Bis­[(R)‐3,5‐di­chloro‐N‐(1‐phenyl­ethyl)­salicyl­idene­aminato‐κ2N,O]­copper(II) and bis­[(R)‐3‐ethoxy‐N‐(1‐phenyl­ethyl)­salicyl­idene­aminato‐κ2N,O]copper(II)

The title compounds, [Cu(C₁₅H₁₂Cl₂NO)₂], (I), and [Cu(C₁₇­H₁₈NO₂)₂], (II), both adopt a compressed tetrahedral trans‐[CuN₂O₂] coordination geometry, the mol­ecules having an umbrella conformation overall. These complexes differ from one another with respect to the 1‐phenyl­ethyl­amine moieties, the direction of the benzene rings being either inside [in (I)] or inside and outside [in (II)] of the mol­ecules. The crystals of (I) and (II) have Δ(R,R) and Λ(R,R) absolute configurations, respectively.     

Tolterodinium (+)‐(2R,3R)‐hydrogen tartrate

In the crystal structure of (R)‐N,N‐diisopropyl‐3‐(2‐hydroxy‐5‐methyl­phenyl)‐3‐phenyl­propyl­aminium (2R,3R)‐hydrogen tartrate, C₂₂H₃₂NO⁺·C₄H₅O₆⁻, the hydrogen tartrate anions are linked by O—H⋯O hydrogen bonds to form helical chains built from (9) rings. These chains are linked by the tolterodine molecules via N—H⋯O and O—H⋯O hydrogen bonds to form separate sheets parallel to the (101) plane.     

Supramolecular structures of 2‐cyano‐3‐di­methyl­amino‐N‐(4‐methyl­phenyl)­acryl­amide and 2‐cyano‐3‐di­methyl­amino‐N‐(2‐methoxy­phenyl)­acryl­amide

In the title compounds, C₁₃H₁₅N₃O, (I), and C₁₃H₁₅N₃O₂, (II), the dihedral angles between the planes of the phenyl ring and the amide group are 4.1 (1) and 20.7 (1)°, respectively. The mol­ecules adopt a fully extended conformation, aided by intramolecular interactions. The molecular structures of (I) and (II) display different crystal packing and hydrogen‐bonding networks.     

3‐(4‐Chloro­benzoyl)‐7‐(N,N‐di­methyl­amino)‐1‐phenyl­indolizine and 3‐(2,4‐di­chloro­benzoyl)‐7‐(N,N‐di­methyl­amino)‐1‐phenyl­indolizine

In both of the title compounds, C₂₃H₁₉ClN₂O, (I), and C₂₃H₁₈Cl₂N₂O, (II), the molecular packing is influenced by weak intermolecular C—H⋯O and C—H⋯π interactions, but despite the chemical similarity of the compounds, the packing in (II) is entirely different from that observed in (I).     

N‐Iso­propyl‐N‐[(E)‐2‐phenyl­propenyl]­thio­benz­amide and N‐iso­propyl‐3‐methoxy‐N‐[(E)‐2‐phenyl­propenyl]­thio­benz­amide

The crystal structures of the two title thio­benz­amides, C₁₉H₂₁NS, (I), and C₂₀H₂₃NOS, (II), were determined to investigate the relationship between the photoreactivity in solid state and the structure. Their geometry was confirmed to be the E isomer in each case.     

(4,6‐Dimercapto‐1,3,5‐triazine‐2‐thiol­ato‐S2)­tris­(tri­phenyl­phosphine‐P)gold(I) di­methyl­form­amide solvate

In the title compound, [Au(C₃H₂N₃S₃)(C₁₈H₁₅P)₃]·C₃H₇NO, the Au^I atom has a distorted tetrahedral geometry consisting of one uncoordinated di­methyl­form­amide mol­ecule, one tri­thio­cyanurate ligand and three PPh₃ ligands. The S—Au distance is 2.909 (2) Å, and the P—Au distances fall in the range 2.400 (14)–2.4074 (13) Å. The S—Au—P angles are 92.81 (6), 99.17 (6) and 104.21 (5)°, and the P—Au—P angles are 114.46 (5), 119.04 (5) and 119.66 (5)°.     

