Methoxy‐ether and crown‐ether ­derivatives of tetrahomodioxa‐ and octahomotetraoxacalix­[4]­arenes

Three methoxy­‐ether and one methoxy‐­ether/crown‐ether derivatives of p‐tert‐butyl­tetrahomodioxa‐ and p‐R‐octahomo­tetraoxacalix­[4]­arenes (R = methyl, tert‐butyl, H) have been investigated. The first three compounds, 7,15,21,27‐tetra‐tert‐butyl‐29,30,31,32‐tetra­methoxy‐3,11‐dioxapenta­cyclo­[23.3.­1.1^5,9.1^13,17.1^19,23]­ditriaconta‐1(29),5,7,­9(30),­13,15,‐17(31),­19,21,23(32),25,27‐dodecaene, C₅₀H₆₈O₆, 33,34,35,36‐tetra­methoxy‐7,15,23,31‐tetra­methyl‐3,11,19,27‐tetra­oxa­penta­cyclo[27.3.1.1^5,9.1^13,17.1^21,25]­hexa­tri­aconta‐1(33),5,7,9(34),13,15,­17(35),21,23,25(36),29,31‐dodecaene, C₄₀H₄₈O₈, and 7,23‐di‐tert‐butyl‐33,34,35,36‐tetra­methoxy‐3,11,19,27‐tetraoxapenta­cyclo­[27.3.1.1^5,9.1^13,17.1^21,25]­hexatriaconta‐1(33),5,7,9(34),13,15,­17(35),‐ 21,23,25(36),29,31‐dodecaene, C₄₄H₅₆O₈, in the partial‐cone or 1,2‐alternate conformations, present the common feature of methoxy‐­ether self‐inclusion, while the fourth, 42,43‐di­methoxy‐7,15,23,31‐tetra­methyl‐3,11,19,27,34,37,40‐heptaoxahexa­cyclo[15.15.9.1^5,9.1^21,25.0^13,41.0^29,33]­tritetra­conta‐5(42),6,8,13(41),­14,16,21(43),22,24,29(33),30,32‐dodecaene, C₄₂H₅₀O₉, adopts the 1,3‐alternate conformation owing to the presence of a 1,3‐polyether chain.     

Dihydro[2.2.2]cryptand di‐μ‐hydroxo‐bis[bis(nitrato‐κ2O,O′)dioxouranium(VI)] monohydrate

In the title dinuclear uranyl complex, (C₁₈H₃₈N₂O₆)[(UO₂)₂(NO₃)₄(OH)₂]·H₂O, each pair of uranyl ions in the two independent centrosymmetric dianionic dimers is bridged by the two hydroxide ions, with the nitrate ions ensuring equatorial hexagonal coordination. The di­hydro[2.2.2]­cryptand (4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]­hexa­cosane) dication presents an `in–in' conformation (endo protonation) and it is hydrogen bonded to the hydroxide ions, either directly or via a water mol­ecule, resulting in the formation of linear hydrogen‐bonded polymers.     

An ion pair formed by protonated Fe(cp*py)2 and the octanuclear cluster U8Cl24O4(cp*py)2 [cp*py is tetramethyl‐5‐(2‐pyridyl)cyclopentadiene]

In bis­[1,1′,2,2′,3,3′,4,4′‐octa­methyl‐5‐(2‐pyridinio)‐5′‐(2‐pyri­dyl)­ferrocene] di‐μ₃‐chloro‐hexadeca‐μ₂‐chloro‐hexa­chloro­di‐μ₄‐oxo‐di‐μ₃‐oxo‐bis­[(η⁵,κN)‐1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­dienyl]octauranium(IV) di­chloro­methane tetrasolvate, [Fe(C₁₄H₁₇N)(C₁₄H₁₆N)]₂[U₈Cl₂₄O₄(C₁₄H₁₆N)₂]·4CH₂Cl₂, (I), two protonated Fe(cp*py)₂ units [cp*py is tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­diene] form an ion pair with the dianionic centrosymmetric cluster U₈Cl₂₄O₄(cp*py)₂. The latter is the highest nuclearity assemblage in the chemistry of uranium (non‐uranyl) compounds reported to date.     

