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.     

Benzoin 4‐ethyl­thio­semicarbazone

In the title compound, 2‐hydr­oxy‐1,2‐diphenyl­ethanone 4‐ethyl­thio­semicarbazone, C₁₇H₁₉N₃OS, the thio­semi­carbazone moiety is planar and has an E configuration. The planar phenyl rings make dihedral angles of 82.34 (8) and 8.07 (17)° with the plane of the thio­semicarbazone moiety. The crystal structure contains two intra­molecular (N—H⋯O and N—H⋯N) and one inter­molecular inter­action (O—H⋯S), as well as two C—H⋯π(benzene) inter­actions. Mol­ecules are stacked in columns running along the a axis. Mol­ecules in each column are connected to each other by means of linear O—H⋯S hydrogen bonds and C—H⋯π inter­actions. In addition, there are also C—H⋯π(benzene) inter­actions between the columns.     

(Z)‐3‐(1‐Methyl‐1H‐indol‐3‐yl)‐2‐(thio­phen‐3‐yl)­acrylo­nitrile

The title compound, C₁₆H₁₂N₂S, has been synthesized by base‐catalyzed condensation of 1‐methyl­indole‐3‐carbox­aldehyde with thio­phene‐3‐aceto­nitrile. The product assumes an approx­imately planar Z configuration. The mol­ecule has a thienyl‐ring flip disorder.     

catena‐Poly[[{4‐bromo‐2‐[2‐(di­methyl­amino)­ethyl­imino­meth­yl]­phenolato}­copper(II)]‐μ‐thio­cyanato]

The title complex, [Cu(C₁₁H₁₄BrN₂O)(NCS)]_n, is an inter­esting thio­cyanate‐bridged polynuclear copper(II) compound, which crystallizes with two independent mol­ecules in the asymmetric unit. Each Cu^II atom is five‐coordinate in a square‐pyramidal configuration, with one O and two N atoms of one Schiff base ligand and one terminal N atom of a bridging thio­cyanate ligand defining the basal plane, and one terminal S atom of another bridging thio­cyanate ligand occupying the apical position. The {4‐bromo‐2‐[2‐(dimethyl­amino)ethyl­imino­meth­yl]phenolato}copper(II) units are linked by the bridging thio­cyanate ligands, forming polymeric chains running along the a axis. There are weak inter­molecular C—H⋯O and C—H⋯S hydrogen bonds between the chains in the crystal structure.     

2,5‐Bis(methylthio)‐1,4‐benzo­quinone and 2‐methyl‐3‐(methylsulfonyl)benzo[b]thiophene

The structure of 2,5‐bis­(methyl­thio)‐1,4‐benzo­quinone, C₈H₈O₂S₂, is composed of an essentially planar centrosymmetric benzo­quinone substituted with two methyl­thio groups. The important bond distances are S—Csp³ 1.788 (2) and S—Csp² 1.724 (2) Å, and the two Csp²—Csp² distances are 1.447 (3) and 1.504 (3) Å, which differ significantly. There are short S?S interactions of 3.430 (1) Å and Csp²—H?O‐type contacts forming a dimeric motif with graph set R₂²(8). The structure of 2‐methyl‐3‐(methyl­sulfonyl)­benzo­[b]­thio­phene, C₁₀H₁₀O₂S₂, is composed of an essentially planar benzo­thio­phene moiety substituted with methyl and methyl­sulfonyl groups. The mean values of the important bond distances are endocyclic S—Csp² 1.734 (3), S=O 1.434 (4) and C—C_aromatic 1.389 (10) Å. The exocyclic S—Csp² and S—Csp³ distances are 1.759 (4) and 1.763 (5) Å, respectively.     

[Di‐2‐pyridyl ketone N4,N4‐(butane‐1,4‐di­yl)­thio­semi­carbazonato‐κ3N,N′,S]­di­oxo­vanadium(V)

The V^V atom in the title complex, [V(C₁₆H₁₆N₅S)O₂], is five‐coordinate in a highly distorted square‐pyramidal geometry, with the pyridyl N, the azomethine N and the thiol­ate S atoms of the di‐2‐pyridyl ketone N⁴,N⁴‐(butane‐1,4‐di­yl)­thio­semi­carbazone ligand and one oxo ligand occupying the basal coordination positions, while the second oxo ligand occupies the apical position. The mol­ecules are inter­connected by weak inter­molecular inter­actions, mainly of the C—H⋯O type, involving the oxo atoms.     