1,1‐Bis­(phenyl­sulfonyl)‐1‐(pyridinio)­methanide

The title di­sulfonyl‐stabilized pyridinium yl­ide, C₅H₅N⁺–C⁻(SO₂C₆H₅)₂ or C₁₈H₁₅NO₄S₂, contains a near planar NCS₂ core. The structure suggests that the formal negative charge of the yl­ide C atom is delocalized to the S atoms rather than the N atom. Structural features of pyridinium yl­ides are briefly discussed.     

2‐Benzoyl‐N‐phenyl‐2‐(1,2,4‐triazol‐1‐yl)­thio­acet­amide and 2‐(4‐methoxy­benzoyl)‐N‐phenyl‐2‐(1,2,4‐triazol‐1‐yl)­thio­acet­amide

In the two title compounds, C₁₇H₁₄N₄OS, (I), and C₁₈H₁₆N₄O₂S, (II), the dihedral angles between the planes of the triazole and N‐phenyl rings and the plane of five of the atoms that link these two rings are 63.5 (8) and 73.2 (6)° for (I), and 65.1 (1) and 72.1 (3)° for (II), respectively. There are some inter‐ and intramolecular interactions in the crystal structure.     

Comparison of the structure of (E)‐2‐(2‐benzylidenehydrazinylidene)quinoxaline with those of its chloro‐ and bromobenzylidene analogues

(E)‐2‐(2‐Benzylidenehydrazinylidene)quinoxaline, C₁₅H₁₂N₄, crystallized with two molecules in the asymmetric unit. The structures of six halogen derivatives of this compound were also investigated: (E)‐2‐[2‐(2‐chlorobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁ClN₄; (E)‐2‐[2‐(3‐chlorobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁ClN₄; (E)‐2‐[2‐(4‐chlorobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁ClN₄; (E)‐2‐[2‐(2‐bromobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁BrN₄; (E)‐2‐[2‐(3‐bromobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁BrN₄; (E)‐2‐[2‐(4‐bromobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁BrN₄. The 3‐Cl and 3‐Br compounds are isomorphous, as are the 4‐Cl and 4‐Br compounds. In all of these compounds, it was found that the supramolecular structures are governed by similar predominant patterns, viz. strong intermolecular N—H...N(pyrazine) hydrogen bonds supplemented by weak C—H...N(pyrazine) hydrogen‐bond interactions in the 2‐ and 3‐halo compounds and by C—H...Cl/Br interactions in the 4‐halo compounds. In all compounds, there are π–π stacking interactions.     

N‐(4‐Nitro­benzyl­idene)‐N′‐phenyl­hydrazine

Molecules of the title compound (alternative name: p‐nitro­benz­aldehyde phenyl­hydrazone), C₁₃H₁₁N₃O₂, adopt an E configuration about the azomethine C=N double bond. Molecules are approximately planar and the dihedral angle between the planes of the phenyl rings is 11.62 (9)°. Hydro­gen bonding links mol­ecules related by 4₂ screw axes to form helices with a pitch of 7.7186 (8) Å.     

2‐Amino derivatives of 5‐nitro­phenyl­acet­amide

The structures of the potential non‐linear optical (NLO) materials N‐[2‐(iso­propyl­amino)‐5‐nitro­phenyl]­acet­amide, (I) C₁₁H₁₅N₃O₃, and N‐[2‐(butyl­amino)‐5‐nitro­phenyl]­acet­amide, (II) C₁₂H₁₇N₃O₃, have been investigated by X‐ray analysis. To compare them with the structure of N‐[2‐(di­methyl­amino)‐5‐nitro­phenyl]­acet­amide, (III) C₁₀H₁₃N₃O₃, a known NLO compound, we had to redetermine the structure of (III), since it was described only briefly in the literature. There are two mol­ecules in the asymmetric unit of compound (I), which have different orientations of the substituents with respect to the benzene ring. The packing of mol­ecules in (II) and (III) contains stacks but both (I) and (II) crystallize in a centrosymmetric space group, which renders them inappropriate for NLO applications.     

