25,27‐(6‐Tosyl‐3,9‐dioxa‐6‐aza­un­decane‐1,11‐diyldioxy)‐26,28‐(3,6,9‐trioxaun­decane‐1,11‐diyldioxy)­calix­[4]­arene

A new calix­[4]‐­crowned aza­crown ether, C₅₁H₅₉NO₁₁S, consisting of four phenyl rings in a 1,3‐alternate conformation was synthesized from the reaction of 25,27‐bis(5‐chloro‐3‐oxa­pentyl­oxy)­calix­[4]­crown‐5 and p‐toluene­sulfon­amide in the presence of Cs₂CO₃. A crown‐5 loop was attached on the two facing lower rims of the calix­[4]­arene and the N‐tosyl aza­crown group was attached on the other set of lower rims of the calix­[4]­arene backbone. This mol­ecule seems to offer an inside cavity for the formation of a host–guest complex.     

Cone and 1,3‐alternate conformers of 1,3‐bis­(ethoxy­carbonyl­methoxy)‐2,4‐di­hydroxy­calix­[4]­arene and 1,2,3,4‐tetrakis­(ethoxy­carbonyl­methoxy)­calix­[4]­arene

The two title ethoxy­carbonyl­methoxy derivatives of calix­[4]­arene, namely diethyl 2,4‐di­hydroxy­calix­[4]­arene‐1,3‐diyldi(oxy­ace­tate), C₃₆H₃₆O₈, (I), and tetraethyl ­calix­[4]­arene‐1,2,3,4‐tetra­yltetra­(oxy­acetate), C₄₄H₄₈O₁₂, (II), form two different conformations, viz. a cone in (I), where intramol­ecular hydrogen bonds are formed through OH groups in a partially substituted calix­[4]­arene, and a 1,3‐alternate form of a completely substituted calix­[4]­arene in (II). A unique three‐dimensional array of mol­ecules exists in (II), with the channels extended along the entire crystal.     

25,27:26,28‐Bis(3,9‐dioxa‐6‐aza­undecane‐1,11‐dioxy)­calix­[4]­arene tetrahydrate

The title compound, C₄₄H₅₄N₂O₈·4H₂O, has twofold crystallographic symmetry and consists of a calix­[4]­arene moiety with four phenyl rings arranged alternately in anti‐orientation fashion and two aza­crown units attached on the lower rims of calix­[4]­arene. This seems to offer a big cavity inside the mol­ecule which might possess a potential for forming host–guest complexes.     

(5,11,17,23‐Tetra‐tert‐butyl‐26,28‐di­hydroxy­calix­[4]­arene‐25,27‐dioxy)­di­acetic acid N,N‐di­methyl­form­amide trisolvate

The title compound, C₄₈H₆₀O₈·3C₃H₇NO, is a derivative of calix­[4]­arene in the cone conformation, modified with distal carboxylic acid functional groups at the lower rim. A clathrate di­methyl­form­amide (DMF) mol­ecule is located within the calix­[4]­arene cone, and two DMF solvate mol­ecules participate in hydrogen bonding with the carboxylic acid groups. Intramolecular hydrogen bonds are also formed between the OH groups and the adjacent ether groups in the partially substituted calix­[4]­arene.     

6‐(2‐Fluorobenzylidene)‐2‐[1‐(2‐fluoro‐4‐biphenyl)ethyl]thiazolo[3,2‐b][1,2,4]triazol‐5(6H)‐one

The title compound, C₂₅H₁₇F₂N₃OS, was synthesized from 6‐(benzyl­idene)­thia­zolo­[3,2‐b][1,2,4]triazol‐5(6H)‐one. The fused thia­zolo­[3,2‐b][1,2,4]triazole system is essentially planar, and bifurcated C—H⋯O, C—H⋯N and C—H⋯F interactions are present between mol­ecules.     

2‐Amino­thia­zole and 2‐amino­thiazolinone derivatives

The reaction of different substituted α‐cyano­oxiranes with thio­urea resulted in the formation of the 2‐amino­thia­zolinone derivative 2‐amino‐5‐(2,5‐di­methoxy­phenyl)‐1,3‐thia­zol‐4(5H)‐one, C₁₁H₁₂N₂O₃S, (I), and the 2‐amino­thia­zole derivative ethyl 2‐amino‐5‐(2,5‐di­methoxy­phenyl)‐1,3‐thia­zole‐4‐carboxyl­ate, C₁₄H₁₆N₂O₄S, (II). The geometries of the two crystallographically independent mol­ecules in (II) are nearly identical but mirror related. The crystal structures of both compounds contain two types of intermolecular hydrogen bonds.     

