Dibromo[5,10,15,20‐tetrakis(4‐methoxyphenyl)porphyrinato‐κ4N]platinum(IV) chloroform acetonitrile solvate

In the title compound, [PtBr₂(C₄₈H₃₆N₄O₄)]·0.896CHCl₃·0.569CH₃CN, the centrosymmetric metal complex is octahedral, with the porphyrin ring essentially planar and the Br atoms occupying axial positions. The two independent methoxy­phenyl substituents are tilted at angles of 89.0 and 67.0° with respect to the porphyrin plane. The Pt—N distances are 2.035 (4) and 2.036 (4) Å and the Pt—Br distance is 2.4666 (6) Å. Chloro­form and aceto­nitrile solvent mol­ecules, exhibiting substantial disorder, occupy positions between the porphyrin mol­ecules. This is the first crystal and molecular structure of a Pt^IV–porphyrin complex to be reported.     

Interwoven hydrogen‐bonded network assembly and supramolecular isomerism of meso‐5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin as its dimethylformamide solvate

Molecules of the title compound, porphyrin‐5⁴,10⁴,15⁴,20⁴‐tetrabenzoic acid, C₄₈H₃₀N₄O₈, lie on sites of 2/m symmetry in the space group Cmca. The crystals consist of doubly interwoven two‐dimensional supramolecular arrays sustained by multiple (COOH)₂ cyclic dimeric hydrogen bonds, each molecule of the porphyrintetrabenzoic acid coordinating to four neighbouring species. This structure, which encloses substantial spaces occupied by disordered dimethylformamide solvent molecules, represents yet another supramolecular isomer of this porphyrin.     

Hydro­gen‐bond networks in tris(4‐hydroxy­phenyl)­methane and its 1:1 molecular complex with 4,4′‐bi­pyridine

In tris(4‐hydroxy­phenyl)­methane (or 4,4′,4′′‐methane­triyl­tri­phenol), C₁₉H₁₆O₃, mol­ecules are connected by O—H⃛O hydrogen bonds [O⃛O = 2.662 (2) and 2.648 (2) Å] into two‐dimensional square networks that are twofold interpenetrated. In tris(4‐hydroxy­phenyl)­methane–4,4′‐bi­pyridine (1/1), C₁₉H₁₆O₃·C₁₀H₈N₂, trisphenol mol­ecules form rectangular networks via O—H⃛O [O⃛O = 2.694 (3) Å] and C—H⃛O [C⃛O = 3.384 (3) Å] hydrogen bonds. Bi­pyridine mol­ecules hydrogen bonded to phenol moieties [O⃛N = 2.622 (3) and 2.764 (3) Å] fill the voids to complete the structure.     

Methoxy[meso‐5,10,15,20‐tetrakis(2,6‐difluorophenyl)porphyrinato]­iron(III), [Fe(TDFPP)(OCH3)]

The crystal structure of the title compound, [Fe(C₄₄H₂₀F₈N₄)(CH₃O)], has been determined. The Fe atom lies 0.485 (1) Å out of the plane of the four N atoms to which it is coordinated and from the inversion centre at the origin of the unit cell. The methoxy group is axially coordinated to the Fe atom with O—Fe—N angles of 106.3 (2) and 102.4 (2)°, a C—O—Fe angle of 128.3 (5)° and an Fe—O distance of 1.788 (5) Å. Di­fluoro­phenyl rings are tilted from the porphyrin (por) plane with torsion angles of ?68.1 (6) and 77.7 (5)° across the two C_por—­C—C—C_ar systems.     

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.     

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.     

Hydro­gen‐bonded molecular ladders in trans‐1,2‐bis(2‐nitro­anilino)­cyclo­hexane

Crystals of the title compound, C₁₈H₂₀N₄O₄, contain equal numbers of (R,R) and (S,S) mol­ecules, but these are not precise enantiomorphs, neither are they related by crystallographic symmetry; in addition, each mol­ecule exhibits approximate, but not exact, twofold rotational symmetry. There are intramolecular N—H?O hydrogen bonds [N?O 2.609 (4)–2.638 (5) Å; N—H?O 125–132°] and the mol­ecules are linked into molecular ladders by C—H?O hydrogen bonds [C?O 3.306 (6)–3.386 (6) Å; C—H?O 146–160°].     