(Aceto­nitrile‐N)(o‐benzo­quinone di­imine‐N,N′)­chloro‐trans‐bis­(tri­phenyl­phosphine‐P)­ruthenium(II) hexa­fluoro­phosphate 0.25‐hydrate

The Ru atom in the title compound, [RuCl(CH₃CN){P(C₆H₅)₃}₂{C₆H₄(NH)₂}]PF₆·0.25H₂O, has a six‐coordinate octahedral geometry, with a trans arrangement of the tri­phenyl­phosphine groups. The asymmetric unit contains two complex mol­ecules and a partially occupied water site. Principal dimensions include Ru—N 1.958 (4)–2.044 (5), Ru—P 2.3897 (16)–2.4092 (15), and Ru—Cl 2.4280 (15) and 2.4295 (16) Å     

N‐(2‐Bromoethyl)‐4‐piperidino‐1,8‐naphthalimide and N‐(3‐bromopropyl)‐4‐piperidino‐1,8‐naphthalimide

N‐(2‐Bromoethyl)‐4‐piperidino‐1,8‐naphthalimide, C₁₉H₁₉BrN₂O₂, (I), and N‐(3‐bromopropyl)‐4‐piperidino‐1,8‐naphthalimide, C₂₀H₂₁BrN₂O₂, (II), are an homologous pair of 1,8‐naphthalimide derivatives. The naphthalimide units are planar and each piperidine substituent adopts a chair conformation. This study emphasizes the importance of π‐stacking interactions, often augmented by other contacts, in determining the crystal structures of 1,8‐naphthalimide derivatives.     

Hydro­gen‐bonded dimers in N‐(2‐nitro­phenyl­thio)­saccharin

In the title compound, 2‐(2‐nitro­phenyl­thio)‐1,2‐benzo­thia­zol‐3(2H)‐one 1,1‐dioxide, 2‐O₂NC₆H₄S(C₇H₄NO₃S) or C₁₃H₈N₂­O₅S₂, the planes of the saccharin and nitro­phenyl­thiol­ate portions are almost orthogonal. The mol­ecules are linked by C—H?O=S hydrogen bonds [C?O 3.308 (3) Å, H?O 2.44 Å and C—H?O 155°] into cyclic centrosymmetric R²₂(16) dimers, reinforced by aromatic π?π stacking interactions between the nitrated aryl rings.     

(Z)‐3‐(1H‐Indol‐3‐yl)‐2‐(3‐thienyl)­acrylo­nitrile and (Z)‐3‐[1‐(4‐tert‐butyl­benzyl)‐1H‐indol‐3‐yl]‐2‐(3‐thienyl)­acrylo­nitrile

(Z)‐3‐(1H‐Indol‐3‐yl)‐2‐(3‐thienyl)­acrylo­nitrile, C₁₅H₁₀N₂S, (I), and (Z)‐3‐[1‐(4‐tert‐butyl­benzyl)‐1H‐indol‐3‐yl]‐2‐(3‐thienyl)­acrylo­nitrile, C₂₆H₂₄N₂S, (II), were prepared by base‐catalyzed reactions of the corresponding indole‐3‐carbox­aldehyde with thio­phene‐3‐aceto­nitrile. ¹H/¹³C NMR spectral data and X‐ray crystal structures of compounds (I) and (II) are presented. The olefinic bond connecting the indole and thio­phene moieties has Z geometry in both cases, and the mol­ecules crystallize in space groups P2₁/c and C2/c for (I) and (II), respectively. Slight thienyl ring‐flip disorder (ca 5.6%) was observed and modeled for (I).     

Penta­chloro‐1,3,6‐tris­(diethyl­phenyl­phosphino)­dirhenium(II,III)

The title complex [systematic name: penta­chloro‐1κ³Cl,2κ²Cl‐tris(diethylphenylphosphino)‐1κP,2κ²P‐dirhenium(II,III)(Re—Re)], 1,3,6‐Re₂Cl₅(PEt₂Ph)₃ or [Re₂Cl₅(C₁₀H₁₅P)₃], consists of dirhenium mol­ecules with eclipsed structures similar to those of previously characterized 1,3,6‐Re₂Cl₅(PR₃)₃ compounds. The Re—Re bond distance is 2.2262 (3) Å and the metal–metal bond order is 3.5.     