(Borohydrido)(18‐crown‐6)potassium and (borohydrido)(dibenzo‐18‐crown‐6)(tetra­hydro­furan)potassium

In the two compounds (borohydrido)(1,4,7,10,13,16‐hexa­oxacyclo­octa­decane‐κ⁶O)potassium, [K(BH₄)(C₁₂H₂₄O₆)], (I), and (borohydrido)(1,4,7,10,13,16‐hexa­oxa‐2,3:11,12‐di­benzo­cyclo­octa­deca‐2,11‐diene‐κ⁶O)(tetra­hydro­furan)­potassium, [K(BH₄)(C₄H₈O)(C₂₀H₂₄O₆)], (II), the K atom is bound to the six O atoms of the crown ether and to a tridentate borohydride group, with further coordination to a tetra­hydro­furan mol­ecule in (II). The alkali metal ion environment is thus distorted hexa­gonal–pyramidal in (I) and bipyramidal in (II).     

Chiral and meso‐bis([2.2]­para­cyclo­phan‐4‐yl)­methane and meso‐bis­([2.2]­para­cyclo­phan‐4‐yl) sulfide

The [2.2]­para­cyclo­phane groups of the title compounds, chiral and meso‐bis­(tri­cyclo­[8.2.2.2^4,7]­hexa­deca‐4,6,10,12,13,15‐hexa­en‐5‐yl)­methane (the former as a racemate), C₃₃H₃₂, and meso‐bis­(tri­cyclo­[8.2.2.2^4,7]­hexa­deca‐4,6,10,12,13,15‐hexa­en‐5‐yl) sulfide, C₃₂H₃₀S, show the characteristic structural features of the parent compound [2.2]­para­cyclo­phane and the related compound di­methylbis([2.2]­para­cyclo­phan‐4‐yl)­silane, C₃₄­H₃₆­Si: the aromatic rings are puckered, resulting in a boat conformation. The planes of the four coplanar C atoms are slightly twisted with respect to each other. The Csp³—Csp³ bond lengths of the ethyl­ene bridges are elongated by the electronic and steric effects of the skeleton.     

The first X‐ray structure of a hexa­ammine­cobalt(III) salt with two different complex chloro­cadmium anions: synthesis,characterization and crystal structure of [Co(NH3)6]4[CdCl6][CdCl4(SCN)(H2O)]2Cl2·2H2O

In the title complex salt, tetra­kis[hexa­ammine­cobalt(III)] hexa­chloro­cadmate(II) bis­[aqua­tetra­chloro­thio­cyanato­cad­mate(II)] dichloride dihydrate, the discrete ions, i.e. [Co(NH₃)₆]³⁺, Cl⁻, [CdCl₆]⁴⁻ (located on an inversion centre) and [CdCl₄(SCN)(H₂O)]³⁻, together with cocrystallized water mol­ecules, are assembled by means of a network of hydrogen‐bonding inter­actions. This is the first X‐ray structure determination of a hexa­amminecobalt(III) salt with two different complex chloro­cadmium anions.     

N‐Ethylazatribenzo‐21‐crown‐7

The structure of the title compound, 25‐ethyl‐2,5,12,15,22,28‐hexa­oxa‐25‐aza­tetra­cyclo­[27.4.0.0^6,11.0^16,21]­tri­tria­conta‐1(29),6(11),7,9,16(21),17,19,30,32‐nona­ene, C₂₈H₃₃NO₆, does not exhibit a binding cavity for cations, but is collapsed in on itself. The conformation is unique among known tri­benzo‐21‐crown‐7 structures, and may be a result of intermolecular (C—H?π) and intramolecular (C—H?O) hydrogen bonding.     

