3,4‐Bis[(4‐methoxy­benzo­yl)methyl­sulfanyl]thio­phene

A new type of thio­phene derivative having α‐thio­ketone groups at the 3‐ and 4‐positions, viz. the title compound, C₂₂H₂₀O₄S₃, has been prepared and studied by NMR spectroscopy and single‐crystal X‐ray diffraction techniques. The mol­ecule is nearly planar, the dihedral angles between the essentially planar thio­phene and benzene rings being 9.4 (1) and 10.6 (1)°. One of the thio­ketone O atoms is involved in an inter­molecular C—H⋯O hydrogen‐bonding inter­action.     

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.     

{3,3′‐[2,2′‐(Ethylenedioxy)dibenzyl­idene]bis(S‐methyl dithiocarbazate)}­nickel(II)

The tetradentate N₂S₂ Schiff base ligand 3,3′‐[2,2′‐(ethyl­ene­di­oxy)di­benzyl­idene]­bis­(S‐methyl di­thio­car­ba­zate) (H₂L), prepared by the condensation of S‐methyl di­thio­carb­aza­te with 1,4‐bis(2‐formyl­phenyl)‐1,4‐dioxa­butane in a 1:2 molar ratio, reacts with nickel acetate to form the title neutral metal complex, [Ni(C₂₀H₂₀N₄O₂S₄)]. The X‐ray structure of the complex shows a distorted square‐planar geometry around the Ni atom. The monomeric units are weakly associated into dimers via a long Ni?S interaction [3.569 (1) Å]. These dimeric units are then linked by C—H?S intermolecular contacts to form a polymeric chain along the a axis.     

Hydrogen‐bonded 1,2‐bis(4‐pyridyl)ethylene and maleic acid

The title compound (systematic name: 4,4′‐ethyl­ene­dipyridinium dimaleate), C₁₂H₁₂N₂²⁺·2C₄H₃O₄^?, is a 1:2 adduct of 1,2‐bis(4‐pyridyl)­ethyl­ene (BPE) and maleic acid (MA). The interaction between the two components in the molecular complex is due to intermolecular hydrogen bonding via an N⁺—H?O^? hydrogen bond.     

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.     

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.     

Dorzolamide hydro­chloride: an anti­glaucoma agent

Dorzolamide hydro­chloride [systematic name: (4S)‐trans‐4‐ethyl­ammonio‐6‐methyl‐5,6‐dihydro‐4H‐thieno[2,3‐b]thio­pyran‐2‐sulfonamide 7,7‐dioxide chloride], C₁₀H₁₇N₂O₄S₂⁺·Cl⁻, belongs to a class of drugs called carbonic anhydrase inhibitors. The ethyl­ammonio side chain is in an extended conformation and is protonated at the N atom, which is hydrogen bonded to the Cl⁻ anion. The dihedral angle between the planes of the thio­phene ring and the sulfonamide group is 80.7 (1)°. A comparison is made with the dorzolamide bound in human carbonic anhydrase in the solid state. Hydrogen bonding is mediated by Cl⁻ anions, resulting in indirect connectivity between the mol­ecules.     

(1R,8R,11R)‐3,3,11‐Tri­methyl‐6,6‐ethyl­ene­dioxy­bi­cyclo­[6.3.0]­undecan‐2‐one and (1R,2R,8R,11R)‐3,3,11‐tri­methyl‐6,6‐ethylenedioxybicyclo[6.3.0]undecan‐2‐ol

The reduction of (1R,8R,11R)‐3,3,11‐tri­methyl‐6,6‐ethyl­ene­dioxy­bi­cyclo­[6.3.0]­undecan‐2‐one, C₁₆H₂₆O₃, (I), gave exclusively an alcohol, C₁₆H₂₈O₃, (II). The stereochemistry of the hydroxyl group in (II) was shown as R. The conformation around the eight‐membered carbocycle in (I) differs markedly from that in (II).     

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.     

(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).     

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)°.     

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.     

[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.     

Two strained hexahelicenophanes

The crystal structures of the [6]­helicenes 4,13‐(1,10‐deca­methyl­ene­dioxy)­hexahelicene, C₃₆H₃₄O₂, (I), and 4,13‐(1,8‐octa­methyl­ene­dioxy)­hexahelicene, C₃₄H₃₀O₂, (II), show strong steric interactions between the terminal benzene rings and the poly­methyl­ene­dioxy chains. The shortest ring A and F distances amount to 2.941 (3) and 2.902 (3) Å, respectively. The increased steric energy of the ground state is responsible for a significantly lower racemization barrier of (I) and (II) in comparison to the unsubstituted [6]­helicene.     