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.     

(4‐Aminopyridine‐κN1)(phthalocyaninato‐κ4N)zinc(II) tetrahydrofuran disolvate

The title compound, [Zn(C₃₂H₁₆N₈)(C₅H₆N₂)]·2C₄H₈O, consists of one (phthalocyaninato)zinc (ZnPc) unit, a coordinated 4‐aminopyridine (4‐ap) molecule and two tetrahydrofuran (THF) solvent molecules. The central Zn atom is (4+1)‐coordinated by four isoindole N atoms of the Pc core and by the pyridine N atom of 4‐aminopyridine. The Zn atom is displaced by 0.4464 (8) Å from the isoindole N₄ plane towards the pyridine N atom. The crystal structure is stabilized by intermolecular amine–phthalocyaninate N—H...N hydrogen bonds and π–π interactions between the aggregated Pc rings, which form molecular layers, and by weak van der Waals interactions between the layers. As well as hindering the aggregation of ZnPc molecules by occupying an axial position, the amino group will add new interactions which will favor applications of ZnPc, for example, as a sensitizer of photodynamic therapy.     

Bis­[1,3‐bis(2‐methyl­tetrazol‐5‐yl‐κN4)­triazenido‐κN2]­nickel(II)

The title compound, [Ni(BMTT)₂], where BMTT is 1,3‐bis(2‐methyl­tetrazol‐5‐yl)­triazenide (C₄H₆N₁₁), presents a molecular complex with tridentate ligands. The tridentate mode of the ligand is realised through the central N atom of the triazene group and two N atoms of the two tetrazole rings. The [Ni(BMTT)₂] mol­ecule is the meridional isomer, with crystallographic symmetry in space group P4₂/n. The nickel centre has a distorted octahedral environment, with two axial Ni—N bonds of 2.041 (2) Å and four equatorial Ni—N bonds of 2.0739 (14) Å. The mol­ecules are linked together by van der Waals interactions only.     

Synthesis of meso‐tetrakis(4‐chlorocoumarin‐3‐yl)porphyrins

meso‐Tetrakis(4‐chlorocoumarin‐3‐yl)porphyrins were prepared by condensation of corresponding 4‐chlorocoumarin‐3‐carboxaldehydes and pyrrole in the presence of trifluoro acetic acid (TFA) in dichloromethane followed by oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ). These porphyrins exhibited the atropisomerism due to ortho substituent of meso aryl groups. The atropisomers of meso‐tetrakis(4‐chloro‐6‐methylcoumarin‐3‐yl)porphyrin were separated and identified by ¹H‐nmr spectra. Zinc complexes of these porphyrins were synthesized and characterized by ms, ¹H nmr, ir and uv‐vis spectra.     

Hydro­gen‐bonded assemblages in 2,6‐bis­(hydroxy­methyl)‐4‐R‐phenol,with R = methyl,methoxy, phenoxy and 1‐(4‐methoxy­phenyl)‐1‐methyl­ethyl

Four derivatives of 2,6‐bis­(hydroxy­methyl)­phenol, with various para substituents, have been investigated; these are 2,6‐bis­(hydroxy­methyl)‐4‐methyl­phenol, C₉H₁₂O₃, (I), 2,6‐bis­(hydroxy­methyl)‐4‐methoxy­phenol, C₉H₁₂O₄, (II), 2,6‐bis­(hydroxy­methyl)‐4‐phenoxy­phenol, C₁₄H₁₄O₄, (III), and 2,6‐bis­(hydroxy­methyl)‐4‐[1‐(4‐methoxy­phenyl)‐1‐methyl­ethyl]­phenol, C₁₈H₂₂O₄, (IV). All four structures display hydrogen‐bonding networks resulting in sheets, with possible weak inter‐sheet π–π interactions in one case. In all the structures but one, the mol­ecules form centrosymmetric dimeric subunits held together by two hydrogen bonds between the hydroxy­methyl groups and, in two cases, by probable π–π interactions.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and dimeric 1:1 adducts with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐­diamino­ethane

In ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–4,4′‐ethyl­enedi­pyridine (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₂N₂, there is an intra­molecular O—H?O hydrogen bond in the ferrocenediol component and a single O—H?N hydrogen bond linking the two components into a finite monomeric adduct. Ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–ethyl­enedi­amine (1/1), [Fe(C₁₈H₁₅O)₂]·C₂H₈N₂, crystallizes with Z′ = 2 in space group P, and there are two independent four‐component aggregates in the structure, both of which are centrosymmetric. In the first type of aggregate, the molecular components are linked by O—H?N and N—H?O hydrogen bonds, in which both di­amine N atoms participate; in the second type of aggregate, the di­amine component is disordered over two sets of sites, but only one N atom is involved in the hydrogen bonding.     

Hydro­gen‐bonded supramolecular motifs in 4,4′‐bipyridinium 8‐hydroxy‐7‐iodo­quinoline‐5‐sulfonate dihydrate

In the title compound, C₁₀H₉N₂⁺·C₉H₅INO₄S⁻·2H₂O, the 4,4′‐bi­pyridine mol­ecule is protonated at one of the pyridine N atoms. These moieties self‐assemble into a supramolecular chain along the a axis through N—H⋯N hydrogen bonds. The quinolinol OH group acts as a donor with respect to a sulfonate O atom [O—H⋯O(sulfonate)] and acts as an acceptor with respect to a C—H group of ferron [C—H⋯O(hydroxy)], forming a supramolecular chain along the b axis. These two types of supramolecular chains (one type made up of bi­pyridine motifs and the other made up of sulfoxine motifs) interact viaπ–π stacking, generating a three‐dimensional framework. These chains are further crosslinked by C—­H⋯O hydrogen bonds and O—H⋯O hydrogen bonds involving water mol­ecules.     

Hydro­gen‐bonding and C—H⋯π interactions in 1,7‐bis(4‐hydroxy‐3‐methoxy­phenyl)­heptane‐3,5‐dione (tetra­hydro­curcumin)

The title compound, C₂₁H₂₄O₆, is the reduced form of curcumin, and exhibits important cosmoceutical properties. The mol­ecule is non‐planar and the benzene rings positioned at the ends of the heptane chain are orthogonally placed, with a dihedral angle of 84.09 (7)° between them. The molecular geometry and H‐atom locations reveal that the `heptane‐3,5‐dione' moiety exists in the keto–enol form, with the hydroxy H atom disordered over two adjacent sites. The packing of the mol­ecules in the lattice is directed by strong O—H⋯O intermolecular hydrogen bonds, which generate two‐dimensional sheets. These sheets are linked by C—H⋯O hydrogen bonds and weak C—H⋯π interactions to develop a three‐dimensional network.     

2‐Hydro­xy‐5‐[(E)‐(4‐methoxy­phenyl)­diazenyl]­benzoic acid

The title compound, C₁₄H₁₂N₂O₄, shows an E conformation about the diazenyl N atoms. The crystal structure features layers of mol­ecules with the primary connection between the layers afforded by carboxyl­ic acid dimer motifs; no evidence for extensive π–π stacking between the layers was found.     

