Inclusion complexes of the natural product gossypol. Clathrate type inclusion complexes of gossypol with carbonyl group containing guests

The crystal structures of 2:1 inclusion complexes of gossypol with methyl propionate (GPMEP) and ethyl acetoacetate (GPEAA) have been determined by X-ray structure analysis. The crystals of GPMEP, C₃₀H₃₀O₈l/2 C₄H₈O₂, are monoclinic, space groupC2/c,a=11.079(3),b = 30.724(7), c = 16.515(5) Å, = 90.46(2)°,V = 5621(3) Å,Z = 8,D _x = 1.33 g cm^–3. The structure has been refined to the finalR value of 0.059 for 1899 observed reflections. The crystals of GPEAA, C₃₀H₃₀O₈l/2 C₆H₁₀O₃, are monoclinic, space groupC2/c,a=11.095(2),b=30.604(9),c = 16.955(5) Å, = 88.27(2)°,V = 5754(3) Å,Z = 8,D _x = 1.35 g cm^–3. The structure has been refined to the finalR value of 0.056 for 2502 observed reflections.In contrast to previously investigated inclusion complexes of gossypol the host molecules do not form centrosymmetric dimersvia hydrogen bonds. In the crystal structures the racemic gossypol is separated into enantiomers forming alternating bimolecular layers. Nearly perpendicular to these chiral bilayers run elongated cavities enclosed on each side by layers of opposite chirality. The surface of these layers is hydrophobic, the polar groups are hidden inside the layer. Guest molecules which are hydrogen bonded to the host are included in cylindrically shaped cavities. Possible hydrogen bonds between host and guest are analysed for this isostructural class of complexes.     

Inclusion complexes of the natural product gossypol. Crystal structure of the 2:1 complex of gossypol with amyl acrylate

The crystal structure of the 2: 1 inclusion complex of gossypol with amyl acrylate has been determined by X-ray structure analysis. The crystals of (C₃₀H₃₀O₈)₂C₈H₁₄O₂ are triclinic, space group P ,a = 14.425(2),b = 15.519(1),c = 16.409(2) Å, =97.89(1), = 117.80(1), =67.01(1)° (reduced cell:a = 14.425(2),b = 15.519(2),c = 16.017(2)Å, = 92.19(1), = 115.01(l), =67.01(1)°],V = 2986.7(5) ų,Z = 2,D _x = 1.31 g cm^–3, (CuK ) = 7.40 cm^–1,T = 292 K. The structure has been solved by direct methods and refined to the final R value of 0.059 for 5155 observed reflections. The gossypol molecules bonded via several hydrogen bonds form centrosymmetric tetramers. The two independent gossypol molecules, A and B, are related within the tetramer by a local noncrystallographic 2-fold axis. The host molecules in the crystal form cavities in which two guest molecules are placed. The ester molecule interacts via a pair of C-...H-O hydrogen bonds with two gossypol molecules of the same chirality and belonging to the same tetramer unit. The amyloxy group of the ester molecule shows a very large thermal motion. It adopts a non-extended conformation in which it can be fitted into the cavity formed by the host molecules.     

Inclusion complexes of the natural product gossypol. Crystal structure of the 2:1 complex of gossypol withm-Xylene

The crystal structure of a 2: 1 inclusion complex of gossypol withm-xylene has been determined by X-ray structure analysis. The crystals of C₃₀H₃₀O₈·0.5C₈ H₁₀ are triclinic, space groupPl^–,a = 8.478(1),b = 14.087(2),c = 14.411(2) Å, = 115,39(1), = 75.11(1), = 86.80(1)°,V = 1475.2(4) ų,Z = 2,D _x = 1.29 g cm^–3,T = 295 K, (CuK ) = 7.01 cm^–1. The structure has been solved by direct methods and refined to the finalR value of 0.079 for 3910 observed reflections. The gossypol molecules are linked by intermolecular hydrogen bonds and form bimolecular layers parallel to the ab plane. Disorderedm-xylene molecules occupy cavities between these layers. All polar groups of the gossypol molecule are packed in the interior of the bilayer while non-polar groups are directed outwards. An analysis of the crystal packing of other inclusion complexes of gossypol shows that such bilayers are formed in four complexes and three of those structures are generically related to each other.Deceased.     

