Self‐assembled hydrogen‐bonded bilayers in 1,4‐diazabicyclo[2.2.2]octane–N‐(phosphonomethyl)iminodiacetic acid–water (1/1/1.5)

The title compound is a hydrated salt, 1,4‐diazo­nia­bi­cyclo­[2.2.2]­octane–N‐[(hydroxy­phosphinato)­methyl]­iminiodi­acetate–water (1/1/1.5), C₆H₁₄N₂²⁺·C₅H₈NO₇P^2?·1.5H₂O, in which one of the water mol­ecules lies across a twofold rotation axis in space group P2/n. The ionic components are linked into sheets by a combination of a three‐centre N—H?(O)₂ hydrogen bond and two‐centre O—H?O and N—H?O hydrogen bonds, and these sheets are pairwise linked by the water mol­ecules into bilayers, by means of further O—H?O hydrogen bonds.     

Halogen‐bonded adduct of 1,2‐dibromo‐1,1,2,2‐tetrafluoroethane and 1,4‐diazabicyclo[2.2.2]octane

Halogen bonding is an intermolecular interaction capable of being used to direct extended structures. Typical halogen‐bonding systems involve a noncovalent interaction between a Lewis base, such as an amine, as an acceptor and a halogen atom of a halofluorocarbon as a donor. Vapour‐phase diffusion of 1,4‐diazabicyclo[2.2.2]octane (DABCO) with 1,2‐dibromotetrafluoroethane results in crystals of the 1:1 adduct, C₂Br₂F₄·C₆H₁₂N₂, which crystallizes as an infinite one‐dimensional polymeric structure linked by intermolecular N...Br halogen bonds [2.829 (3) Å], which are 0.57 Å shorter than the sum of the van der Waals radii.     

2‐Cyano‐4‐iodoacetanilide: a hydrogen‐bonded chain of R22(12) and R22(14) rings

The molecules of 2‐cyano‐4‐iodoacetanilide, C₉H₇IN₂O, are linked by N—H...N and C—H...O hydrogen bonds into chains of alternating R₂²(12) and R₂²(14) rings.     

Methyl 4‐amino‐2,3‐dihydro‐6‐methoxy‐1,3‐dioxo‐1H‐pyrrolo[3,4‐c]pyridine‐7‐carboxylate forms hydrogen‐bonded sheets built from R22(8) and R66(42) rings

In the title compound, C₁₀H₉N₃O₅, which was formed by the reaction of 6‐amino‐2‐methoxy‐4(3H)‐pyrimidinone with di­methyl acetyl­enedi­carboxyl­ate, the mol­ecules are linked by N—H?O hydrogen bonds [N?O 2.8974 (15) and 3.0300 (15) Å, and N—H?O 165 and 174°] into planar sheets built from alternating R₂²(8) and R₆⁶(42) rings.     

Tetrakis(bicyclo[2.2.2]oct‐2‐ene)‐Fused Calix[4]pyrrole

Tetrakis(bicyclo[2.2.2]oct‐2‐ene)‐fused calix[4]pyrrole, 5 , was obtained starting from (E)‐1,2‐bis(phenylsulfonyl)ethylene. This new calixpyrrole derivative is the prospective precursor of tetrabenzocalix[4]pyrrole, a potential ion‐pair receptor and an attractive species as a possible deep‐walled ‘molecular container’.     

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.     

5‐Amino‐3‐tert‐butyl‐1‐(4‐nitro­phen­yl)‐1H‐pyrazole forms hydrogen‐bonded sheets of alternating R(20) and R(32) rings

Molecules of the title compound, C₁₃H₁₆N₄O₂, are linked by one N—H⋯O hydrogen bond [H⋯O = 2.47 Å, N⋯O = 3.326 (2) Å and N—H⋯O = 166°] and one N—H⋯N hydrogen bond [H⋯N = 2.19 Å, N⋯N = 3.063 (2) Å and N—H⋯N = 173°] into sheets containing alternating (20) and (32) rings, both types of which are centrosymmetric.     

2‐Amino‐5‐nitro­thia­zole monoethanol solvate: triply‐interwoven hydrogen‐bonded sheets containing centrosymmetric R(8) and R(38) rings

2‐Amino‐5‐nitro­thia­zole crystallizes from solution in ethanol as a monosolvate, C₃H₃N₃O₂S·C₂H₆O, in which the thia­zole component has a strongly polarized molecular–electronic structure. The thia­zole mol­ecules are linked into centrosymmetric dimers by paired N—H⋯N hydrogen bonds [H⋯N = 2.09 Å, N⋯N = 2.960 (6) Å and N—H⋯N = 169°], and these dimers are linked by the ethanol mol­ecules, via a two‐centred N—H⋯O hydrogen bond [H⋯O = 1.98 Å, N⋯O = 2.838 (5) Å and N—H⋯O = 164°] and a planar asymmetric three‐centred O—H⋯(O)₂ hydrogen bond [H⋯O = 2.07 and 2.53 Å, O⋯O = 2.900 (5) and 3.188 (5) Å, O—H⋯O = 169 and 136°, and O⋯H⋯O = 55°], into sheets built from alternating (8) and (38) rings. These sheets are triply interwoven.     

