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.     

1,4‐Bis{[hydroxy(phenyl)phosphoryl]methyl}piperazine‐1,4‐diium tetrachloridocadmate(II) dihydrate and the cobaltate(II) analogue

The reaction of aminophosphinic acid with CdCl₂·2.5H₂O or CoCl₂·6H₂O in concentrated hydrochloric acid yielded the isostructural compounds 1,4‐bis{[hydroxy(phenyl)phosphoryl]methyl}piperazine‐1,4‐diium tetrachloridocadmate(II) dihydrate, (C₁₈H₂₆N₂O₄P₂)[CdCl₄]·2H₂O, (I), and 1,4‐bis{[hydroxy(phenyl)phosphoryl]methyl}piperazine‐1,4‐diium tetrachloridocobaltate(II) dihydrate, (C₁₈H₂₆N₂O₄P₂)[CoCl₄]·2H₂O, (II). The asymmetric unit of each contains two half dications, both located on crystallographic centres of inversion, a tetrachloridometallate(II) dianion and two solvent water molecules. The residues are linked into two‐dimensional layers in the ab plane by O—H...O hydrogen bonds.     

A Novel Reaction of 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU) or 1,5‐Diazabicyclo[4.3.0]non‐5‐ene (DBN) with Benzyl Halides in the Presence of Water

1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU) reacted with benzyl halides in CH₂Cl₂/H₂O 1 : 1 (v/v) to afford a mixture of eleven‐membered cyclic amide 1 and seven‐membered cyclic amide 2 . When the reaction was carried out in EtOH/H₂O 1 : 1 (v/v), product 2 was obtained as the major product. 1,5‐Diazabicyclo[4.3.0]non‐5‐ene (DBN) gave the five‐membered cyclic amide 3 as the sole product under the same reaction conditions.     

2,3‐Dihydro‐3,3‐dimethylspiro[1H‐4‐oxanthracene‐5,2′‐oxiran]‐10(5H)‐one

The central six‐membered ring in the title compound, C₁₆H₁₆O₃, is almost planar (and almost coplanar with the aromatic ring), despite one of its C atoms being formally sp³ hybridized. The planarity is a consequence of the C atom at the centre of the spiro­cyclic system also being part of the three‐membered epoxide ring. The mol­ecules are linked by π–­π and C—H?π interactions.     

New organic–inorganic frameworks incorporating iso‐ and heteropolymolybdate units and a 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium multiple hydrogen‐bond donor

Poly[bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) γ‐octamolybdate(VI) dihydrate], {(C₁₀H₁₆N₄)₂[Mo₈O₂₆]·2H₂O}_n, (I), and bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) α‐dodecamolybdo(VI)silicate tetrahydrate, (C₁₀H₁₆N₄)₂[SiMo₁₂O₄₀]·4H₂O, (II), display intense hydrogen bonding between the cationic pyrazolium species and the metal oxide anions. In (I), the asymmetric unit contains half a centrosymmetric γ‐type [Mo₈O₂₆]⁴⁻ anion, which produces a one‐dimensional polymeric chain by corner‐sharing, one cation and one water molecule. Three‐centre bonding with 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium, denoted [H₂Me₄bpz]²⁺ [N...O = 2.770 (4)–3.146 (4) Å], generates two‐dimensional layers that are further linked by hydrogen bonds involving water molecules [O...O = 2.902 (4) and 3.010 (4) Å]. In (II), each of the four independent [H₂Me₄bpz]²⁺ cations lies across a twofold axis. They link layers of [SiMo₁₂O₄₀]⁴⁻ anions into a three‐dimensional framework, and the preferred sites for pyrazolium/anion hydrogen bonding are the terminal oxide atoms [N...O = 2.866 (6)–2.999 (6) Å], while anion/aqua interactions occur preferentially viaμ₂‐O sites [O...O = 2.910 (6)–3.151 (6) Å].     

5,10‐dihydr­oxy‐5H,10H‐diimidazo[1,2‐a:1′,2′‐d]pyrazine

Crystallization of the title compound, C₈H₈N₄O₂, results in the formation of one‐dimensional chains of imidazole (im) mol­ecules linked together by strong hydrogen bonds. The O⋯N(im) separation and O—H(⋯N) distance are 2.6906 (17) and 1.74 (2) Å, respectively, and the O—H⋯N angle is 173 (2)°. The one‐dimensional chains are weakly π stacked along the b axis, with centroid‐to‐centroid separations of 3.678 (2) Å between five‐ and six‐membered rings and 3.963 (2) Å between six‐membered rings. Each mol­ecule is arranged around an inversion center.     