Tetrakis(3,4‐ethylenedioxy‐2‐thienyl)silane carbon tetrachloride solvate

The structure of tetrakis(3,4‐ethyl­ene­dioxy‐2‐thienyl)­silane carbon tetrachloride solvate, Si(C₆H₅O₂S)₄·CCl₄, has been determined in the noncentrosymmetric space group I. The Si and C atoms of the CCl₄ are located on the fourfold inversion axes. The Si atom has a tetrahedral geometry. The thio­phene ring in the 3,4‐ethyl­ene­dioxy­thio­phene group is nearly planar to within 0.005 Å, and the ethyl­ene­dioxy moiety is in a half‐chair conformation.     

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 biologically active thio­phene‐3‐carbox­amide derivatives

The compounds 2‐{[(E)‐(4‐methoxy­phenyl)­methyl­ene]­amino}‐N‐(3‐methyl­phenyl)‐4,5,6,7‐tetra­hydro‐1‐benzo­thio­ph­ene‐3‐carbox­amide, C₂₄H₂₄N₂O₂S, (I), and N‐(4‐meth­yl­phenyl)‐2‐{[(E)‐(4‐methyl­phenyl)­methyl­ene]­amino}‐4,5,6,7‐tetra­hydro‐1‐benzo­thio­phene‐3‐carbox­amide, C₂₄H₂₄N₂OS, (II), show antibacterial and antifungal activities. The m‐toluidine ring in (I) and the p‐toluidine ring in (II) are coplanar with their respective thio­phene rings. In (I), an intermolecular C—H⋯O hydrogen bond is present, whereas (II) does not exhibit any significant intermolecular interactions. However, in both compounds, an intramolecular N—H⋯N hydrogen bond forms a pseudo‐six‐membered ring, thus locking the molecular conformation and eliminating conformational flexibility.     

A novel thio­cyanate‐bridged dinuclear cadmium(II) complex: di‐μ‐thio­cyanato‐bis­((methanol){4‐nitro‐2‐[2‐(dimethyl­amino)ethyl­imino­meth­yl]phenolato}cadmium(II))

The title complex, [Cd₂(C₁₁H₁₄N₃O₃)₂(NCS)₂(CH₄O)₂], is an inter­esting thio­cyanate‐bridged dinuclear cadmium(II) compound. It is located on a crystallographic inversion center. The Cd^II atom is six‐coordinated in an octa­hedral configuration by one O and two N atoms of one Schiff base ligand and by the terminal N atom of a bridging thio­cyanate ligand, defining the basal plane, and by the terminal S atom of another bridging thio­cyanate ligand and by the O atom of a coordi­nated methanol mol­ecule, occupying the axial positions. The mol­ecules are linked through inter­molecular O—H⋯O hydrogen bonds, forming chains running along the b axis.     

3,3,4,4,5,5‐Hexa­fluoro‐1,2‐bis(5‐hydroxy­methyl‐2‐methyl‐3‐thienyl)­cyclo­pent‐1‐ene

The title compound, C₁₇H₁₄F₆O₂S₂, a photochromic di­aryl­ethene, is one of the most promising materials for optical memories and other optoelectronic devices. The hexafluoro­cyclopentene group and the two thio­phene rings are all planar, and the dihedral angles between the cyclo­pentene ring and the adjacent thio­phene rings are 46.4 (1) and 49.5 (1)°.     

(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).     