4‐Methyl‐2‐[N‐(3,4‐methyl­ene­dioxy­benzyl­idene)hydrazino]­thia­zole and its reduction product, 4‐methyl‐2‐[N‐(3,4‐methyl­ene­dioxybenzyl­idene)hydrazono]‐4,5‐di­hydro­thia­zole

The crystal structures of 4‐methyl‐2‐[N‐(3,4‐methyl­ene­dioxybenzyl­idene)hydrazino]­thia­zole, C₁₂H₁₁N₃O₂S, and its reduction product 4‐methyl‐2‐[N‐(3,4‐methyl­ene­dioxybenzyl­idene)hydrazono]‐4,5‐di­hydro­thia­zole, C₁₂H₁₃N₃O₂S, have been determined and compared. In the reduction product, the tautomer observed bears an H atom on the exocyclic N atom. Both compounds form hydrogen‐bonded dimers over centers of inversion.     

trans‐Bis­[N‐(2‐hydroxy­ethyl)­ethyl­ene­di­amine‐κ2N,N′]­bis­(iso­thio­cyanato‐κN)­nickel(II)

The crystal structure of the title compound, [Ni(NCS)₂(C₄H₁₂N₂O)₂], has two crystallographically independent half‐mol­ecules in the asymmetric unit, with each Ni atom residing on a centre of symmetry. The two mol­ecules exhibit similar coordination geometry but display differences with regard to other structural features. Each Ni^II centre is octahedrally coordinated by two mutually trans chelating hydroxy­ethyl­ethyl­ene­di­amine ligands and two mutually trans iso­thio­cyanate ions. The two independent mol­ecules form chains through different types of non‐covalent interactions. In the case of one of the mol­ecules, only NCS and free OH groups participate in hydrogen bonding, while in the chain based on the second mol­ecule, the NCS, NH, NH₂ and free OH groups are involved in intermolecular hydrogen bonding. The two chains interact with one another through hydrogen bonding, forming planar sheets. The third packing direction is mediated only by van der Waals interactions.     

{(E)‐ and {(Z)‐2‐[α,β‐bis­(methoxy­carbonyl)­vinyl]­cyclo­pentadien‐1‐yl­idene}tri­phenyl­phospho­rane

The Ramirez yl­ide undergoes electrophilic substitution with di­alkyl acetyl­ene­di­carboxyl­ates, yielding a mixture of the Z and E adducts. The crystal structure analyses of the two adducts formed using di­methyl­acetyl­ene, viz. di­methyl (E)‐ and (Z)‐1‐[2‐(tri­phenyl­phospho­ranyl­idene)­cyclo­pentadien‐1‐yl]­ethyl­ene­di­carboxyl­ate, both C₂₉H₂₅O₄P, explain an unusual chemical shift observed for the vinyl H atom of the Z adduct, which had previously precluded a definitive assignment of the isomers. In addition, the structures explain why only one of the isomers reacts further with acetyl­ene esters to produce azulenes with a rare substitution pattern.     

(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.     

Bis­(ethyl­enedi­amine)copper(II) bis(O,O′‐diethyl di­thio­phosphate)

In the structure of the title compound, [Cu^II­(en)₂][(EtO)₂P(S)S]₂ (en is ethyl­ene­di­amine) or [Cu(C₂H₈N₂)₂](C₄H₁₀O₂PS₂)₂, the Cu atom lies on a center of inversion and is coordinated in a slightly distorted square coordination geometry by four N atoms from two ethyl­enedi­amine mol­ecules. The diethyl di­thio­phosphate moieties, (EtO)₂P(S)S^?, act as counter‐anions.     

A lithium ethyl­ene­diphos­phon­ate containing lithium chains and symmetric hydrogen bonds

In the title compound, catena‐poly[lithium‐μ₃‐ethyl­ene­diphos­phon­ato], [Li(C₂H₇O₆P₂)]_n, the supra­molecular monoclinic (C2/c) structure consists of one‐dimensional lithium chains [Li⋯Li = 2.7036 (8) Å] that are embedded within ethyl­ene­diphosphon­ate anions linked by strong symmetric hydrogen bonds [O⋯O = 2.473 (3) Å]. The Li atoms and the H atom in the symmetric hydrogen bond reside on twofold rotation axes and there is an inversion center at the mid‐point of the C—C bond of the ethylenediphosphonate ligand.