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 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. Crystal structures of gossypol complexes with benzene and chloroform as guests

The crystal structures of the lattice inclusion complexes of gossypol with benzene and chloroform have been determined by X-ray structure analysis. The crystals of (C₃₀H₃₀O₈)₂ · C₆H₆ (GPBNZ) are triclinic, space groupPI,a = 11.241(3),b = 14.986(4),c = 17.380(4) Å, = 98.89(2), = 99.86(2), = 98.91(2)°,V = 2800(2) ų,Z = 2,D _x = 1.32 g cm^–3, (CuK ) = 7.35 cm^–1. The structure has been refined to a finalR value of 0.050 for 6146 observed reflections. The crystals of C₃₀H₃₀O₈·CHCl₃ (GPCLF) are monoclinic, space groupC2/c,a = 28.464(4),b = 8.948(1),c = 26.480(4) Å, = 108.93(2)°,V = 6380(2) ų,Z = 8,D _x = 1.33 g cm^–3, (CuK) = 30.42 cm^–1. The structure has been refined to a finalR value of 0.100 for 1980 observed reflections.GPCLF forms an intercalate-type structure and GPBNZ a clathrate-type structure. There are, however, some similarities in the packing mode of the host molecules in these two structures. On a basis of comparison of the crystal packing of GPCLF and GPBNZ one can postulate that in the desorption process of the intercalate-type GPCLF complex an intermediate clathrate structure of the GPBNZ-type should be formed.     

Stabilization of H2O ⁗ BF3 by hydrogen bonding to 18-crown-6

The decomposition of H₂O BF₃ in both the solid and solution states is rapid at room temperature, but 18-crown-6 H₂O BF₃,1, is stable to its melting point, 72°C.1 crystallizes in the monoclinic space groupC2/c witha = 27.273(9),b = 8.432(5),c = 22.936(9) Å, = 128.33(4)°, andD _c = 1.27 g cm^–3 forZ = 8. Least-squares refinement based on 1409 observed reflections led to a finalR = 0.083. The BF₃ is covalently bonded to the oxygen atom of the water molecule which in turn is hydrogen bonded to the 18-crown-6.     

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. 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).     

X-ray Diffraction Structural Study of Acid Pyridinium Hexamolybdochromate(III)

Acid pyridinium hexamolybdochromate(III) (₅₅NH)H₂[CrMo₆O₁₈(OH)₆] · 6H₂O was synthesized and structurally characterized. The crystals are monoclinic, space group P2₁/c, a = 11.400(2) Å, b = 11.165(2) Å, c = 11.665(2) Å, = 104.39(3)°, Z = 2, _calcd = 2.789 g/cm³.     

Complexation with diol host compounds. Part 1. Structures of the 1:2 molecular complexes oftrans-9, 10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone and with 3-methylcyclopentanone

The structures of the 1:2 molecular complexes of trans -9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone (1), (C₂₆H₂₀O₂·2 C₈H₈O) and with 3-methylcyclopentanone (2), (C₂₆H₂₀O₂·2C₆H₁₀O) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P ,a =8.979(5) Å,b =9.316(3) Å,c = 11.12(1) Å, =94.40(6)°, = 106.53(6)°, = 109.92(5)°,V = 822.94 ų,Z = 1,R = 0.097 for 2549 unique reflections. Compound (2):P ,a = 8.958(7) Å,b =9.815(4) Å,c = 9.807(4) Å, = 96.88(3)°, = 109.21(8)°, = 103.33(7)°,V = 774.10 ų,Z = 1,R = 0.059 for 2494 unique reflections. The intermolecular arrangements in both structures are characterised by host-to-guest hydrogen bonding interactions. The thermal properties of compound (2) have been characterised by DTA and TGA thermograms.     

Synthesis and X-Ray Crystal Structure Study of ]2-Methyl-4-(2-methylbenzoyl)-phenoxy] Acetic Acid Hydrazide

Benzophenone analog 3 has been synthesized and characterized by the X-ray diffraction (XRD) method. The compound crystallizes in a monoclinic space group P2₁/c with cell parameters a = 7.701(8) Å, b = 7.151(5) Å, c= 28.323(3) Å, = 104.639(4)°, Z = 4. The structure exhibits intra- and intermolecular hydrogen bonding of the type N–HO, C–HO, and N–HN. The molecules are interlinked through hydrogen bonds forming an infinite chain. This polymeric-like structure may play an important role in biological activity.     