Inclusion complexes of the natural product gossypol. Crystal structure of the 1 : 1 complex of gossypol with isovaleric acid

The crystal structure of the 1 : 1 lattice inclusion complex of gossypol with isovaleric acid has been determined by X-ray structure analysis. The crystals of C₃₀H₃₀O₈C₅H₁₀O₂ are monoclinic, space groupC2/c,a=28.835(7),b=9.063(2),c=26.880(4)Å, =109.66(1)°,V=6615(2) ų,Z=8,D _x = 1.25 g cm^–3, (CuK) = 7.14 cm^–1,T = 295 K. The structure was solved by direct methods and refined with isotropic thermal parameters to the finalR value of 0.132 for 1114 observed reflections. Hydrogen bonded gossypol molecules form columns along the [1 0 1] direction. These columns pack into layers parallel to the (101) plane. The layers of gossypol molecules are separated by the layers of isovaleric acid. The acid molecules are connectedvia a pair of O-H...O hydrogen bonds forming centrosymmetric dimers. There is no hydrogen bond interaction between the carboxylic acid dimers and gossypol molecules.     

Inclusion complexes of the natural product gossypol. Strong influence of the guest on the host structure in channel-type isostructural inclusion complexes of gossypol

The crystal structures of 1 : 1 inclusion complexes of gossypol with tetrahydrofuran (GPTHF), cyclohexanone (GPCHN) and butanal (GPBTA) have been determined by X-ray structure analysis. The crystals of GPTHF are triclinic, space group P,a = 10.788(2),b = 10.979(3),c = 13,880(2) Å, = 80. 11(2), = 103.87(1), = 77.96(2)°,V = 1517.8(6) ų,Z = 2,R = 0.052 for 2701 observed reflections. The crystals of GPCHN are triclinic, space groups P,a = 10.803(4),b = 11.157(5),c = 15.428(6) Å, = 108.75(3), = 106.93(3), = 103.34(3)°,V = 1573(1) ų,Z = 2,R = 0.071 for 1879 observed reflections. The crystals of GPBTA are triclinic, space group P,a = 10.190(2),b = 11.335(1),c = 14.665(2) Å, = 73.04(1), = 103.74(1), = 81.07(1)°,V = 1529.9(5) ų,Z = 2,R = 0.068 for 2964 observed reflections. Crystal data for another 13 isostructural inclusion complexes are given.[/p]In this isostructural group of complexes guest molecules are accommodated in channels and are hydrogen bonded to the host molecules via an 0(1)-H....O(1) hydrogen bond. The molecular association changes significantly with the shape and size of the guest component. In GPTHF centrosymmetric dimers of gossypol formedvia O(5)-H...O(3) hydrogen bonds are associated in columns via a weak O(4)-H...O(8) hydrogen bond. In GPCHN the latter bond disappears as the distance O(4)-O(8) is increased to 3.73 Å. In GPBTA the O(5)-H...O(3) bond is replaced by three centre hydrogen bonds O(5)-H...O(2) and O(3)-H...O(5), and a centrosymmetric dimer of a new type is formed. These dimers are further connected by two weak hydrogen bonds to form columns. The butanal molecule interacts with the host structure via two hydrogen bonds. This indicates that a guest component can activate or deactivate different functional groups of the host in channel inclusion complexes of gossypol for hydrogen bond formation.     

Crystal and molecular structure of the hydrochloride of the diterpene alkaloid hetisine

The molecular and crystal structure of hetisine hydrochloride has been obtained and compared with those of the hydrobromide and perchlorate salts. These structures have been investigated as coordinatoclathrates and it has been shown that on changing from chloride to bromide and then to perchlorate a morphotropic transition is observed.Supplementary Data relevant to this article have been deposited with the British Library as Supplementary Publication No. SUB 82140 (9 pages).     