C—H⋯O,C—H⋯π and π–π inter­actions in three benzofuran‐2‐yl ketone derivatives

The mol­ecules of 2‐benzoyl‐1‐benzofuran, C₁₅H₁₀O₂, (I), inter­act through double C—H⋯O hydrogen bonds, forming dimers that are further linked by C—H⋯O, C—H⋯π and π–π inter­actions, resulting in a three‐dimensional supramolecular network. The dihedral angle between the benzo­yl and benzofuran fragments in (I) is 46.15 (3)°. The mol­ecules of bis­(5‐bromo‐1‐benzofuran‐2‐yl) ketone, C₁₇H₈Br₂O₃, (II), exhibit C₂ symmetry, with the carbon­yl group (C=O) lying along the twofold rotation axis, and are linked by a combination of C—H⋯O and C—H⋯π inter­actions and Br⋯Br contacts to form sheets. The stability of the mol­ecular packing in 3‐mesit­yl‐3‐methyl­cyclo­but­yl 3‐methyl­naphtho[1,2‐b]furan‐2‐yl ketone, C₂₈H₂₈O₂, (III), arises from C—H⋯π and π–π stacking inter­actions. The fused naphthofuran moiety in (III) is essentially planar and makes a dihedral angle of 81.61 (3)° with the mean plane of the trimethyl­benzene ring.     

Two biologically active thio­phene‐3‐carbox­amide derivatives

The two title compounds, 2‐({(1Z)‐[4‐(di­methyl­amino)phenyl]methylene}amino)‐4,5‐dimethyl‐N‐(2‐methylphenyl)thiophene‐3‐carboxamide, C₂₃H₂₅N₃OS, (I), and 2‐({(1E)‐[4‐(dimethylamino)phenyl]methylene}amino)‐N‐(4‐methylphenyl)‐4,5,6,7‐tetrahydro‐1‐benzothiophene‐3‐carboxamide,C₂₅H₂₇N₃OS, (II), show antibacterial and antifungal activities. The asymmetric unit of (II) contains two crystallographically independent mol­ecules. The o‐toluidine ring in (I) lies gauche with respect to the thio­phene ring. In (II), the p‐toluidine ring is coplanar with the thio­phene ring in one mol­ecule, but is tilted from it in the other mol­ecule. Neither structure exhibits any significant intermolecular interactions, but in both, an intramolecular N—H⋯N hydrogen bond forms a pseudo‐six‐membered ring, thus locking the molecular conformation and removing conformational flexibility.     

catena‐Poly[[aqua­(3,4,7,8‐tetra­methyl‐1,10‐phenanthroline‐κ2N,N′)cadmium(II)]‐μ3‐thio­sulfato‐κ3S:S:O]

The title compound, [Cd(S₂O₃)(C₁₆H₁₆N₂)(H₂O)]_n, presents a polymeric one‐dimensional structure running along the P2₁/c glide direction, with elementary units defined by six‐coordinate Cd^II atoms bonded to three symmetry‐related thio­sulfate groups, a bidentate tetra­methyl­phenanthroline ligand and one aqua ligand. The bridging thio­sulfates bind metal centers through two different sequences, viz. Cd—S—Cd′ and Cd′—S′—S′—O′—Cd, defining a closed six‐membered ring. Individual chains are held together viaπ–π inter­actions to generate two‐dimensional networks parallel to the (100) plane. These, in turn, are connected by much weaker van der Waals inter­actions.     

A novel potent non‐nucleoside reverse transcriptase inhibitor acyl­thio­carbamate derivative with extensive intra­molecular π–π inter­actions

In the crystal structure of the novel acyl­thio­carbamate derivative O‐[2‐(1,3‐dioxo‐2,3‐dihydro‐1H‐isoindol‐2‐yl)­ethyl] N‐(4‐methyl­phenyl)‐N‐(3‐nitro­benzoyl)thio­carbamate, C₂₅H₁₉N₃O₆S, intra‐ and inter­molecular π–π inter­actions occur between the phthalimide and N‐benzoyl moieties. The partial atomic charges, calculated by ab initio methods, are consistent with the observed structure.     

N‐Benzyl‐2,5‐bis(2‐thienyl)­pyrrole

The solid‐state structure of the title compound, C₁₉H₁₅NS₂, is unusual among substituted thiophene/pyrrole derivatives in that the molecular packing is dominated by π–π interactions between the benzyl substituents. This may be due to the large torsion angles observed between adjacent heterocycles. Torsion angles between adjacent rings in poly­pyrrole and poly­thio­phene conducting polymers are related to conjugation length and the conductivity properties of the polymer materials. The title compound crystallizes in space group P2₁/c with two mol­ecules in the asymmetric unit, both of which exhibit disorder in one of their thio­phene rings.     