A novel PtII–dibenzo‐18‐crown‐6 (DB18C6) complex

The novel Pt^II–dibenzo‐18‐crown‐6 (DB18C6) title complex, μ‐[tetrakis­(thio­cyanato‐S)­platinum(II)]‐N:N′‐bis{[2,5,8,­15,18,21‐hexa­oxa­tri­cyclo­[20.4.0.1^9,14]­hexa­cosa‐1(22),9(14),10,12,23,25‐hexaene‐κ⁶O]­potassium(I)}, [K(C₂₀H₂₄O₆)]₂[Pt(SCN)₄], has been isolated and characterized by X‐ray diffraction analysis. The structure analysis shows that the complex displays a quasi‐one‐dimensional infinite chain of two [K(DB18C6)]⁺ complex cations and a [Pt(SCN)₄]^2? anion, bridged by K⁺?π interactions between adjacent [K(DB18C6)]⁺ units.     

Hydrogen bonding and π–π stacking in methyl­aminium 4′,7‐dihydroxy­isoflavone‐3′‐sulfonate dihydrate and hexa­aqua­iron(II) bis­(4′,7‐diethoxy­isoflavone‐3′‐sulfonate) tetra­hydrate

In methyl­aminium 4′,7‐dihydroxy­isoflavone‐3′‐sulfonate dihydrate, CH₆N⁺·C₁₅H₉O₇S⁻·2H₂O, 11 hydrogen bonds exist between the methyl­aminium cations, the iso­flavone‐3′‐sulfonate anions and the solvent water mol­ecules. In hexa­aqua­iron(II) bis­(4′,7‐diethoxy­isoflavone‐3′‐sulfonate) tetra­hydrate, [Fe(H₂O)₆](C₁₉H₁₇O₇S)₂·4H₂O, 12 hydrogen bonds exist between the centrosymmetric [Fe(H₂O)₆]²⁺ cation, the isoflavone‐3′‐sulfonate anions and the solvent water mol­ecules. Additional π–π stacking inter­actions generate three‐dimensional supramolecular structures in both compounds.     

3,4‐(4‐Methoxy­benzo):8,9‐benzo­bicyclo­[4.4.1]­undeca‐3,8‐dien‐11‐one ethyl­ene acetal

The title compound, 5‐methoxy­spiro­[tetra­cyclo­[8.8.1.0^3,8.0^12,17]­nonadeca‐3,5,7,12,14,16‐hexene‐19,2′‐[1,3]­dioxolane], C₂₂H₂₄O₃, exhibits a twin‐chair conformation with the aromatic rings overlying each other. Comparison of the dihedral angle between these two rings with those from previously reported [3.3]­ortho­cyclo­phanes of this type suggests the presence of a weak attractive charge‐transfer interaction between the two, different, stacked arenes.     

1,3‐Bridged p‐methyloctahomotetraoxacalix[4]arene–bis‐crown‐3

The title compound, 13,21,35,43‐tetra­methyl‐3,6,9,17,25,28,31,39,46,49‐decaoxahepta­cyclo­[21.21.3.3^11,33.0^2,41.0^10,15.0^19,24.0^32,37]pentaconta‐1,10,12,14,19,21,23,32,34,36,41,43‐dodecaene, C₄₄H₅₂O₁₀, differs from previously reported 1,3‐bridged calix­[4]­arene–bis‐crown compounds in having an enlarged calixarene ring and shorter polyoxy­ethyl­ene bridges. The cavity is partly filled by the bridges.     

The monoclinic polymorph of rac‐5,7,7,12,12,14‐hexa­methyl‐1,4,8,11‐tetraazonia­cyclo­tetra­decane bis­(hexa­fluoro­germanate) tetrahydrate

X‐ray data were obtained for the monoclinic polymorph of rac‐5,7,7,12,12,14‐hexa­methyl‐1,4,8,11‐tetraazonia­cyclo­tetra­decane bis­(hexa­fluoro­germanate) tetrahydrate, (C₁₆H₄₀N₄)[GeF₆]₂·4H₂O. The tetra­aza‐macrocyclic cations lie across inversion centers in space group P2₁/c. Water mol­ecules and [GeF₆]²⁻ anions form zigzag chains, which alternate in a three‐dimensional network with the macrocyclic cations. The structure is sustained by multiple hydrogen bonds.     