X-Ray Crystal Structure of Four Inclusion Complexes of the Novel Host Gossindane: An Oxidation Product of Gossypol

Gossindane, the oxidation product of gossypol, demonstrates inclusion properties towards four solvents chosen accidentally. The crystal data of these complexes with ethanol (I), ethylacetate (II), dichloromethane (III) and water (IV) are: (I): C26H30O6· 2C2H5OH, monoclinic, P2/c, a = 8.687(2) Å, b = 10.986(3) Å, c = 14.778(3) Å = 110.94° V = 1317 Å3, Z = 2, R = 0.069, N = 1368; (II): C26H30O6· 0.5C4H8O2, monoclinic, P21/c, a = 8.960(2) Å, b = 21.937(5) Å, c = 14.712(3) Å, = 111.98(2)°, V = 2681 Å3, Z = 4, R = 0.083, N = 2653; (III): C26H30O6· CH2Cl2, monoclinic, P21/c, a = 8.886(2) Å, b = 21.778(6) Å, c = 14.996(4) Å, = 111.31(3)°, V = 2704 Å3, Z = 4, R = 0.131, N = 1580; (IV): C26H30O6·2H2O, monoclinic, C2/c, a = 29.422(9) Å, b = 6.720(2) Å, c = 27.525(9) Å, = 117.43(2)°, V = 4830 Å3, Z = 8. R = 0.096, N = 2240.In the solvates H-bonded host molecules form bilayers with very similar structures and a nearly hydrophobic surface. Guest molecules are placed in channels formed between these bilayers and may be H- bonded to host molecules (ethanol). In the hydrate two water molecules using their H-bonding capacity incorporate gossindane molecules into bilayers.     

Inclusion complexes of the natural product gossypol. Recognition by gossypol of halogeno methanes. Structure of the dichloromethane complex of gossypol and single crystal conservation after decomposition

The structures of gossypol complexes are extremely sensitive to the halogenomethane present as the guest; e.g. changing the number of Cl atoms in chloromethane derivatives changes the structure of the gossypol complex. The crystals of C₃₀H₃₀O₈·CH₂Cl₂ are monoclinic, space groupC2/c,a=21.320(4),b=19.199(6),c=15.765(2)Å, =113.05(2)^o,V=5916(2)ų,Z=8,D _x=1.35 g/cm³,T=295 K. The structure has been solved by direct methods and refined to the finalR value of 0.084 for 1828 reflections. In the structure H-bonded gossypol molecules form columns, generating channels in the structure which are filled by guest molecules. After decomposition (desolvation) monocrystals of the complexes are conserved without destruction, in which there are rather wide and empty channels though slightly smaller than in the complex. An attempt is made to explain some peculiarities of the behavior of the gossypol polymorph formed on the basis of its structure with empty channels. Supplementary data relevant to this article have been deposited with the British Library Publication No. SUP 82165 (17 pages).     

Inclusion complexes of the natural product gossypol. The formation of different gossypol polymorphs on decomposition of channel type inclusion complexes

The existence of seven gossypol polymorphs has been established. Two of them are obtained by direct crystallization from solution. The remaining five polymorphs are the products of desolvation of channel type complexes (tubulates). Each isostructural group of the complexes on decomposition gives one polymorph. Gossypol thus possesses specific peculiarities in terms of the decomposition of its tubulates, and also the absence of thermotropic polymorphic transitions.     

Crystal structures and DNA cleavage activities of two mononuclear nickel(II) complexes

Two new nickel complexes, [Ni(L₁)₂]?·?2(CH₃OH) (1) and [Ni(L₂)₂]?·?2(CH₃OH) (2), where HL₁ is 4-chloro-2-((2-hydroxy-ethylimino)methyl)phenol and HL₂ is 4-fluoro-2-((2-hydroxy-ethylimino)methyl)phenol, have been synthesized and characterized by single-crystal X-ray diffraction and UV-Vis absorption spectra. The coordination polyhedron of nickel(II) in each complex can be described as distorted octahedral. The interactions between the complexes and calf thymus (CT)-DNA/DNA were investigated by UV-Vis spectra and agarose gel electrophoresis. The results show that the complex transforms supercoiled to nicked form and exhibits effective DNA cleavage activity via hydrolytic cleavage mechanism.     

Polymorphism of Inclusion Complexes and Unsolvated Hosts. III. Dimorphism of the Alkaloid Colchicine Hydrate. The Structure of Colchicine Monohydrate

The alkaloid colchicine forms, in addition to the previously known dihydrate host–guest complex, a monohydrate complex. The crystal structure of the monohydrate was determined by direct methods and refined to a final R value of 0.046 for 1425 observed reflections. Crystal data are: orthorhombic, space group P2 12 12 1, a = 9.145(2) Å; b = 13.270(3) Å; c = 17.942(4) Å, V = 2177(1) Å3, Z= 4, Dx = 1.22 g cm-3, T = 293 K. The conformation of the molecule is practically identical with the conformation in the dihydrate inclusion complex. Water molecules show proton donor as well as proton acceptor properties and are hydrogen bonded with the three colchicine molecules giving rise to the three dimensional H-bonded network.     

