{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.     

The 2:1 cocrystal of benzamide and penta­fluoro­benzoic acid

The crystal structure of the title compound, benzamide–2,3,4,5,6‐penta­fluoro­benzoic acid (2/1), 2C₇H₇NO·C₇HF₅O₂, consists of centrosymmetric hexa­meric supermolecules composed of four amide and two carboxylic acid mol­ecules connected via O—H⋯O and N—H⋯O hydrogen bonds. No phen­yl–perfluoro­phenyl π–π stacking inter­actions are observed in this cocrystal.     

Bis(μ‐diphenyl­phosphinato‐κ2O:O′)bis­[aqua­(diphenyl­phosphinato‐κO)bis­(pyridine‐κN)cobalt(II)]

In the centrosymmetric title compound, [Co₂(C₁₂H₁₀O₂P)₄(C₅H₅N)₄(H₂O)₂], each approximately octa­hedral Co atom features two trans‐coordinated pyridine mol­ecules, one water mol­ecule, a terminally coordinated monodentate diphenyl­phosphinate ligand, and two bidentate diphenyl­phosphinate ligands that bridge the two Co atoms across a centre of inversion to form a dimeric binuclear complex. The discrete mol­ecules are linked by double hydrogen bonds between the terminally coordinated diphenyl­phosphinate ligand and the water mol­ecule to form a continuous chain along the crystallographic b axis.     

Two N‐substituted 3,5‐diphenyl‐2‐pyrazoline‐1‐thiocarboxamides

The structures of N‐ethyl‐3‐(4‐fluoro­phen­yl)‐5‐(4‐methoxy­phen­yl)‐2‐pyrazoline‐1‐thio­carboxamide, C₁₉H₂₀FN₃OS, (I), and 3‐(4‐fluoro­phen­yl)‐N‐methyl‐5‐(4‐methyl­phen­yl)‐2‐pyrazoline‐1‐thio­carboxamide, C₁₈H₁₈FN₃S, (II), have similar geometric parameters. The meth­oxy/methyl‐substituted phenyl groups are almost perpendicular to the pyrazoline (pyraz) ring [inter­planar angles of 89.29 (8) and 80.39 (10)° for (I) and (II), respectively], which is coplanar with the fluoro­phenyl ring [inter­planar angles of 5.72 (9) and 10.48 (10)°]. The pyrazoline ring approximates an envelope conformation in both structures, with the two‐coordinate N atom involved in an intra­molecular N—H⋯N_pyraz inter­action. In (I), N—H⋯O and C—H⋯S inter­molecular hydrogen bonds are the primary inter­actions, whereas in (II), there are no intermolecular hydrogen bonds.     

(Z)‐2‐Methylbuten‐1‐yl(aryl)iodonium trifluoromethanesulfonates containing electron‐withdrawing groups on the aryl moiety

The crystal structures of [(Z)‐2‐methyl­but‐1‐en‐1‐yl]­[4‐(tri­fluoro­methyl)­phenyl]­iodo­nium tri­fluoro­methane­sulfonate, C₁₂H₁₃F₃I⁺·CF₃O₃S^?, (I), (3,5‐di­chloro­phenyl)­[(Z)‐2‐methyl­but‐1‐en‐1‐yl]­iodo­nium tri­fluoro­methane­sulfonate, C₁₁H₁₂­Cl₂I⁺·CF₃O₃S^?, (II), and bis{[3,5‐bis­(tri­fluoro­methyl)­phenyl][(Z)‐2‐methyl­but‐1‐en‐1‐yl]­iodo­nium} bis­(tri­fluoro­methane­sulfonate) di­chloro­methane solvate, 2C₁₃H₁₂F₆I⁺·­2CF₃­O₃S^?·CH₂Cl₂, (III), are described. Neither simple acyclic β,β‐di­alkyl‐substituted alkenyl­(aryl)­idonium salts nor a series containing electron‐deficient aryl rings have been described prior to this work. Compounds (I)–(III) were found to have distorted square‐planar geometries, with each I atom interacting with two tri­fluoro­methane­sulfonate counter‐ions.     