A uranyl ion complex of N‐methyl‐p‐tert‐butyl­dihomo­ammonio­calix­[4]­arene with di­aqua­di­pyridine­lithium as counter‐ion

The title complex, di­aqua­di­pyridine­lithium (N‐methyl‐p‐tert‐butyl­dihomo­ammonio­calix­[4]­arene‐κ⁴O)­dioxouranium(VI) tri­pyridine solvate monohydrate, [Li(C₅H₅N)₂(H₂O)₂][UO₂(C₄₆H₅₈NO₄)]·3C₅H₅N·H₂O, contains an `internal' tetraphenoxide‐coordinated uranyl complex of the macrocycle, in which the protonated N atom is involved in an intramolecular hydrogen bond with the uranyl oxo group located in the cavity. The Li⁺ ion is in a tetrahedral environment and its two water ligands are involved in hydrogen bonds with two phenoxide O atoms, two pyridine mol­ecules and one water mol­ecule. This arrangement is compared with those obtained previously for other homo­aza­calixarenes and also for homo­oxa­calixarenes in the presence of alkali metal hydro­xides.     

6‐(3,4‐Di­fluoro­benzoyl)‐3‐[2‐(4‐pyridyl)­ethyl]‐1,3‐benzo­thia­zol‐2(3H)‐one

A new type of benzo­thia­zolinone derivative with potential pharmacological activity, viz. 6‐(3,4‐di­fluoro­benzoyl)‐3‐[2‐(4‐pyridyl)­ethyl]‐1,3‐benzo­thia­zol‐2(3H)‐one, C₂₁H₁₄F₂N₂O₂S, has been prepared and studied by NMR, IR and single‐crystal X‐ray diffraction techniques. The mol­ecule is not planar, the pyridine and di­fluoro­benzene moieties being located above and below the benzo­thia­zole ring system. The carbonyl O atoms are involved in an intramolecular hydrogen‐bond‐type interaction.     

20‐Di­cyano­methyl­ene‐5,8,11,14‐tetraoxa‐2,17‐di­thia­bi­cyclo­[16.4.1]­tricosa‐1(23),18,21‐triene and its mercury(II) dichloride complex

The structures of the title compound, C₂₀H₂₄N₂O₄S₂, and its mercury(II) dichloride complex, dichloro{20‐di­cyano­methyl­ene‐5,8,11,14‐tetraoxa‐2,17‐di­thia­bi­cyclo­[16.4.1]­tricosa‐1(23),18,­21‐tri­ene‐κ⁴O,κS¹⁷}mercury(II), [HgCl₂(C₂₀­H₂₄­N₂­O₄­S₂)], have been determined by X‐ray crystallographic analyses. The mercury(II) dichloride complex has two independent mol­ecules of [HgCl₂(C₂₀H₂₄N₂O₄S₂)] in the lattice. The mercury(II) ion has pentagonal bipyramidal coordination which involves one S atom, four O atoms and two Cl^? ions.     

2,3‐Dihydro‐3‐methyl‐2‐nitrimino‐1,3‐thiazole

The title compound {alternatively, 3‐methyl‐2‐[oxido(oxo)hydrazono]‐2,3‐dihydro‐1,3‐thiazole}, C₄H₅N₃O₂S, was obtained by methyl­ation of N‐(2‐thia­zolyl)­nitr­amine. The molecule lies on a mirror plane and the thia­zole ring is planar, regular in shape and aromatic. The S atom participates in the aromatic sextet via an electron pair on the 3p_z orbital. In the crystal, the mol­ecules are arranged in parallel layers, bound to each other by weak C—H?O and C—H?N hydrogen bonds and by S?O dipolar interactions, with an interlayer separation of 3.23 Å.     