Inclusion complexes of cryptophane-E with dichloromethane and chloroform: A thermodynamic and kinetic study using the 1D-EXSY NMR method

Complexation equilibria and kinetics of exchange of chloroform and dichloromethane molecules between the cavity of cryptophane-E and bulk solution were investigated using NMR methods. Using one-dimensional magnetization transfer (1D-EXSY type sequence), chemical exchange rates were measured in different temperature ranges, limited by the equilibrium constant values of the complexes and the boiling points of the guest substances. From the kinetic data, activation energies were calculated using the Arrhenius equation. From the temperature-dependence of the association constant data, the enthalpy and entropy of complexation were estimated and compared with values for similar complexes of other cryptophanes.     

Tetraphenylene molecular inclusion complexes. Crystal structures of 2(tetraphenylene)·X,with X=benzene cyclohexane

The crystal structures of two compounds belonging to the isomorphous series of clathrate inclusion complexes of tetraphenylene, 2C₂₄H₁₆·X (with X=benzene (I) and X-cyclohexane (II), were solved. For (I),a=10.0691(1),c=18.431(5) Å, space groupP4₂/n,Z=2; (II) has a very similar cell.Crystal structure analyses (Nicolet R3m four-circle diffractometer, graphite-monochromated MoK; (I) 926 reflections,R _F =12.8%; (II) 1180 reflections,R _F =10%) showed that the tetraphenylene molecules use crystallographicC ₂ symmetry in the construction of a nearly spherical cavity of point symmetry 4 located about 1/4 1/4 1/4. The geometry of the tetraphenylene molecule agrees well with that reported earlier for the crystals of neat tetraphenylene. The enclosed benzene and cyclohexane guests are necessarily disordered. Thedisorder found for the cyclohexane guest is consistent with its expectedchair conformation. Analysis of the cell dimensions of a number of complexes shows that the tetraphenylene framework adjusts itself according to the steric requirements of the guests. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82003. To obtain copies, see page ii of this issue.Also known as N. Z. Huang.     

Synthesis,characterizations and crystal structures of new antimony (III) complexes with dithiocarbamate ligands

Eight new antimony (III) complexes containing dithiocarbamate ligands (R₂NCS₂)₂SbBr [R₂NCS₂ = OC₄H₈NCS₂ (1), C₂H₅NC₄H₈NCS₂ (2), Me₂NCS₂ (3), C₄H₈NCS₂ (4)] and (R₂NCS₂)₃Sb[R₂NCS₂ = C₅H₁₀NCS₂ (5), Bz₂NCS₂ (6), Et₂NCS₂ (7), (HOCH₂CH₂)₂NCS₂ (8)] have been synthesized by the reactions of antimony (III) halides with dithiocarbamate ligands in 1:2 or 1:3 stoichiometries. All the complexes have been characterized by elemental analysis, melting point as well as spectral [IR and NMR (¹H and ¹³C)] studies. The crystal structures of complexes 1, 5 and 8 have been determined by X-ray single crystal diffraction, and their electrochemical character has also been studied.     

Synthesis and crystal structures of magnesium complexes with NNO Schiff base ligands bearing quinolyl pendant donors

A series of ketoimines bearing quinolyl pendants was prepared through Schiff base condensation of 1,3-diketones (2,4-pentanedione, benzoylmethane, and 1-benzoylacetone) and 8-aminoquinoline or 8-amino-2-methylquinoline. The ketoimines were isolated in 46–90% yield and characterized spectroscopically and crystallographically. Reaction of the ketoimines with magnesium 4-methylbenzylalkoxide yielded octahedral magnesium complexes in 67–90% yield. The spectroscopic and crystallographic properties of the magnesium complexes were explored. Structures of 1, 4, 8, 10, and 11 are reported.     