The titanium–thiolate complex [Li(C4H8O)4][Ti2(SC6H5)9]

In the title compound, tetrakis­(tetra­hydro­furan)­lithium(I) tri‐μ‐phenyl­thiol­ato‐bis­[tris­(phenyl­thiol­ato)­titanate(IV)], [Li(C₄H₈O)₄][Ti₂(C₆H₅S)₉], (I), the central structural motif of the [Ti₂(SC₆H₅)₉]^? anion features a face‐sharing bi‐octa­hedron. The charge is balanced with a [Li(C₄H₈O)₄]⁺ cation. The asymmetric unit contains Ti, Li and a heavily disordered tetra­hydro­furan mol­ecule on a threefold axis, and two terminal and a bridging thio­phenolate moiety and a slightly disordered tetra­hydro­furan mol­ecule on general positions.     

The binary adduct of 3,6,9,16,19,22‐hexaazatricyclo[22.2.2.211,14]triaconta‐11,13,24,26(1),27,29‐hexaene and benzene‐1,2,4,5‐tetracarboxylic acid

The crystals of the title salt, 6,21‐di­aza‐3,9,18,24‐tetraazoniatri­cyclo­[22.2.2.2^11,14]­triaconta‐11,13,24,26(1),27,29‐hexaene benzene‐1,2,4,5‐tetra­carboxyl­ate(4?) hexahydrate, C₂₄H₄₂N₆⁴⁺·C₁₀H₂O₈^4?·6H₂O, are formed by the intermolecular interaction of a macrocyclic hex­amine with a mol­ecule of C₆H₂(COOH)₄ in aqueous solution. Both the cation and the anion are on inversion centres. Hydro­gen bonds are formed between the four ammonium cations in the hex­amine and the four carboxyl­ate anions in the aromatic acid. Stacks exist along the crystallographic a axis in the solid state. The water mol­ecules also take part in a hydrogen‐bonding network which joins these stacks together.     

Two novel bis­(2,9‐dimeth­yl‐1,10‐phenanthroline)copper(I) complexes: [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN and [Cu(dmp)2][N(CN)2]

Two new salts of the cation [Cu^I(dmp)₂]⁺ (dmp is 2,9‐dimeth­yl‐1,10‐phenanthroline, C₁₄H₁₂N₂), namely bis­[bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4‐pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C₁₄H₁₂N₂)₂]₂(PF₆)₂·0.5C₁₂H₁₀N₄·C₂H₃N or [Cu(dmp)₂]₂(PF₆)₂·0.5(bpmh)·CH₃CN [bpmh is bis­(4‐pyridylmethyl­idene)hydrazine, C₁₂H₁₀N₄], (I), and bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I) dicyanamide, [Cu(C₁₄H₁₂N₂)₂](C₂N₃) or [Cu(dmp)₂][N(CN)₂], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter‐ion.     

The molecular and supramolecular structures of four 1,5,6,10b‐tetrahydropyrazolo[1,5‐c]quinazolines

The supramolecular structures of the title compounds, 2‐phenyl‐5‐p‐tolyl‐1,5,6,10b‐tetra­hydro­pyrazolo­[1,5‐c]quinazoline, C₂₃H₂₁N₃, (I), 5‐(4‐bromo­phenyl)‐2‐phenyl‐1,5,6,10b‐tetra­hydro­pyrazolo­[1,5‐c]­quinazoline, C₂₂H₁₈BrN₃, (II), 2‐(4‐chlorophenyl)‐5‐phenyl‐1,5,6,10b‐tetrahydropyrazolo[1,5‐c]quinazoline, C₂₂H₁₈ClN₃, (III), and 5‐(4‐bromo­phenyl)‐2‐(4‐chlorophenyl)‐1,5,6,10b‐tetrahydropyrazolo[1,5‐c]quinazoline, C₂₂H₁₇BrClN₃, (IV), are of two general types. Compounds (I), (II) and (III) form base‐paired dimers via N—H?N hydrogen bonds, where (I) and (II) are isomorphous, while in (IV), there are no conventional hydrogen bonds.     