Three 5H‐indeno­[1,2‐c]­pyridazin‐5‐one derivatives,potent type‐B mono­amine oxidase inhibitors

The structures of three compounds, namely 7‐methoxy‐2‐[3‐(tri­fluoro­methyl)­phenyl]‐9H‐indeno­[1,2‐c]­pyridazin‐9‐one, C₁₉H₁₁F₃N₂O₂, (Id), 6‐methoxy‐2‐[3‐(tri­fluoro­methyl)­phenyl]‐9H‐indeno­[1,2‐c]­pyridazin‐9‐one, C₁₉H₁₁F₃N₂O₂, (IId), and 2‐methyl‐6‐(4,4,4‐tri­fluoro­butoxy)‐9H‐indeno­[1,2‐c]­pyridazin‐9‐one, C₁₆H₁₃F₃N₂O₂, (IIf), which are potent reversible type‐B mono­amine oxidase (MAO‐B) inhibitors, are presented and discussed. Compounds (Id) and (IId) crystallize in a nearly planar conformation. The crystal structures are stabilized by weak C—H⋯O hydrogen bonds. The packing is dominated by π–π stacking interactions between the heterocyclic central moieties of centrosymmetrically related mol­ecules. In compound (IIf), the tri­fluoro­ethyl termination is almost perpendicular to the plane of the ring.     

1‐(4‐Chloro­phenyl­sulfanyl)‐2‐nitro‐4‐(tri­fluoro­methyl)­benzene and 1‐(4‐chloro­phenyl­sulfanyl)‐4‐nitro‐2‐(tri­fluoro­methyl)­benzene

Two chemical isomers of 3‐nitro­benzotrifluoride, namely 1‐(4‐chloro­phenyl­sulfanyl)‐2‐nitro‐4‐(tri­fluoro­methyl)­benzene, C₁₃H₇ClF₃NO₂S, (I), and 1‐(4‐chloro­phenyl­sulfanyl)‐4‐nitro‐2‐(tri­fluoro­methyl)­benzene, C₁₃H₇ClF₃NO₂S, (II), have been prepared and their crystal structures determined with the specific purpose of forming a cocrystal of the two. The two compounds display a similar conformation, with dihedral angles between the benzene rings of 83.1 (1) and 76.2 (1)°, respectively, but (I) packs in P while (II) packs in P2₁/c, with C—H⋯O interactions. No cocrystal could be formed, and it is suggested that the C—H⋯O associations in (II) prevent intermolecular mixing and promote phase separation.     

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°).     

New electron‐deficient chiral phosphines: (4R,5R)‐1,3‐bis(trifluoromethanesulfonyl)perhydro‐1,3,2‐benzodiazaphosphol‐2‐yl] substituted amines

Three chiral electron‐deficient phosphine ligands, [(4R,15R)‐,3‐bis­(tri­fluoro­methane­sulfonyl)­per­hydro‐1,3,2‐benzodiazaphosphol‐2‐yl]­diethyl­amine, C₁₂H₂₀F₆N₃O₄PS₂, (IIIa), [(4R,5R)‐1,3‐bis­(tri­fluoro­methane­sulfonyl)­per­hydro‐1,3,2‐benzodi­aza­phosphol‐2‐yl]­di­methyl­amine, C₁₀H₁₆F₆N₃O₄PS₂, (IIIb), and bis­[(4R,5R)‐1,3‐bis­(tri­fluoro­methane­sulfonyl)­per­hydro‐1,3,2‐benzodi­aza­phosphol‐2‐yl]­methyl­amine, (IV), as the chloroform solvate, C₁₇H₂₃F₁₂N₅O₈P₂S₄·0.98CHCl₃, have been prepared from (1R,2R)‐N,N′‐bis­(tri­fluoro­methane­sulfonyl)‐1,2‐cyclo­hexane­di­amine and diethyl phosphor­amido­us dichloride, dimethyl phosphoramidous dichloride or methyl imidodi­phosphorus tetrachloride. The π‐acceptor abilities of these new types of ligands have been evaluated by X‐ray determination of the P—N bond lengths; it has been found that the most promising ligand is the bis­(phosphine) (IV).     

Hydrogen‐bonded one‐dimensional networks in 1:1 complexes of N,N′‐bis(2‐pyridyl)aryldiamines with anilic acid

The 1:1 complexes N,N′‐bis(2‐pyridyl)­benzene‐1,4‐di­amine–anilic acid (2,5‐di­hydroxy‐1,4‐benzo­quinone) (1/1), C₁₆H₁₄N₄·C₆H₄O₄, (I), and N,N′‐bis(2‐pyridyl)­bi­phenyl‐4,4′‐di­amine–anilic acid (1/1), C₂₂H₁₈N₄·C₆H₄O₄, (II), have been prepared and their solid‐state structures investigated. The component mol­ecules of these complexes are connected via conventional N—H?O and O—H?N hydrogen bonds, leading to the formation of an infinite one‐dimensional network generated by the cyclic motif R(9). The anilic acid molecules in both crystal structures lie around inversion centres and the observed bond lengths are typical for the neutral mol­ecule. Nevertheless, the pyridine C—N—C angles [120.9 (2) and 120.13 (17)° for complexes (I) and (II), respectively] point to a partial H‐atom transfer from anilic aicd to the bispyridyl­amine, and hence to H‐atom disorder in the OHN bridge. The bispyridyl­amine mol­ecules of (I) and (II) also lie around inversion centres and exhibit disorder of their central phenyl rings over two positions.     