Felodipine–diazabicyclo[2.2.2]octane–water (1/1/1)

The title compound, C₁₈H₁₉Cl₂NO₄·C₆H₁₂N₂·H₂O, is a cocrystal hydrate containing the active pharmaceutical ingredient felodipine and diazabicyclo[2.2.2]octane (DABCO). The DABCO and water molecules are linked through O—H...N hydrogen bonds into chains around 2₁ screw axes, while the felodipine molecules form N—H...O hydrogen bonds to the water molecules. The felodipine molecules adopt centrosymmetric back‐to‐back arrangements that are similar to those present in all of its four reported polymorphs. The dichlorophenyl rings also form π‐stacking interactions. The inclusion of water molecules in the cocrystal, rather than formation of N—H...N hydrogen bonds between felodipine and DABCO, may be associated with steric hindrance that would arise between DABCO and the methyl groups of felodipine if they were directly involved in hydrogen bonding.     

Hydrogen‐bonded sheets of R22(10) and R44(24) rings in 1‐deoxy‐1‐morpholino‐d‐fructopyranose

In the title compound, C₁₀H₁₉NO₆, both rings adopt almost perfect chair conformations and their mutual orientation is influenced by an intramolecular O—H...N hydrogen bond. The molecules are linked by three independent O—H...O hydrogen bonds into sheets containing equal numbers of R₂²(10) and R₄⁴(24) rings.     

Tetraethylammonium dihydrogenarsenate bis(arsenic acid) and 1,4‐diazoniabicyclo[2.2.2]octane bis(dihydrogenarsenate) arsenic acid: hydrogen‐bonded networks containing dihydrogenarsenate anions and neutral arsenic acid molecules

The title compounds, (C₈H₂₀N)[H₂AsO₄][H₃AsO₄]₂, (I), and (C₆H₁₄N₂)[H₂AsO₄]₂[H₃AsO₄], (II), are unusual salts containing organic cations, dihydrogenarsenate anions and neutral arsenic acid molecules. In (I), the dihydrogenarsenate anion lies across a twofold rotation axis in the space group C2/c, while the cation is disordered across a centre of inversion. The [H₂AsO₄]⁻ and H₃AsO₄ species interact by way of O—H...O hydrogen bonds, leading to sheets and a three‐dimensional network for (I) and (II), respectively.     

Two closely related,and unexpected,quinolinone derivatives: a three‐dimensional hydrogen‐bonded framework structure and a hydrogen‐bonded molecular ribbon of R22(18) and R44(24) rings

1,5‐Bis(4‐chlorophenyl)‐3‐(2‐oxo‐1,2‐dihydroquinolin‐3‐yl)pentane‐1,5‐dione, (Ia), and 1,5‐bis(2‐chlorophenyl)‐3‐(2‐oxo‐1,2‐dihydroquinolin‐3‐yl)pentane‐1,5‐dione, (Ib), crystallize as an 84:16 mixture, 0.84C₂₆H₁₉Cl₂NO₃·0.16C₂₆H₁₉Cl₂NO₃, in the space group I4₁/a, where the molecules of the two isomers occupy very similar sites in the unit cell. A combination of one N—H...O hydrogen bond and one C—H...O hydrogen bond links the molecules, regardless of isomeric form, into a single three‐dimensional framework structure. The molecules of (9RS,10RS)‐8,9‐bis(4‐chlorobenzyl)‐10‐(2‐oxo‐1,2‐dihydroquinolin‐3‐yl)‐5,6,9,10‐tetrahydrophenanthridine, C₃₆H₂₂Cl₂N₂O₄, (II), are linked by two hydrogen bonds, one each of the N—H...O and C—H...O types, into a molecular ribbon in which centrosymmetric rings of R₂²(18) and R₄⁴(24) types alternate. The hydrogen‐bonded ribbons enclose channels, which contain highly disordered solvent molecules.     

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.     

Poly[[diaquabis(μ2‐1‐oxo‐2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane‐4‐carboxylato)copper(II)] dihydrate]

The asymmetric unit of the title complex, {[Cu(C₅H₆O₆P)₂(H₂O)₂]·2H₂O}_n, consists of half a Cu atom, one complete 1‐oxo‐2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane‐4‐carboxylate anion ligand and two non‐equivalent water molecules. The Cu atom lies on a crystallographic inversion centre and has an elongated axially distorted octahedral environment. A two‐dimensional layer structure parallel to (100) is formed as a result of the connectivity brought about by each anion bonding to two different Cu atoms via a carboxylate O atom and a bridging O atom of a C—O—P group. The water molecules participate in extensive O—H...O hydrogen bonding. Neighbouring layers are linked together by intermolecular hydrogen‐bonding interactions. The crystal structure is characterized by intra‐ and interlayer motifs of a hydrogen‐bonded network. This study demonstrates the usefulness of carboxylates with caged phosphate esters in crystal engineering.     