Unusual conformations of 1,3‐dialk­oxy­thia­calix[4]arenes in the solid state

The structures of three syn‐1,3‐dialkoxy­thia­calix[4]arenes with unusual conformations in the solid state are reported. The pinched cone conformation of syn‐2²,4²‐dihydroxy‐1²,3²‐bis­(prop‐2‐enyl­oxy)thia­calix[4]arene, C₃₀H₂₄O₄S₄, (3a), is stabilized by two intra­molecular hydrogen bonds, remarkably formed from both OH groups to the same ether O atom. In syn‐2²,4²‐dihydroxy‐1⁵,2⁵,3⁵,4⁵‐tetra­nitro‐1²,3²‐bis­(prop‐2‐enyl­oxy)thia­calix[4]arene acetone disolvate, C₃₀H₂₀N₄O₁₂S₄·2C₃H₆O, (3b1), the mol­ecule is found in the 1,3‐alternate conformation. The crystallographic C2 symmetry is due to a twofold rotation axis running through the centre of the calixarene ring. The hydroxy groups cannot form intra­molecular hydrogen bonds as in (3a) and both are bonded to an acetone solvent mol­ecule. The mol­ecule of the pseudo‐polymorph of (3b1) in which the same compound crystallized without any solvent, viz. (3b2), is located on a crystallographic mirror plane. Only one of the two hydroxy groups forms a hydrogen bond, and this is with a nitro group of a neighbouring mol­ecule as acceptor. Mol­ecular mechanics calculations for syn‐1,3‐diethers suggest a preference of the 1,3‐alternate over the usual cone conformation for thia­calix[4]arene versus calix[4]arene and for para‐nitro versus para‐H derivatives.     

3,6‐Di­chloro‐4‐[2‐(4‐thia­morpholino)­ethanesulfanyl]­pyridazine and 3,6‐bis­(pyrazol‐1‐yl)‐4‐[2‐(4‐thia­mor­pho­lino)­ethanesulfanyl]­pyridazine

The trans–trans conformations adopted by the derivatized bis­(bidentate) chelating N₄‐donor ligand 3,6‐bis­(pyrazol‐1‐yl)‐4‐[2‐(4‐thia­morpholino)­ethanesulfanyl]­pyridazine, C₁₆H₁₉N₇S₂, and an intermediate in its formation, 3,6‐di­chloro‐4‐[2‐(4‐thia­morpholino)­ethanesulfanyl]­pyridazine, C₁₀H₁₃Cl₂N₃S₂, con­trast with the cis–cis conformation found previously for 3,6‐bis­(thio­phen‐2‐yl)­pyridazine [Ackers, Blake, Hill & Hubberstey (2002). Acta Cryst. C 58 , o640–o641], which places all four heteroatoms on the same side of the mol­ecule.     

A new pseudopolymorph of hexa­kis(4‐cyano­phenyl)benzene

The title compound (systematic name: benzene‐4,4′,4′′,4′′′,4′′′′,4′′′′′‐­hexayl­hexa­benzo­nitrile dichloro­methane disolvate), C₄₈H₂₄N₆·2CH₂Cl₂, crystallizes as an inclusion compound during the slow diffusion of methanol into a solution of hexa­kis(4‐cyano­phenyl)­benzene in CH₂Cl₂. The hexa­kis(4‐cyano­phenyl)benzene mol­ecule lies on an axis of twofold rotation in the space group Pbcn. Weak C—H⋯N inter­actions between hexa­kis(4‐cyano­phenyl)benzene mol­ecules define an open network with space for including guests. The resulting structure is a new pseudopolymorph of hexa­kis(4‐cyano­phenyl)benzene. The eight known pseudopolymorphs have few shared architectural features, in part because none of the inter­molecular inter­actions that are present plays a dominant role or forces neighboring mol­ecules to assume particular relative orientations.     

N‐(3H‐Thia­zol‐2‐yl­idene)­nitr­amine and N‐methyl‐N‐(thia­zol‐2‐yl)­nitr­amine

The geometries of the thia­zole ring and the nitr­amino groups in N‐(3H‐thia­zol‐2‐yl­idene)­nitr­amine, C₃H₃N₃O₂S, (I), and N‐­methyl‐N‐(thia­zol‐2‐yl)­nitr­amine, C₄H₅N₃O₂S, (II), are very similar. The nitr­amine group in (II) is planar and twisted along the C—N bond with respect to the thia­zole ring. In both structures, the asymmetric unit includes two practically equal mol­ecules. In (I), the mol­ecules are arranged in layers connected to each other by N—H⋯N and much weaker C—H⋯O hydrogen bonds. In the crystal structure of (II), the mol­ecules are arranged in layers bound to each other by both weak C—H⋯O hydrogen bonds and S⋯O dipolar interactions.     

Model porphyrin precursors: 1,2,4,5‐tetrakis(cyanomethyl)­benzene,methyl 3,4,5‐triacetoxy­benzoate and 2‐(N‐phthalimidomethyl)benzoic acid

In the crystalline state, the centrosymmetric mol­ecule 1,2,4,5‐tetrakis­(cyano­methyl)­benzene, C₁₄H₁₀N₄, has one cyano­methyl group in the benzene plane and one cyano­methyl group rotated 67.2 (2)° out of the benzene plane. Molecules of methyl 3,4,5‐tri­acetoxy­benzoate, C₁₄H₁₄O₈, form chains with each mol­ecule twisted 89.6 (1)° from the preceding mol­ecule. In this orientation, a close C—H?O contact is formed, with an H?O distance of 2.34 Å. The structure of 2‐(N‐phthalimido­methyl)­benzoic acid, C₁₆H₁₁NO₄, reveals hydrogen‐bonded dimers linked by the carboxyl groups of adjacent mol­ecules. The O4?O3 distance is 2.636 (2) Å and the O4—H?O3 angle is 171 (2)°.     