A New Tetraaza Macrotricycle and Its Inclusion Compound with Chloroform. Synthesis and Crystal Structures

A new tetrasubstituted tetraaza macrotricycle 1 was prepared and shown to form a crystalline inclusion compound with chloroform, 1 chloroform (1:2). Crystal structures of the two compounds are reported. In the unsolvated 1, tightly interlocked packing of the molecules involving -stacking interactions of the aromatic groups is determined while in the inclusion compound with chloroform the solvent molecules are accommodated into channels possessing C—H···FFN contact to 1.Supplementary Datarelevant to this publication have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication Nos. CCDC 221992 and 221993.     

Synthesis, characterizations and crystal structures of new organoantimony(V) complexes with various isomers of fluoromethylbenzoate ligands

Six new organoantimony(V) complexes containing various isomers of fluoromethylbenzoate ligands [RC₆H₃COO]₂SbPh₃ and [RC₆H₃COO]SbPh₄ [R = 3-F-4-(CH₃) (1, 4), 4-F-2-(CH₃) (2, 5), 5-F-2-(CH₃) (3, 6)] have been synthesized by the reactions of triphenylantimony(V) dichloride or tetraphenylantimony(V) bromide with various isomers of fluoromethylbenzoate ligands in 1:2 or 1:1 stoichiometries. All the complexes have been characterized by elemental analysis, IR and NMR [¹H, ¹³C and ¹⁹F] studies. The crystal structures of complexes 1, 3, 4, 5 and 6 have been determined by X-ray single crystal diffraction. The structure of complexes show that the five-coordinated antimony(V) atom adopts a distorted trigonal bipyramidal geometry. Furthermore, weak but significant intermolecular C–H···O, C–H···F hydrogen bonds, C–H···pi stacking lead to aggregation and assembly of these complexes into 1D and 2D supramolecular frameworks.     

Synthesis and structures of pyridinologous linear tri- and tetrapyrrole metal complexes

Summary The Cu(II) complexes of a pyridinologous tri- and tetrapyrrole ligand which have recently been shown to be catalytically active were investigated by X-ray crystallography together with the Ni(II), Co(II), and Zn(II) complexes of the first ligand. These ligands displayed an astonishingly variable complexation behavior which uniquely allows to accommodate specific ligand field demands of a certain metal ion. This behavior seems to be an ideal prerequisite to provide catalytically active systems.

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Zur Struktur von pyridinologen linearen Tri- und Tetrapyrrolmetallkomplexen

Zusammenfassung Die Cu(II)-Komplexe eines pyridinologen Tri- und Tetrapyrrolliganden, für welche katalytische Aktivität nachgewiesen worden war, wurden zusammen mit den (Ni(II)-, Co(II)- und Zn(II)-Komplexen des erstgenannten Liganden röntgenstrukturanalytisch untersucht. Diese Liganden zeigten ein erstaunlich variables Komplexierungsverhalten, welches auf einzigartige Weise die Anpassung des Liganden an die spezifischen Bedürfnisse des Ligandfeldsystems eines bestimmten Metallions erlaubt. Dieses Verhalten scheint eine ideale Voraussetzung für katalytisch aktive Systeme zu sein.

     

Synthesis and Inclusion Properties of the Host Compound 1,3-Dihydro-1,1,3,3-tetraphenylisobenzofuran. X-Ray Crystal Structures of the Free Host and of an Inclusion Compound with 1,4-Dioxane

A novel host molecule, 1, suitable for crystalline lattice-type inclusion, has been synthesized, and its cocrystal formation ability has been investigated. Host 1 proved to be of potential use for organic solvent separation and retrieval, and a promising auxiliary for solidification of certain odorous substances. The crystal structures of the solvent-free host 1, and its complex with 1,4-dioxane (1 : 1), have been determined by single crystal X-ray diffraction. The structure of 1 (guest-free) is triclinic, P , with a = 9.452(2), b = 10.359(3), c = 13.116(3) Å, = 101.80(2), = 106.53(1) and = 104.32(1)°. The spacious, propeller-like molecules are held together by weak van der Waals' forces. The dioxane inclusion compound is monoclinic, P21/a, with a = 15.050(1), b = 8.641(1) and c = 20.658(1) Å, and = 94.56(1)°, and contains two crystallographically independent guest molecules, both located around symmetry centres. The molecular packing seems to be governed by C—H···O type bonds (C···O = 3.31 and 3.48 Å) from the host to the dioxane oxygens.