Two new [Ni(tren)2]2+ complexes: [Ni(tren)2]Cl2 and [Ni(tren)2]WS4

Both title compounds, bis­[tris(2‐amino­ethyl)­amine]­nickel(II) dichloride, [Ni(tren)₂]Cl₂, (I), and bis­[tris(2‐amino­ethyl)­amine]­nickel(II) tetra­thio­tungstate, [Ni(tren)₂]WS₄, (II), contain the [Ni(tren)₂]²⁺ cation [tren is tris(2‐amino­ethyl)­amine, C₆H₁₈N₄]. The tren mol­ecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni²⁺ is located on a centre of inversion surrounded by one crystallographically independent tren mol­ecule. In the [Ni(tren)₂]²⁺ cation of (II), the Ni atom is bound to two crystallographically independent tren mol­ecules. The Ni atoms in the [Ni(tren)₂]²⁺ complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren mol­ecules. The counter‐ions are chloride anions in (I) and the tetrahedral [WS₄]^2? anion in (II). Hydro­gen bonding is observed in both compounds.     

Two triethylammonium ion complexes of monoanionic calix[4]arene

Two complexes between mono‐deprotonated calix­[4]­arene and Et₃HN⁺ are reported. The first, triethylammonium 26,27,28‐tri­hydroxy­penta­cyclo­[19.3.1.1^3,7.1^9,13.1^15,19]­octacosa‐1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23‐dodecaen‐25‐olate, C₆H₁₆N⁺·C₂₈H₂₃O₄^?, comprises only the cationic and anionic species, whereas the second, tris­(triethyl­ammonium) tris[26,27,28‐tri­hydroxy­penta­cyclo­[19.3.1.1^3,7.1^9,13.1^15,19]­octacosa‐1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23‐dodecaen‐25‐olate] aceto­nitrile solvate, 3C₆H₁₆N⁺·3C₂₈H₂₃O₄^?·C₂H₃N, comprises one aceto­nitrile solvent mol­ecule for three such units. In both cases, the units are stacked in columns so that the ammonium cation is hydrogen bonded to a phenolic or phenolate O atom of one mol­ecule and included in the hydro­phobic cavity of another neighbouring calixarene. The short contacts present indicate that cation?π and C—H?π interactions are likely to be involved in the inclusion phenomena.     

5,7,7,12,14,14‐Hexamethyl‐4,11‐diaza‐1,8‐diazonia­cyclo­tetra­decane penta­cyano­nitroso­ferrate(II) dihydrate: a supramolecular compound constructed by hydrogen bonds

The title compound, (C₁₆H₃₈N₄)[Fe(CN)₅(NO)]·2H₂O, contains one [Fe(CN)₅(NO)]²⁻ dianion, two half [H₂teta]²⁺ dications (teta is 5,7,7,12,14,14‐hexa­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane), each lying about an independent inversion centre, and two solvent water mol­ecules, all of which are held together by hydrogen bonds to form a three‐dimensional supramolecular framework.     

Copper(I) and copper(II) complexes of an ethylene cross‐bridged cyclam

The preparation and crystal structures of (4,11‐di­benzyl‐1,4,8,11‐tetra­aza­bi­cyclo­[6.6.2]­hexa­decane‐κ⁴N)copper(I) hexa‐fluorophosphate, [Cu(C₂₆H₃₈N₄)]PF₆, and acetonitrile(4,11‐dibenzyl‐1,4,8,11‐tetraazabicyclo[6.6.2]hexadecane‐κ⁴N)‐copper(II) bis(hexafluorophosphate), [Cu(C₂H₃N)(C₂₆H₃₈‐N₄)](PF₆)₂, are described. The Cu^I ion is tetracoordinated in a very distorted tetrahedron, while the Cu^II analogue is pentacoordinated in a square pyramid.