On the short carbonyl bond in bis[μ‐1,2‐benzisothiazol‐3(2H)‐one 1,1‐dioxido‐κ2N:O]bis{[1,2‐benzisothiazol‐3(2H)‐one 1,1‐dioxido‐κN]bis(imidazole)copper(II)}

The short carbonyl bond in the title compound, [Cu₂(C₇H₄­NO₃S)₄(C₃H₄N₂)₄] [Liu, Huang, Li & Lin (1991). Acta Cryst. C 47 , 41–43], is an artifact of disorder in the iso­thia­zol‐3(2H)‐one 1,1‐dioxide part of the 1,2‐benziso­thia­zol‐3(2H)‐one entity. In the present redetermination, all bond dimensions in the centrosymmetric dinuclear mol­ecule are normal. The five‐coordinate Cu atom shows trigonal–bipyramidal coordination. Hydro­gen bonds from the imidazole donor ligand link adjacent mol­ecules into a two‐dimensional layer structure.     

Di­spiro­[fluorene‐9,5′‐[1,2,3,4]­tetra­thia­ne‐6′,9′′‐fluorene]

The tetra­thia­ne ring of the title compound, C₂₆H₁₆S₄, has a chair conformation and the mol­ecule has approximate C₂ symmetry. Each of the two fluorene ring systems is virtually planar, with the ring planes intersecting at an angle of 67.58 (5)°. This novel compound has been formed as a side product from the treatment of 9H‐fluorene‐9‐thione with methyl N‐[(benzyl­idene)­phenyl]­glycinate in the presence of LiBr and 1,6‐di­aza­bi­cyclo­[5.4.0]­un­decane.     

Bis{4‐[N,N‐bis(2‐cyano­ethyl)­amino]­pyridine‐κN1}silver(I) perchlorate,with the perchlorate anion located in the cation cavity

The title complex, bis­[3,3′‐(pyridine‐4‐imino‐κN¹)­di­propane­nitrile]silver(I) perchlorate, [Ag(CEAP)₂]ClO₄ {CEAP is 4‐[N,N‐bis(2‐cyano­ethyl)­amino]­pyridine, C₁₁H₁₂N₄}, has been prepared and characterized. The unit cell consists of two crystallographically non‐equivalent mol­ecules. Cation cavities are constructed by [Ag(CEAP)₂]⁺ cations through hydrogen bonds, and the ClO₄⁻ anions are incorporated into the cavities in μ₄‐ and μ₂‐ClO₄⁻ bridging modes through C—H⃛O hydrogen bonds.     

cis‐Di­chloro(5,8‐dioxa‐2,11‐dithia[12]‐o‐cyclo­phane)­palladium(II)

The preparation and crystal structure of the title compound, cis‐di­chloro­[6,9‐dioxa‐3,12‐di­thia­bi­cyclo­[12.4.0]­octadeca‐14,‐16,­18(1)‐tri­ene‐S,S′]­palladium(II), [PdCl₂(C₁₄H₂₀O₂S₂)], are described. The Pd atom has a square‐planar environment, coordinated to two S atoms of the di­thia­dioxa macrocycle and to two Cl^? ions. The non‐coordinating O atoms are oriented away from the metal coordination plane. Upon complexation, a bicyclic chelate structure, which consists of a seven‐ and an eleven‐membered ring, is formed.     

4,4′‐Bis(4‐iodo­phenyl­amino­methyl)­azoxy­benzene: hydrogen‐bonded sheets built from C—H⃛O and C—H⃛π(arene) hydrogen bonds

Borohydride reduction of N‐(4‐nitro­benzyl­idene)‐4‐iodo­aniline has yielded the title compound, 1,2‐bis­[4‐(4‐iodo­phenyl­amino­methyl)­phenyl]­diazene 1‐oxide, C₂₆H₂₂I₂N₄O. The mol­ecules lie across centres of inversion in P2₁/c, with the azoxy O atom disordered over two sites, each having an occupancy of 0.5. The mol­ecules are linked into sheets by a combination of C—H⃛O and C—H⃛π(arene) hydrogen bonds.