Crystal structure of copper(II) bis-hexafluoroacetylacetonate

An X-ray diffraction investigation has performed for copper(II) bis-hexafluoroacetylacetonate (Bruker AXS P4 automatic diffractometer, MoK radiation, t = –25°C). Crystal data for C₁₀H₂CuF₁₂O₄: a = 5.530(1) Å, b = 6.038(1) Å, c = 11.266(2) Å, = 95.948(3)°, = 101.743(3)°, = 92.298(3)°, space group; P1, V = 365.6(1) ų, Z = 1, d _calc = 2.169 g/cm³. The square-planar environment of the copper atom (Cu-O_av 1.912 Å, O-Cu-O_av 93°) is completed to bipyramidal by two fluorine atoms of the neighboring molecules, Cu...F 2.71 Å and 2.75 Å.Original Russian Text Copyright © 2004 by S. A. Gromilov, I. A. Baidina, P. A. Stabnikov, and G. V. RomanenkoTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 502–507, May–June 2004.     

Calixcrown Binding to Caesium – X-Ray Structural Determination of a 1,3-Alternate Calix[4]arenebiscrown-7 Ligand

The crystal structure of calix[4]biscrown-7, 1, (C₅₂H₆₈O₁₄), (triclinic,space group P1, Z = 2, a = 11.115 (5), b = 11.710 (5), c = 18.990 (7)Å, = 85.12 (4), = 93.11 (5), = 91.01 (5)4°,V = 2458.9 ų, Rw = 0.0737 for 4170 observed, I 3 (I),reflections) has been determined. It is suggested that the polyether loopswith a radius of ca. 2.1 Å are too shallow to efficiently complex theCs⁺ cation (radius = 1.69 Å).     

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.     

19-Electron arenecyclopentadienyl complexes of ruthenium

A series of are necyc lope ntadienyl complexes,i. e., [Ru(⁵-c₅R₅)(⁶- are ne)]⁺ (1, R= H, arene = C₆H₆; 2, R = Me, arme = C₆H₆; 3, R = H, arctic = C₆H₃Me₃; 4, R = Me, arene = C₆H₃Me₃; 5, R = H, arene = C₆Me₆; 6, R = Me, arene = C₆Me₆) was studied by cyclic voltammetry. These compounds are capable of both oxidation and reduction. The reduction potential values depend on the number of methyl groups in the complex. Reduction of benzene complexes I and 2 by sodium amalgam in THF leads to the formation of decomplexation products, the addition of hydrogen to benzene, and dimerization of the benzene ligands. Both chemical and electrochemical reductions of mesitylene complexes3 and4 result in dimeric products [(⁵-C₅R₅)Ru(-⁵;⁵-Me₃H₃C₆H₃Me₃)Ru(⁵-C₅R₅)] (14, R = H; 15, R = Me). The action of sodium amalgam on compound5 gives products of hydrogen addition to both hexamethylbenzene (17) and cyclopentadienyl (18) ligands along with the major product, the dimer [⁵-C₅H₅)Ru(-⁵; ⁵-Me₆C₆C₆Me₆)Ru(⁵-C₅H₅)] (16). In contrast to5, its permcthylated analog 6 is only capable of adding hydrogen to the hexamethylbenzene ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1691–1697, July, 1996.     

Structure of Complexes Formed in the CuX2–Cu–N-Allylisoquinolinium Chloride System (X = Cl,Br)

The crystals of N-allylisoquinolinium chlorides of the compositions [C₉H₇N(C₃H₅)]₂Cu^IICl₄ (I), [C₉H₇N(C₃H₅)]Cu^ICl₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^ICl_1.43Br_0.57 · H₂O (III) were prepared by alternating-current electrosynthesis. X-ray diffraction analysis (using diffractometer models DARCH1 for I, STOE for II, and KUMA/CCD for III, MoK radiation) showed that the crystals of I are monoclinic, space group P2₁/n, a = 14.91(1) Å, b = 10.41(1) Å, c = 16.90(1) Å, = 109.73(8)°, V = 2470(8) ų, Z = 4. The crystals of isostructural compounds II and III are triclinic, space group P, Z = 2; crystals II: a = 7.2446(6) Å, b = 7.4379(6) Å, c = 12.110(1) Å, = 80.95(1)°, = 85.55(1)°, = 86.60(1)°, V = 641.8(2) ų; crystals III: a = 7.253(2) Å, b = 7.459(4) Å, c = 12.151(5) Å, = 80.82(4)°, = 83.73(3)°, = 86.81(4)°, V = 644.6(9) ų. The structure of I is composed of Cu^IICl₄ ^2– tetrahedra and N-allylisoquinolinium cations united by C–H···Cl hydrogen bonds in corrugated layers. The crystal structures of -complexesII and III are built of [C₉H₇(C₃H₅)]₂Cu₂ ^IX₄ dimers, which form layers along the c axis due to the C–H···X hydrogen bonds. An important role in the structure formation is played by water molecules, which crosslink the organometallic layers to form a three-dimensional framework through the O–H···X contacts.     