(E)‐1‐(2′‐Deoxy‐β‐d‐ribo­furan­osyl)‐2,4‐di­fluoro‐5‐(2‐iodo­vinyl)­benzene

This analysis of the title compound, C₁₃H₁₃F₂IO₃, establishes the orientation of (E)‐5‐(CH=CH—I) as antiperiplanar (ap) to the C—C bond (5–6 position) of the 2,4‐di­fluoro­phenyl ring system, with the (E)‐5‐(CH=CH—I) H atom located in close proximity (2.17 Å) to the F4 atom of the 2,4‐di­fluoro­phenyl moiety.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

cis‐Bis­[1,3‐bis(2‐fluoro­phenyl)­triazenido‐κ2N1,N3]­bis­(pyridine‐κN)cadmium(II)

In the title compound, [Cd(C₁₂H₈F₂N₃)₂(C₅H₅N)₂], the Cd atom lies on a crystallographic twofold axis in space group Iba2. The coordination geometry about the Cd^II ion corresponds to a rhombically distorted octahedron, with two deprotonated 1,3‐bis(2‐fluoro­phenyl)­triazenide ions, viz. FC₆H₄NNNC₆H₄F⁻, acting as bidentate ligands (four‐electron donors). Two neutral pyridine (py) mol­ecules complete the coordination sphere in positions cis with respect to one another. The triazenide ligand is not planar (r.m.s. deviation = 0.204 Å), the dihedral angle between the phenyl rings of the terminal 2‐fluoro­phenyl substituents being 24.6 (1)°. The triazenide and pyridine Cd—N distances are 2.3757 (18)/2.3800 (19) and 2.3461 (19) Å, respectively. Intermolecular C—H⋯F interactions generate sheets of mol­ecules in the (010) plane.     

Form III of 2,2′,4,4′,6,6′‐hexanitro­azobenzene (HNAB‐III)

The crystal structure of form III of the title compound, HNAB [systematic name: bis(2,4,6‐trinitro­phenyl)diazene], C₁₂H₄N₈O₁₂, has finally been solved as a pseudo‐merohedral twin (monoclinic space group P2₁, rather than the ortho­rhombic space group C222₁ suggested by diffraction symmetry) using a dual space recycling method. The significant differences in the room‐temperature densities of the three crystalline forms allow examination of molecular differences due to packing arrangements. An interesting relationship with the stilbene analog, HNS, is discussed. Interatomic separations are compared with other explosives and/or nitro‐containing compounds.     

An oxonium hydrogen sulfate of 3a,6a‐diphenyl­glycoluril

In the title compound, (5‐oxo‐3a,6a‐diphenyl­perhydro­imidazo[4,5‐d]imidazol‐2‐ylidene)oxonium hydrogen sulfate, C₁₆H₁₅N₄O₂⁺·HSO₄⁻, the asymmetric unit contains a hydrogen sulfate anion and a 3a,6a‐diphenyl­glycoluril oxonium cation. The hydrogen sulfate anion is joined to the oxonium cation via a strong O—H⋯O hydrogen bond (H⋯O = 1.69 Å). The crystal packing is mainly dominated by inter­actions involving the hydrogen sulfate anion. The diphenyl­glycoluril oxonium cations also self‐assemble through N—H⋯O hydrogen bonds, forming mol­ecular chains along the [001] vector. Four intra­molecular C—H⋯N hydrogen bonds are observed, having an S(5) motif.     

Crystal engineering via C—H⋯F and C—H⋯π interactions in two substituted indoles

The crystal structures of 1‐(4‐fluoro­phenyl)‐2‐phenyl‐4,5,6,7‐tetra­hydro‐1H‐indole, C₂₀H₁₈FN, and 1‐(4‐fluoro­phenyl)‐6,6‐di­methyl‐2‐phenyl‐4,5,6,7‐tetra­hydro‐1H‐indole, C₂₂H₂₂FN, have been determined in order to study the role of `organic fluorine' in crystal engineering. These mol­ecules pack in the crystal structure via different types of molecular motifs utilizing weak C—H⋯F and C—H⋯π interactions.     