Synthesis,characterization and cytotoxic activity of 5,10,15,20‐tetrakis[4‐(triorganostannyloxy)phenyl]porphyrins

5,10,15,20‐Tetrakis[4‐(triorganostannyloxy)phenyl]porphyrins, (R₃SnO)₄TPP [2, R = Cy (a), Ph (b), PhC(CH₃)₂CH₂ (c)], have been synthesized by the condensation of 4‐(triorganostannyloxy)benzaldehyde, 4‐(R₃SnO)C₆H₄CHO (1), with pyrrole in the presence of BF₃ followed by oxidation by p‐chloranil and characterized by means of elemental analysis, IR, UV–visible and NMR (¹H, ¹³C and ¹¹⁹Sn) spectra. The results of X‐ray single‐crystal diffraction show that 1a and 1b possess a trans‐C₃SnO₂ trigonal bipyramidal geometry with the axial positions occupied by the phenolate oxygen and formyl group oxygen of an adjacent molecule and form a one‐dimensional zigzag chain. In 2a, the macrocyclic core of the porphyrin is coplanar and each tin atom possesses a distorted tetrahedral geometry. These compounds (1 and 2) have potent in vitro cytotoxic activity against two human tumor cell lines – CoLo205 and MCF‐7 – and the activity decreases in the order Ph > Cy > PhC(CH₃)₂CH₂ for the R group bound to tin. Copyright © 2013 John Wiley & Sons, Ltd.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and polymeric adducts with 1,2‐bis(4‐pyridyl)­ethene and 1,6‐di­amino­hexane

In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,2‐bis(4‐pyridyl)­ethene (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₀N₂, there is an intramolecular O—H?O hydrogen bond in the ferro­cene­diol component and a single O—H?N hydrogen bond linking the diol to the di­amine, which is disordered over two sets of sites, so forming a finite monomeric adduct. In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,6‐di­amino­hexane (2/1), 2[Fe(C₁₈H₁₅O)₂]·C₆H₁₆N₂, the amine lies across a centre of inversion in space group P. There is an intramolecular O—H?O hydrogen bond in the ferrocenediol, and the molecular components are linked by O—H?N and N—H?O hydrogen bonds, one of each type, into a C(13)[R(12)] chain of rings.     

Hydrogen‐bonded assemblies of 5,10,15,20‐tetrakis(4‐hydroxyphenyl)porphyrin with dimethylformamide,dimethylacetamide and water

The title free base porphyrin compound forms hydrogen‐bonded adducts with N,N‐dimethylformamide, C₄₄H₃₀N₄O₄·4C₃H₇NO, (I), a mixture of N,N‐dimethylformamide and water, C₄₄H₃₀N₄O₄·4C₃H₇NO·H₂O, (II), and a mixture of N,N‐dimethylacetamide and water, C₄₄H₃₀N₄O₄·6C₃H₇NO·2H₂O, (III). Total solvation of the four hydroxy functions of the porphyrin molecules characterizes all three compounds, thus preventing its supramolecular association into extended network architectures. In (I), the asymmetric unit consist of two five‐component adduct species, while in (III), the nine‐component entities reside on centres of inversion. This report provides the first structural characterizations of the free base tetra(hydroxyphenyl)porphyrin. It also demonstrates that the presence of strong Lewis bases, such as dimethylformamide or dimethylacetamide, in the crystallization mixture prevents direct supramolecular networking of the porphyrin ligands via O—H...O—H hydrogen bonds, due to their competing O—H...N(base) interaction with the hydroxy functions. The crystal packing of compounds (I)–(III) resembles that of other hydrogen‐bonding‐assisted tetraarylporphyrin clathrates.     

Bis(5‐hydroxy‐2‐hydroxy­methyl‐4‐pyrone‐κ2O4,O5)bis(2‐hydroxy­methyl‐5‐oxido‐4‐pyrone‐κ2O4,O5)­calcium(II) tetrahydrate

In the title compound, [Ca(C₆H₅O₄)₂(C₆H₆O₄)₂]·4H₂O, which is a kojic acid–Ca²⁺ complex, the Ca atom is on a twofold axis and is octacoordinated by O atoms from four pyrone ligand mol­ecules. The hydroxyl and ketone O atoms of each ligand form a five‐membered chelate ring with the Ca atom. The crystal structure is stabilized by partial stacking and O—H?O hydrogen bonds.