2‐Acetamido‐N‐benz­yl‐2‐(methoxy­amino)acetamides: functionalized amino acid anticonvulsants

In the crystal structure of 2‐acetamido‐N‐benz­yl‐2‐(methoxy­amino)acetamide (3L), C₁₂H₁₇N₃O₃, the 2‐acetyl­amino­acetamide moiety has a linearly extended conformation, with an inter­planar angle between the two amide groups of 157.3 (1)°. In 2‐acetamido‐N‐benz­yl‐2‐[meth­oxy(meth­yl)­amino]­acetamide (3N), C₁₃H₁₉N₃O₃, the planes of the two amide groups inter­sect at an angle of 126.4 (4)°, resulting in a chain that is slightly more bent. The replacement of the methoxy­amino H atom of 3L with a methyl group to form 3N and concomitant loss of hydrogen bonding results in some positional/thermal disorder in the meth­oxy­(methyl)­amino group. In both structures, in addition to classical N—H⋯O hydrogen bonds, there are also weak non‐standard C—H⋯O hydrogen bonds. The hydrogen bonds and packing inter­actions result in planar hydro­philic and hydro­phobic areas perpendicular to the c axis in 3L and parallel to the ab plane in the N‐meth­yl derivative. Stereochemical comparisons with phenytoin have identified two O atoms and a phenyl group as mol­ecular features likely to be responsible for the anticon­vulsant activities of these compounds.     

2‐[(E)‐(4‐Chloro­phenyl)­methyl­ene­amino]‐N‐(X‐methyl­phenyl)‐4,5,6,7‐tetra­hydro‐1‐benzo­thio­phene‐3‐carbox­amide,where X = 2 and 3

The title compounds, both C₂₃H₂₁ClN₂OS, are isomeric, with (I) and (II) being the N‐3‐methyl­phenyl and N‐2‐methyl­phenyl derivatives, respectively. The dihedral angle between the 4‐chloro­phenyl group and the thio­phene ring in (II) [38.1 (1)°] is larger than that in (I) [7.1 (1)°], indicating steric repulsion between the chloro­phenyl and o‐toluidine groups in (II). In both compounds, an intramolecular N—H⋯N hydrogen bond forms a pseudo‐six‐membered ring, thus locking the molecular conformation. In the crystal structures, mol­ecules are connected via N—H⋯O hydrogen bonds, forming chains along the b axis in (I) and along the c axis in (II). Intermolecular C—H⋯O/S and π–π interactions are also observed in (II), but not in (I).     

Two‐dimensional square‐grid frameworks formed by self‐associating copper(II) complexes with 1‐(3‐pyridyl)‐ and 1‐(4‐pyridyl)‐substituted butane‐1,3‐diones

In bis­[1‐(3‐pyridyl)butane‐1,3‐dionato]copper(II) (the Cu atom occupies a centre of inversion), [Cu(C₉H₈NO₂)₂], (I), and bis­[1‐(4‐pyridyl)butane‐1,3‐dionato]copper(II) methanol solvate, [Cu(C₉H₈NO₂)₂]·CH₃OH, (II), the O,O′‐chelating diketonate ligands support square‐planar coordination of the metal ions [Cu—O = 1.948 (1)–1.965 (1) Å]. Weaker Cu⋯N inter­actions [2.405 (2)–2.499 (2) Å], at both axial sides, occur between symmetry‐related bis­(1‐pyridylbutane‐1,3‐dion­ato)copper(II) mol­ecules. This causes their self‐organization into two‐dimensional square‐grid frameworks, with uniform [6.48 Å for (I)] or alternating [4.72 and 6.66 Å for (II)] inter­layer separations. Guest methanol mol­ecules in (II) reside between the distal layers and form weak hydrogen bonds to coordinated O atoms [O⋯O = 3.018 (4) Å].