5‐Methyl‐N‐[2‐nitro‐4‐(trifluoromethyl)phenyl]‐1H‐pyrazole‐3‐amine: a chain of hydrogen‐bonded R22(6) and R22(16) rings

The molecular skeleton of the title compound, C₁₁H₉F₃N₄O₂, is almost planar and exhibits a polarized (charge‐separated) electronic structure in the nitroaniline portion. Molecules are linked by N—H...N and C—H...O hydrogen bonds to form a chain in which centrosymmetric R₂²(6) and R₂²(16) rings alternate.     

A hydrogen‐bonded chain of rings in 5‐amino‐1‐(4‐methoxybenzoyl)‐3‐methylpyrazole and a three‐dimensional hydrogen‐bonded framework in 5‐amino‐3‐methyl‐1‐(2‐nitrobenzoyl)pyrazole

The molecules of 5‐amino‐1‐(4‐methoxybenzoyl)‐3‐methylpyrazole, C₁₂H₁₃N₃O₂, (I), and 5‐amino‐3‐methyl‐1‐(2‐nitrobenzoyl)pyrazole, C₁₁H₁₀N₄O₃, (II), both contain intramolecular N—H...O hydrogen bonds. The molecules of (I) are linked into a chain of rings by a combination of N—H...N and N—H...π(arene) hydrogen bonds, while those of (II) are linked into a three‐dimensional framework structure by N—H...N and C—H...O hydrogen bonds.     

1,4‐Diazabicyclo[2.2.2]octane‐Catalyzed One‐Pot Synthesis of Pyrazolo[1,2‐a][1,2,4]triazole‐1,3‐diones under Ultrasound Acceleration

1,4‐Diazabicyclo[2.2.2]octane has been explored as an efficient catalyst to effect the three‐component condensation reactions between malononitrile, 4‐arylurazoles, and aromatic aldehydes in ethanol under ultrasound irradiation conditions. The reactions proceeded very rapidly under mild conditions to furnish the corresponding pyrazolo[1,2‐a][1,2,4]triazole‐1,3‐dione derivatives in excellent yields.     

Synthesis and Biological Activity of 4‐[(Substituted Phenoxyacetoxy)methyl]‐2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane‐1‐one

A series of novel 4‐[(substituted phenoxyacetoxy)methyl]‐2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane‐1‐one 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 4i , 4j , 4k , 4l , 4m , 4n , 4o were synthesized. Their structures were confirmed by IR, ¹H NMR, mass spectroscopy, and elemental analyses. The results of preliminary bioassays show that some of the title compounds exhibit moderate to good herbicidal and fungicidal activities. For example, the title compounds 4b , 4c , 4f , 4h , 4i , and 4j possess 90–100% inhibition against the growth of roots of both rape and barnyard grass at 10 mg/L. Moreover, the title compounds 4f , 4g , and 4h possess 75–89% inhibition against Botrytis cinerea at the concentration of 50 mg/L.     

μ‐1,4‐Benzenedicarboxylato‐bis[trans‐aqua(1,4,8,11‐tetraazacyclotetradecane)nickel(II)] diperchlorate forms a three‐dimensional hydrogen‐bonded framework

The title compound, [Ni₂(C₈H₄O₄)(C₁₀H₂₄N₄)₂(H₂O)₂](ClO₄)₂, contains two independent octahedral Ni^II centres with trans‐NiN₄O₂ chromophores. The bridging benzene­dicarboxyl­ate ligand is bonded to the two Ni atoms, each via one O atom of each carboxyl­ate, while the other O atom participates in an intramolecular N—H?O hydrogen bond, forming an S(6) motif. The cations are linked to the perchlorate anions via O—H?O and N—H?O hydrogen bonds [O?O 2.904 (6) and 2.898 (6) Å; O—H?O 158 (6) and 165 (6)°; N?O 3.175 (7) and 3.116 (7) Å; N—H?O 168 and 166°] to form molecular ladders. These ladders are linked by further O—H?O and N—H?O hydrogen bonds [O?O 2.717 (6) and 2.730 (5) Å; O—H?O 170 (4) and 163 (6)°; N?O 3.373 (7) and 3.253 (7) Å; N—H?O 163 and 167°] to form a continuous three‐dimensional framework. The perchlorate anions both participate in three hydrogen bonds, and both are thus fully ordered.