An analysis of C—H⋯O and C—H⋯π interactions in three substituted 4‐ketotetra­hydro­indoles

The crystal and molecular structures of the three 4‐ketotetrahydro­indoles 2‐(4‐chloro­phenyl)‐1‐(4‐fluoro­phenyl)‐6,6‐dimethyl‐4,5,6,7‐tetra­hydro‐1H‐indol‐4‐one (C₂₂H₁₉ClFNO), (I), 1‐(4‐fluoro­phenyl)‐2‐(4‐methoxy­phenyl)‐6,6‐di­methyl‐4,5,6,7‐tetra­hydro‐1H‐indol‐4‐one (C₂₃H₂₂FNO₂), (II), and 6,6‐dimethyl‐1,2‐di­phenyl‐4,5,6,7‐tetra­hydro‐1H‐indol‐4‐one (C₂₂H₂₁NO), (III), have been determined via single‐crystal X‐ray diffraction in order to study the intermolecular interactions therein. All three structures are stabilized via intermolecular C—H⋯O and C—H⋯π interactions, generating different molecular motifs.     

trans‐Bis[3‐(2‐fluorophenyl)‐1‐(4‐nitrophenyl)triazenido‐κN3]bis(pyridine‐κN)palladium(II)

In the title complex, [Pd(C₁₂H₈FN₄O₂)₂(C₅H₅N)₂] or trans‐[Pd(FC₆H₄N=N—NC₆H₄NO₂)(C₅H₅N)₂], the Pd atom lies on a centre of inversion in space group P. The coordination geometry about the Pd²⁺ ion is square planar, with two deprotonated 3‐(2‐fluoro­phenyl)‐1‐(4‐nitro­phenyl)­triazenide ions, FC₆H₄N=N—NC₆H₄NO₂^?, acting as monodentate ligands (two‐electron donors), while two neutral pyridine mol­ecules complete the metal coordination sphere. The whole triazenide ligand is not planar, with the largest interplanar angle being 16.8 (5)° between the phenyl ring of the 2‐­fluorophenyl group and the plane defined by the N=N—N moiety. The Pd—N(triazenide) and Pd—N(pyridine) distances are 2.021 (3) and 2.039 (3) Å, respectively.     

(E)‐N‐Benzyl­idene‐3‐chloro‐4‐fluoro­aniline

The title mol­ecule, C₁₃H₉ClFN, is substantially planar. The phenyl and 3‐chloro‐4‐fluoro­phenyl rings are on opposite sides of the C=N bond. There is an intermolecular C—H?F short contact with a C?F distance of 3.348 (2) Å and a C—H?F angle of 137.4 (1)°. The mol­ecules are held in layers parallel to the bc plane.     

Adducts of hexa­methyl­ene­tetr­amine with ferrocene­carboxyl­ic acid and ferrocene‐1,1′‐di­carboxyl­ic acid: multiple disorder in space groups Fmm2 and Cmcm

Hexa­methyl­ene­tetr­amine, C₆H₁₂N₄, and ferrocene­carboxyl­ic acid, C₁₁H₁₀FeO₂, form a 1:2 adduct, (I), which is a salt, viz. hexa­methyl­ene­tetramin­ium(2+) bis(ferro­cene­car­box­yl­ate), (C₆H₁₄N₄)[Fe(C₅H₅)(C₆H₄O₂)]₂. The dication in (I) is disordered with two orientations at a site of mm2 symmetry in space group Fmm2, while the anion lies across a mirror plane with its unsubstituted cyclo­penta­dienyl ring disordered over two sets of sites. With ferrocene‐1,1′‐di­carboxyl­ic acid, C₁₂H₁₀FeO₄, hexa­methyl­enetetr­amine forms a 1:1 adduct, (II), in which both components are neutral, viz. hexa­methyl­ene­tetramine–ferro­cene‐1,1′‐di­car­box­ylic acid (1/1), [Fe(C₆H₅O₂)₂]·C₆H₁₂N₄. The amine component in (II) is disordered with two orientations at a site of mm2 symmetry in space group Cmcm, while the acid component is disordered with two orientations at a site of 2/m symmetry. The components in (I) are linked into a finite three‐ion aggregate by a single N—H⃛O hydrogen bond, while the components of (II) are linked into continuous chains by a single O—H⃛N hydrogen bond.