Ethyl N‐[2‐(hydroxy­acetyl)­phenyl]­carbamate,ethyl N‐[2‐(hydroxy­acetyl)‐4‐iodo­phenyl]­carbamate and ethyl N‐[2‐(hydroxy­acetyl)‐4‐methyl­phenyl]­carbamate

In ethyl N‐[2‐(hydroxy­acetyl)phenyl]carbamate, C₁₁H₁₃NO₄, all of the non‐H atoms lie on a mirror plane in the space group Pnma; the mol­ecules are linked into simple chains by a single C—H⋯O hydrogen bond. The mol­ecules of ethyl N‐[2‐(hydroxy­acetyl)‐4‐iodo­phenyl]carbamate, C₁₁H₁₂INO₄, are linked into sheets by a combination of O—H⋯I and C—H⋯O hydrogen bonds and a dipolar I⋯O contact. Ethyl N‐­[2‐(hydroxy­acetyl)‐4‐methyl­phenyl]carbamate, C₁₂H₁₅NO₄, crystallizes with Z′ = 2 in the space group P; pairs of mol­ecules are weakly linked by an O—H⋯O hydrogen bond and these aggregates are linked into chains by two independent aromatic π–π stacking inter­actions.     

3,5‐Bis{3‐[4‐(dimethylamino)phenyl]prop‐2‐enylidene}‐1‐methyl‐4‐piperidone and 3,5‐bis[3‐(4‐methoxyphenyl)prop‐2‐enylidene]‐1‐methyl‐4‐piperidone: potential biophotonic materials

The structures of the title compounds, C₂₈H₃₃N₃O, (I), and C₂₆H₂₇NO₃, (II), together with their two‐photon absorption properties and fluorescence activities are reported. Molecules of (II) reside on crystallographic mirror planes containing the piperidone C=O group and N‐methyl H atoms. Because of the conjugation between the donor and acceptor parts, the central heterocycle in both (I) and (II) exhibits a flattened boat conformation, with deviations of the N atom and the opposite C atom from the planar fragment. The dihedral angles between the coplanar heterocyclic atoms and terminal C₆ rings are less than 20° in both (I) and (II). In (I), the N‐methyl group of the ring occupies an equatorial position, but in (II) it is positioned in an axial site. In the crystal structure of (I), weak intermolecular C—H...π(arene) and C—H...O steric contacts link the molecules along the a axis. In the crystal structure of (II), molecules form stacks along the b axis.     

Ethyl 2‐form­amido‐2‐(4‐iodo­benzyl)‐3‐(4‐iodo­phenyl)­propionate and ethyl 2‐(3‐bromo­benzyl)‐3‐(3‐bromo­phenyl)‐2‐form­amidopropionate

The title compounds, C₁₉H₁₉I₂NO₃ and C₁₉H₁₉Br₂NO₃, are derivatives of α‐amino­isobutyric acid with halogen substituents at the para and meta positions, respectively. The ethoxycarbonyl and formamide side chains attached to the C_α atom of the mol­ecule adopt extended and folded conformations, respectively. The crystal structures are stabilized by N—H⃛O, C—H⃛O, C—Br⃛O and C—I⃛O interactions.     

Bis­[4‐(2‐pyridyl­methyl­ene­amino)­phenyl] ether

The title compound, C₂₄H₁₈N₄O, is a bis‐bidentate Schiff base ligand exhibiting pseudo‐C₂ symmetry. The mol­ecule is twisted about the central ether linkage and exhibits an imine E configuration. In the crystal, the mol­ecules are linked by weak intermolecular C—H?N hydrogen bonds.     

1‐[4‐(Methyl­sulfonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole derivatives

Three related compounds containing a pyrazole moiety with vicinal phenyl rings featuring a methyl­sulfonyl substituent are described, namely 3‐methyl‐1‐[4‐(methyl­sulfonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole, C₁₇H₁₆N₂O₂S, ethyl 1‐[4‐(methyl­sul­fonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole‐3‐carboxyl­ate, C₁₉H₁₈N₂O₄S, and 1‐[4‐(methyl­sulfonyl)­phenyl]‐3‐[3‐(morpholino)­phenoxy­methyl]‐5‐phenyl‐1H‐pyrazole, C₂₇H₂₇N₃O₄S. The design of these compounds was based on celecoxib, a selective cyclo­oxy­genase‐2 (COX‐2) inhibitor, in order to study the influence of various substituents on COX‐2 and 5‐lipoxy­genase (5‐LOX) inhibition.     