Retroracemization using new forms of Belokon's original ligand: ­intermediate NiII complexes of N‐({2‐[N‐(S)‐alkylprolylamino]phenyl}phenylmethylene)‐(S)‐phenylalanine (alkyl is 2‐picolyl, 3‐picolyl or ethyl)

In the title compounds, [N‐(phenyl{2‐[N‐(S)‐(2‐picolyl)­prolyl­amino]­phenyl}methyl­ene)‐(S)‐phenyl­alaninato]­nickel(II), [Ni(C₃₃H₃₀N₄O₃)], (I), [N‐(phenyl{2‐[N‐(S)‐(3‐picolyl)­prolyl­amino]­phenyl}methyl­ene)‐(S)‐phenyl­alaninato]­nickel(II) hemihydrate, [Ni(C₃₃H₃₀N₄O₃)]·0.5H₂O, (II), and [N‐({2‐[N‐(S)‐ethyl­prolyl­amino]­phenyl}phenyl­methyl­ene)‐(S)‐phenyl­ala­nin­ato]­nickel(II), [Ni(C₂₉H₂₉N₃O₃)], (III), the Ni^II centres have approximate square‐planar coordination geometries from N₃O donor sets. The picolyl N atoms in (I) and (II) are too remote from the metal centres to interact significantly, but the metal coordination geometries experience tetrahedral distortion and/or displacement of the metal centre from the N₃O plane. These are linked to conformational differences between the ligands of the symmetry‐independent complexes (Z′ = 2), which in turn are related to molecular packing. In (III), where a less sterically demanding ethyl group replaces the picolyl substituents, there are none of the distortions or displacements seen in (I) and (II).     

(2S,3S)‐2,6‐Dimethylheptane‐1,3‐diol,the oxygenated side chain of 22(S)‐hydroxycholestrol,and its synthetic precursor (R)‐4‐benzyl‐3‐[(2R,3S)‐3‐hydroxy‐2,6‐dimethylheptanoyl]‐1,3‐oxazolidin‐2‐one

(2S,3S)‐2,6‐Dimethylheptane‐1,3‐diol, C₉H₂₀O₂, (I), was synthesized from the ketone (R)‐4‐benzyl‐3‐[(2R,3S)‐3‐hydroxy‐2,6‐dimethylheptanoyl]‐1,3‐oxazolidin‐2‐one, C₁₉H₂₇NO₄, (II), containing C atoms of known chirality. In both structures, strong hydrogen bonds between the hydroxy groups form tape motifs. The contribution from weaker C—H...O hydrogen bonds is much more evident in the structure of (II), which furthermore contains an example of a direct short Osp³...Csp² contact that represents a usually unrecognized type of intermolecular interaction.     

4‐(Di­phenyl­phosphinoyl)‐3‐methyl‐N‐phenyl‐1,2‐isoxazole‐5‐carbox­amide

The title compound, C₂₃H₁₉N₂O₃P, was prepared by the reaction of ethynyldi­phenyl­phosphine oxide with phenyl isocyanate, triethyl­amine and nitoethane in benzene. The molecular structure is stabilized by an intramolecular N—H?O hydrogen bond.     

3‐Methoxy‐5‐(4‐methyl­phenyl­diazenyl)­salicyl­aldehyde and 3‐methoxy‐5‐(2‐methyl­phenyl­diazenyl)­salicyl­aldehyde

The two title mol­ecules, both C₁₅H₁₄N₂O₃, are roughly planar and display a trans conformation with respect to the –N=N– double bond, as found for other diazene derivatives. In both compounds, there are intramolecular O—H⋯O hydrogen bonds and the crystal packing is governed by weak intermolecular C—H⋯O hydrogen bonds and π–π stacking.