Isomorphous rare‐earth bis[bis(2,6‐diisopropylphenyl)phosphate] complexes and their self‐assembly into two‐dimensional frameworks by intramolecular hydrogen bonds

The crystal structures of rare‐earth diaryl‐ or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]chloridotetrakis(methanol‐κO )neodymium methanol disolvate, [Nd(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (1), and of the lutetium, [Lu(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (2), and yttrium, [Y(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (3), analogues have been obtained by reactions between lithium bis(2,6‐diisopropylphenyl)phosphate and LnCl₃(H₂O)₆ (in a 2:1 ratio) in methanol. Compounds (1)–(3) crystallize in the C 2/c space group. Their crystal structures are isomorphous. The molecule possesses C ₂ symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6‐diisopropylphenyl)phosphate ligands all display a κ¹O‐monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O₂P(O‐2,6‐ⁱPr₂C₆H₃)₂}₂Cl(CH₃OH)₄] molecular unit exhibits two intramolecular O—H…O hydrogen bonds, forming six‐membered rings, and two intramolecular O—H…Cl interactions, forming four‐membered rings. Intermolecular O—H…O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two‐dimensional hydrogen‐bond network. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]tetrakis(methanol‐κO )(nitrato‐κ²O ,O ′)neodymium methanol disolvate, [Nd(C₂₄H₃₄O₄P)(NO₃)(CH₄O)₄]·2CH₃OH, (4), have been obtained in an analogous manner from NdCl₃(H₂O)₆. Compound (4) also crystalizes in the C 2/c space group. Its crystal structure is similar to those of (1)–(3). The κ²O ,O ′‐bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CN_Nd = 8). Unlike (1)–(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO₃⁻ ligand. The structure of (4) displays intra‐ and intermolecular O—H…O hydrogen bonds similar to those in (1)–(3). Compounds (1)–(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl)phosphate] rare‐earth complexes.     

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.     

HBr or not HBr? That is the question: crystal structure of 6‐hydroxy‐1,4‐diazepane‐1,4‐diium dibromide redetermined

Liu et al. [Chin. J. Struct. Chem. (1996). 15 , 371–373] reported the structure of 6‐hydroxy‐1,4‐diazepane di(hydrogen bromide), C₅H₁₂N₂O·2HBr, which was interpreted in terms of neutral diazepane and HBr molecules. We found, however, ample evidence that the formation of an organic salt, consisting of a diammonium cation and two bromide anions, is more plausible. This interpretation is also in agreement with thermogravimetric analysis and with the observed solution behaviour. The crystal structure of 6‐hydroxy‐1,4‐diazepane‐1,4‐diium dibromide, C₅H₁₄N₂O²⁺·2Br^?, measured at 142 K, crystallized in the orthorhombic space group P2₁2₁2₁. The structure displays O—H…Br and N—H…Br hydrogen bonding. Contact distances are given. A search in the Cambridge Structural Database for the singly‐bonded H—Br moiety revealed a total of 69 structures. The question, whether these structures really include HBr as neutral molecules or rather Br^? anions and a protonated substrate such as an amine, is addressed.     

Four 2‐amino‐6‐aryl‐4‐methoxy‐11H‐pyrimido[4,5‐b][1,4]benzodiazepines: similar molecular structures but different crystal structures

2‐Amino‐4‐methoxy‐6‐phenyl‐11H‐pyrimido[4,5‐b][1,4]benzodiazepine, C₁₈H₁₅N₅O, (I), and its 6‐(2‐fluorophenyl)‐, 6‐(3‐nitrophenyl)‐ and 6‐(4‐methoxyphenyl)‐ analogues, viz. C₁₈H₁₄FN₅O, (II), C₁₈H₁₄N₆O₃, (III), and C₁₉H₁₇N₅O₂, (IV), respectively, all adopt molecular conformations which are almost identical, containing boat‐shaped seven‐membered rings. In each structure, paired N—H...N hydrogen bonds link the molecules into centrosymmetric dimers. In each of (I)–(III), the dimers are further linked, forming a different three‐dimensional framework in each case, while in compound (IV) the dimers are linked into sheets. The significance of this study lies in the observation of different crystal structures in four compounds whose molecular structures are very similar.     

Bis[N‐(2‐hydroxy­ethyl)‐β‐alaninato]copper(II)

The Cu^II ion in the title complex, [Cu(C₅H₁₀NO₃)₂] or [Cu(He‐ala)₂] [He‐ala = N‐(2‐hydroxy­ethyl)‐β‐alaninate], resides at the inversion centre of a square bipyramid comprised of two facially arranged tridentate He‐ala ligands. Each He‐ala ligand binds to a Cu^II ion by forming one six‐membered β‐alaninate chelate ring in a twist conformation and one five‐membered ethanol­amine ring in an envelope conformation, with Cu—N = 2.017 (2) Å, Cu—O_COO = 1.968 (1) Å and Cu—O_OH = 2.473 (2) Å. The [Cu(He‐ala)₂] mol­ecules are involved in a network of O—H⋯O and N—H⋯O hydrogen bonds, forming layers parallel to the (10) plane. The layers are connected into a three‐dimensional structure by van der Waals inter­actions, so that the mol­ecular centres form pseudo‐face‐centered close packing.     