3‐[4‐(4‐Fluoro­phenyl)­piperazin‐1‐yl­methyl]‐5‐methyl‐1,3‐benzoxazol‐2(3H)‐one and 3‐[4‐(2‐fluoro­phenyl)­piperazin‐1‐yl­methyl]‐5‐methyl‐1,3‐benzoxazol‐2(3H)‐one

The title compounds, both C₁₉H₂₀FN₃O₂, contain essentially planar benzoxazolinone ring systems, within which the C—N bond distances and angles do not differ significantly between the two compounds. In both cases, the piperazine ring adopts an almost perfect chair conformation and the benzoxazo­l­inone ring system lies nearly perpendicular to it. The structures contain intermolecular C—H⋯O contacts, and the interactions between the benzoxazolinone and fluoro­phenyl­piperazine portions of the mol­ecules are segregated.     

N‐[1‐(Penta­fluoro­phenyl)­ethyl]­acetamide

The title compound, C₁₀H₈F₅NO, crystallizes as a racemate with four symmetry‐independent mol­ecules in the asymmetric unit. The four mol­ecules form two hydrogen‐bonded pairs. Each pair is a building unit of an independent C(4) chain propagating parallel to the ab plane.     

Two new polymorphs of di­phenyl(4‐pyridyl)­methyl methacryl­ate

The title compound (D4PyMA), C₂₂H₁₉NO₂, exhibits polymorphism after crystallization by slow evaporation from a binary mixture of chloro­form and hexane. Long needle‐like crystals have an orthorhombic structure (space group Fdd2), with one mol­ecule in the asymmetric unit, while small tablet‐like crystals exhibit a monoclinic crystal structure (space group P2₁/n), in which two independent but chemically identical mol­ecules comprise the asymmetric unit. The bond lengths and angles are normal, while the torsion angles around the –C—O– bond linking the di­phenyl(4‐pyridyl)methyl and methacryl­ate groups show the flexibility of the mol­ecule by way of packing effects. The two polymorphs both contain weak C—H⋯π and C—H⋯O/N contacts but have different conformations.     

(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).     

Tri­benzyl{η5‐[2‐(p‐tolyl)­prop‐2‐yl]­cyclo­penta­dienyl}­zirconium

The title compound, [Zr(C₇H₇)₃(C₁₅H₁₇)], (I), crystallizes from light petroleum with two independent mol­ecules in the asymmetric unit. Whereas in the parent mol­ecule, Zr(η⁵‐C₅H₅)(CH₂Ph)₃, all three Zr—CH₂Ph angles are equal, in (I), they differ significantly. In spite of their different environments, both independent mol­ecules in (I) exhibit a small, an expected, and a large Zr—CH₂Ph angle. The angles are similar to those of the closely related tri­benzyl­[η⁵‐(benzyl­di­methyl­silyl)­cyclo­penta­dienyl]­zirconium complex. The smallest Zr—CH₂Ph angle and the consequently relatively short Zr?C_ipso distance are indicative of η²‐bonding of the benzyl group.     

Polymorphism and solvolysis of 2‐cyano‐3‐[4‐(N,N‐diethyl­amino)­phenyl]­prop‐2‐ene­thio­amide

