the mol­ecules in the latter compound have local C₂ symmetry. The mol­ecule of the hexasulfane has crystallographic C₂ symmetry. Most of the cyclo­butanyl rings are not perfectly planar and have slight but varying degrees of distortion towards a flattened tetrahedron. The polysulfane chain in each structure has a helical conformation, with each additional S atom in the chain adding approximately one quarter of a turn to the helix.