1,1′‐Diethyl‐4,4′‐bipyridine‐1,1′‐diium bis(1,1,3,3‐tetracyano‐2‐ethoxypropenide): multiple C—H...N hydrogen bonds form a complex sheet structure

In the title salt, C₁₄H₁₈N₂²⁺·2C₉H₅N₄O⁻, the 1,1′‐diethyl‐4,4′‐bipyridine‐1,1′‐diium dication lies across a centre of inversion in the space group P2₁/c. In the 1,1,3,3‐tetracyano‐2‐ethoxypropenide anion, the two independent –C(CN)₂ units are rotated, in conrotatory fashion, out of the plane of the central propenide unit, making dihedral angles with the central unit of 16.0 (2) and 23.0 (2)°. The ionic components are linked by C—H...N hydrogen bonds to form a complex sheet structure, within which each cation acts as a sixfold donor of hydrogen bonds and each anion acts as a threefold acceptor of hydrogen bonds.     

2‐(exo‐Tricyclo[5.2.1.02,6]deca‐4,8‐dien‐3‐endo‐yl)acetaldehyde 2,4‐dinitrophenylhydrazone

The six‐membered ring of the norbornene moiety in the title compound, C₁₈H₁₈N₄O₄, is in a slightly distorted boat conformation, and the two five‐membered rings within it adopt envelope conformations. The structure is stabilized by inter‐ and intramolecular N—H?O hydrogen bonds.     

Spiro[pyrido[3,2,1‐ij]pyrimido[4,5‐b]quinoline‐7,5′‐pyrrolo[2,3‐d]pyrimidines] and Spiro[pyrimido[4,5‐b]quinoline‐5,1′‐pyrrolo[3,2,1‐ij]quinolines] Derived from 5,6‐Dihydro‐4H‐pyrrolo[3,2,1‐ij]quinoline‐1,2‐dione

Reaction of 5,6‐dihydro‐4H‐pyrrolo[3,2,1‐ij]quinoline‐1,2‐dione ( 1 ) with two equivalents of some 6‐aminouracils (or 6‐amino‐2‐thiouracil) generates spirocyclic tetrahydrobenzo[if]quinolizines ( 7 ). The one‐pot, three‐component reaction of amido ketone ( 1 ) with 6‐aminouracil (or 6‐amino‐2‐thiouracil) and a cyclic six‐membered 1,3‐diketone produces spirocyclic tetrahydropyrrolo[3,2,1‐ij]quinolinones ( 15 ).     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

1‐Phosphabicyclo[2.2.1]heptane

1‐Phosphabicyclo[2.2.1]heptanes Exo‐endo‐ and exo‐exo‐2.6‐dimethyl‐1‐phosphabicyclo [2.2.1]heptane have been obtained by cyclization of 2‐methyl‐4‐(2‐propenyl)phospholane in the presence of the complex base, sodium salt of diethylenglycolmonoethylether ‐ sodium amide in THF (NAMEDEG). The bicyclic phosphanes are characterized by reac‐tions with selenium, sulfur, (CH₃)₂SeO, CH₃I and HSO₃F, respectively, elemental analysis, X‐ray crystal structure analysis as well as ¹H, ¹³C, ³¹P NMR spectral measurements. The steric demand of these phosphanes as complex ligands has been estimated from the P, H coupling constants of the phosphonium fluorosulphates according to the Tolman model. The phosphane selenides were found to display the lowest values for the ¹J(Se, P) coupling constant, found up to now for alicyclic and cyclic aliphatic tertiary phosphane selenides. The ⁿJ(P, H)‐ and ⁿJ(H, H)_{n=2, 3} coupling constants have been extracted from the proton spectra at 600 MHz by computerized analysis.     