Two new polymorph forms, (Ia) and (Ib), of the title compound, C₁₄H₁₇N₃S, and its solvate with aceto­nitrile, C₁₄H₁₇N₃S·0.25C₂H₃N, (Ic), have been investigated. Crystals of the two polymorphs were grown from different solvents, viz. ethanol and N,N‐di­methyl­form­amide, respectively. The polymorphs have different orientations of the thio­amide group relative to the CN substituent, with s‐cis and s‐trans geometry of the C=C—C=S diene fragment, respectively. Compound (Ic) contains two independent mol­ecules, A and B, with s‐cis geometry, and the solvate mol­ecule lies on a twofold axis. The core of each mol­ecule is slightly non‐planar; the dihedral angles between the conjugated C=C—CN linkage and the phenyl ring, and between this linkage and the thio­amide group are 13.4 (2) and 12.0 (2)° in (Ia), 14.0 (2) and 18.2 (2)° in (Ib), 2.3 (3) and 12.7 (4)° in molecule A of (Ic), and 23.2 (3) and 8.1 (4)° in molecule B of (Ic). As a result of strong conjugation between donor and acceptor parts, the substituted phenyl rings have noticeable quinoid character. In (Ib), there exists a very strong intramolecular steric interaction (H⋯H = 1.95 Å) between the bridging and thio­amide parts of the mol­ecule, which makes such a form less stable. In the crystal structure of (Ia), intermolecular N—H⋯N and N—H⋯S hydrogen bonds link mol­ecules into infinite tapes along the [10] direction. In (Ib), such intermolecular hydrogen bonds link mol­ecules into infinite (101) planes. In (Ic), intermolecular N—H⋯N hydrogen bonds link mol­ecules A and B into dimers, which are connected via N—H⋯S hydrogen bonds and form infinite chains along the c direction.     

The E and Z isomers of 3‐(benzoxazol‐2‐yl)­prop‐2‐enoic acid

The carboxyl­ic acid group and the double bond are coplanar in (E)‐3‐(benzoxazol‐2‐yl)­prop‐2‐enoic acid, C₁₀H₇NO₃, whereas in isomeric (Z)‐3‐(benzoxazol‐2‐yl)­prop‐2‐enoic acid, also C₁₀H₇NO₃, they are almost orthogonal. In both isomers, a strong O—H⋯N hydrogen bond, with the carboxyl­ic acid group as a donor and the pyridine‐like N atom as an acceptor, and weak C—H⋯O interactions contribute to the observed supramolecular structures, which are completed by π–π stacking interactions between oxazole and benzenoid rings.     

(E)‐4‐(4‐Bromo­phenyl­diazen­yl)‐2,6‐dimethyl­phenyl acrylate and (E)‐2,6‐dimethyl‐4‐(4‐methyl­phenyl­diazen­yl)­phenyl acrylate

The crystal structures of the title compounds, C₁₇H₁₅BrN₂O₂, (I), and C₁₈H₁₈N₂O₂, (II), determined at room temperature, have a trans configuration with respect to the diazene linkage, as found for other azo (diazene) derivatives. The aromatic mean planes are nearly coplanar, with a dihedral angle between these planes of 8.31 (2)° for (I) and 3.74 (2)° for (II). In both complexes, the mean plane of the ester group is nearly perpendicular to the aromatic ring planes. In both compounds, the crystal packing involves only π–π and π–ring inter­actions, which combine to stabilize the extended structure.     

1‐(2‐{4‐[6‐Hydro­xy‐2‐(4‐hydroxy­phenyl)­benzo­[b]­thiol‐3‐yl­carbonyl]­phenoxy}ethyl)­piperidinium chloride

The title compound, raloxifene hydro­chloride, C₂₈H₂₈NO₄S⁺·Cl^?, belongs to the benzo­thio­phene class of antiosteoporotic drugs. In the molecular cation, the 2‐phenol ring sustains a dihedral angle of 45.3 (1)° relative to the benzo­[b]­thio­phene system. The benzo­[b]­thio­phene and phenyl ring planes are twisted with respect to the carbonyl plane, with the smallest twist component occurring between the phenyl and carbonyl planes. The N atom bears the positive charge in the molecular cation and the piperidine ring adopts an almost perfect chair conformation. The Cl^? anion is involved in the formation of N—H?Cl and O—H?Cl intermolecular hydrogen bonds, which lead to the formation of a layer of molecular cations.     

Two rhod­amine derivatives: 9‐[2‐(ethoxycarbonyl)phenyl]‐3,6‐bis(ethyl­amino)‐2,7‐di­methyl­xanthyl­ium chloride monohydrate and 3,6‐di­amino‐9‐[2‐(methoxy­carbonyl)­phenyl]xanthyl­ium chloride trihydrate