Three new [XC(O)NH]P(O)[N(CH2C6H5)2]2 phosphoric triamides (X = CClF2, 3‐F‐C6H4 and 3,5‐F2‐C6H3): a database analysis of tertiary N‐atom geometry in compounds with a C(O)NHP(O)[N]2 core

In the phosphoric triamides N,N,N′,N′‐tetrabenzyl‐N′′‐(2‐chloro‐2,2‐difluoroacetyl)phosphoric triamide, C₃₀H₂₉ClF₂N₃O₂P, (I), N,N,N′,N′‐tetrabenzyl‐N′′‐(3‐fluorobenzoyl)phosphoric triamide, C₃₅H₃₃FN₃O₂P, (II), and N,N,N′,N′‐tetrabenzyl‐N′′‐(3,5‐difluorobenzoyl)phosphoric triamide, C₃₅H₃₂F₂N₃O₂P, (III), the tertiary N atoms of the dibenzylamido groups have sp² character with minimal deviation from planarity. The sums of the three bond angles about the N atoms in (I)–(III) deviate by less than 8° from the planar value of 360°. The geometries of the tertiary N atoms in all phosphoric triamides with C(O)NHP(O)[N]₂ skeletons deposited in the Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B 58 , 380–388] have been examined and the bond‐angle sums at the two tertiary N atoms (SUM1 and SUM2) and the parameter ΔSUM (= SUM1 − SUM2) considered. It was found that in compounds with a considerable ΔSUM value, the more pyramidal N atoms are usually oriented so that the corresponding lone electron pair is anti with respect to the P=O group. In (I), (II) and (III), the phosphoryl and carbonyl groups, separated by an N atom, are anti with respect to each other. In the C(O)NHP(O) fragment of (I)–(III), the P—N bond is longer and the O—P—N angle is contracted compared with the other two P—N bonds and the O—P—N angles in the molecules. These effects are also seen in analogous compounds deposited in the CSD. Compounds with [C(O)NH]P(O)[N]X (X≠ N), such as compounds with a [C(O)NH]P(O)[N][O] skeleton, have not been considered here. Also, compounds with a [C(O)NH]₂P(O)[N] fragment have not been reported to date. In the crystal structures of all three title compounds, adjacent molecules are linked via pairs of P=O...H—N hydrogen bonds, forming dimers with C_i symmetry.     

Monoreduced 1,2‐dihydrocorannulene versus the parent corannulene

The monoanion of dihydrogenated corannulene isolated in the form of its potassium salt, namely tris(diglyme‐κ³O,O′,O′′)potassium hexacyclo[11.5.2.0^4,17.0^7,16.0^10,15.0^14,18]icosa‐1,3,5,7(16),8,10(15),11,13,17‐nonaenide, [K(C₆H₁₄O₃)₃](C₂₀H₁₂), has been structurally characterized for the first time. The X‐ray study confirms the previous NMR spectroscopic prediction that the two H atoms are attached to the same six‐membered ring to form 1,2‐dihydrocorannulene, thus destroying the aromaticity of only one arene ring of the corannulene core. The direct comparison of (C₂₀H₁₂)⁻ with the parent corannulene anion, (C₂₀H₁₀)⁻, is provided to illustrate the geometry perturbations caused by rim hydrogenation.     

{2,5‐Bis[3‐(tert‐butyl­aminoxyl)­phenyl]‐1,1‐dimethyl‐3,4‐diphenyl­silole‐κO}bis­(1,1,1,5,5,5‐hexa­fluoro­pentane‐2,4‐dionato)­manganese(II)

In the structure of the first bis‐adduct of 2,5‐bis­[3‐(tert‐butyl­aminoxyl)­phenyl]‐1,1‐dimethyl‐3,4‐diphenyl­silole with bis­(hexa­fluoro­acetyl­acetonato)­manganese(II), [Mn(C₅HF₆O₂)₂(C₃₈H₄₂N₂O₂Si)₂], the Mn atom lies on a crystallographic inversion centre and is bound to two chelating hexafluoro­acetylacetonate ligands and two monodentate nitroxide groups in a distorted octa­hedral configuration. The silole ligands present a propeller‐like arrangement of the benzene rings around the Si‐containing five‐membered ring. The dihedral angles between the complexed nitroxides and the benzene rings to which they are bound are smaller than those found in the free ligand.     

μ‐Aqua‐penta­aqua­[μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine]­chloro­dinickel(II) trichloride trihydrate

The title compound, μ‐aqua‐1:2κ²O‐penta­aqua‐1κ²O,2κ³O‐μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine‐1κ²N¹,N⁶:2κ²N²,N³‐chloro‐1κCl‐dinickel(II) trichloride trihydrate, [Ni₂Cl(C₁₆H₁₄­N₄)(H₂O)₆]Cl₃·3H₂O, consists of two Ni^II atoms, a 3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine mol­ecule, four Cl atoms and nine water mol­ecules. The two Ni atoms are octahedrally coordinated by N and Cl atoms, and by water mol­ecules, and the three six‐membered rings, a pyridazine and two picolines, are planar to within 0.181 (3) Å. The crystal structure is stabilized by an intra‐ and intermolecular hydrogen‐bonding scheme involving water–water and water–chlorine interactions.