The title compounds, C₂₈H₃₁N₂O₃⁺·Cl^?·H₂O (common name rhod­amine‐6g), (I), and C₂₁H₁₇N₂O₃⁺·Cl^?·3H₂O (common name rhod­amine‐123), (II), both have planar xanthene skeletons with a formal +1 charge on the amino N atoms delocalized through the π‐electron system so that the N—Csp² bond distances indicate significant double‐bond character. The substituted planar phenyl groups make angles of 63.29 (8) and 87.96 (11)° with the xanthene planes in (I) and (II), respectively. In both mol­ecules, the carbonyl bond vectors point toward the xanthene rings. The ethyl­amine groups in (I) are oriented similarly with their CH₂–CH₃ bond vectors pointing nearly perpendicular to the xanthene plane. The chloride ions and water mol­ecules are disordered in both structures. In (I), the chloride ion and water mol­ecule are disordered between two sites. One water and chloride alternately occupy the same site with occupancy factors of 0.5. The other 0.5‐chloride and 0.5‐water occupy two distinct positions separated by 0.747 (8) Å. In (II), the chloride ion is disordered between three sites and one of the waters is disordered about two other sites. Both crystal structures are stabilized by hydrogen bonds involving the chloride ions, amino groups and water mol­ecules, as well as by π–π stacking between xanthene planes.     

Similarities and differences between bis[2‐(bromomethyl)phenyl] diselenide,bis[2‐(chloromethyl)phenyl] diselenide and bis[2‐(hydroxymethyl)phenyl] diselenide

The title compounds, C₁₄H₁₂Br₂Se₂, (I), C₁₄H₁₂Cl₂Se₂, (II), and C₁₄H₁₄O₂Se₂, (III), feature a diselenide bridge between two o‐benzyl bromide [in (I)], two o‐benzyl chloride [in (II)] or two o‐benzyl alcohol units [in (III)]. In the molecular structure of (I) and in both independent molecules of (II), close contacts are observed between the halogen centres and the diselenide unit. In the case of modification (IIIa), strong hydrogen bonds between the –OH groups dominate, whereas the molecular structures of modification (IIIb) and bis{2‐[(dimethylamino)methyl]phenyl} diselenide, C₁₈H₂₄N₂Se₂, (IV), are comparable with those of (I) and (II). A correlation between the strength of the contacts and the angle between the benzene planes and the Se—Se units is found.     

The solid‐state emmissive chalcone (2E)‐1‐(5‐chlorothiophen‐2‐yl)‐3‐[4‐(dimethylamino)phenyl]prop‐2‐en‐1‐one

Orange rectangular blocks suitable for X‐ray diffraction analysis were obtained for the previously reported [Ahmad & Bano (2011). Int. J. ChemTech Res. 3 , 1470–1478] title chalcone, C₁₅H₁₄ClNOS. This solid‐emissive chalcone exhibits a planar structure and the bond parameters are compared with related compounds already described in the literature. The determination of the structure of this chalcone is quite relevant because it will play an important role in theoretical calculations to investigate potential two‐photon absorption processes and could also be useful for studying the interaction of such compounds with a biological target.     

1‐(2‐Hydro­xy‐4‐methoxy­phenyl)‐3‐(2,3,4‐tri­methoxy­phenyl)­prop‐2‐en‐1‐one

The title compound, C₁₉H₂₀O₆, crystallizes in the centrosymmetric space group P2₁/c with one mol­ecule in the asymmetric unit. The mol­ecule is approximately planar and the dihedral angle between the phenyl rings is 11.0 (1)°. The H atoms of the central propenone group are trans. There is an intramolecular O—H⃛O hydrogen bond and the mol­ecules are crosslinked by four intermolecular C—H⃛O hydrogen bonds, producing a three‐dimensional network.     

2‐[N‐(X‐Chlorophenyl)carbamoyl]benzenesulfonamide (with X = 2 and 4)

The structures of 2‐[N‐(2‐chlorophenyl)carbamoyl]benzenesulfonamide and 2‐[N‐(4‐chlorophenyl)carbamoyl]benzenesulfonamide, both C₁₃H₁₁ClN₂O₃S, are stabilized by extensive intra‐ and intermolecular hydrogen bonds. In both structures, sulfonamide groups are hydrogen bonded via the N and O atoms and form chains of molecules. The carbamoyl groups are also hydrogen bonded, involving the O and N atoms, further strengthening the polymeric chains running along the c and a axes in the 2‐ and 4‐chloro derivatives, respectively. Carbamoylsulfonamide derivatives are novel compounds with a great potential for medicinal applications.