Inclusion compounds of (±) gossypol. Structure of the gossypol-n-valeric acid (1/2) coordinato-clathrate

The crystal structure of the inclusion compound of gossypol withn-valeric acid as a guest molecule has been determined by X-ray structure analysis. The crystals of C₃₀H₃₀O₈·(C₅H₁₀O₂)₂, are triclinic, space group ,a=6.912(2),b=14.506(3),c=19.387(4) Å, =78.85(2)°, =83.92(3)°, =86.78(3)°V=1895(1) ų,Z=2,D _x=1.267 g cm^–3, (CuK )=0.768 mm^–1,T=292 K. The structure has been solved by direct methods on intensity data collected for a twinned crystal and refined to the finalR value of 0.062 for 1606 observed reflections and 470 refined parameters.Gossypol-n-valeric acid (1/2) coordinato-clathrate is not isostructural with any of the previously investigated gossypol inclusion compounds but shows some structural similarities to gossypol-acetic acid (1/1). The host and one of the carboxylic acid molecules are connected via hydrogen bonds into molecular assemblies of a column type which are further bonded to centrosymmetric dimers of the secondn-valeric acid molecule. In effect, host and guest molecules are assembled into layer-type H-bonded aggregates. Structural features common to gossypol-n-valeric acid (1/2) and other earlier reported gossypol inclusion compounds are discussed.Supplementary Data relevant to this article have been deposited with the British Library under the number SUP 82194 (9 pages)     

Crystal and molecular structures of benzophenone phenylhydrazone derivatives with anticancer activity

The X-ray crystal structures of 4,4-dihydroxybenzophenone-2,4-dinitrophenylhydrazone (I) and 2,2-dihydroxybenzophenone-2,4-dinitrophenylhydrazone (II) have been determined in order to study the structural characteristics of these molecules that may contribute to their antiestrogenic and cytotoxic properties. These structures have been compared to other hydrazone derivatives as well as tamoxifen, an antiestrogen drug presently used clinically for the treatment of breast cancer.Crystal data: (I) C₁₉H₁₄N₄O₆ · C₄H₁₀O; MW=468.0; monoclinic,P2₁;a=8.601(2), b=15.502(8), c=16.851(4) Å,=98.58(2)°;Z=8; finalR=0.036 for 1904 observed reflections. (II C₁₉H₁₄N₄O₆ · H₂O; MW=410.0; monoclinic,P2₁/c;a=7.603(2),b=19.552(4),c=12.493(3) Å,=92.11(1)°;Z=4; finalR=0.045 for 1171 observed reflections.     

Deuterated benzene and benzene as guest in the copper(II)-en type of tetracyanonickelates

New host-guest complexes of tetracyanonickelates with deuterated benzene and benzene were prepared having the chemical composition Cu(en)₂Ni(CN)₄ 1 C₆D₆ and Cu(en)₂Ni(CN)₄ 2C₆H₆. The spectroscopic behaviour in the range 4000-200 cm^–1, as well as the thermal properties, were investigated and compared with those of similar clathrate compounds.     

Characteristic Features of the Formation of Copper(I) π-Complexes with N-Allyl Derivatives of Piperazinium Sulfamate

The crystals of two copper(I) complexes and piperazinium sulfamate were synthesized by ac electrochemical technique from Cu(NH₂SO₃)₂· xH₂O and N,N-diallylpiperazine, N-allylpiperazine, or piperazine titrated by sulfamic acid in aqueous methanol to pH 4. The crystal structures of the complexes were determined (DARCh diffractometer, MoK radiation, /2 scan mode). The crystal data: [C₃H₅NH(CH₂)₄NHC₃H₅]_0.5[Cu(NH₂SO₃)₂] · H₂O (I), space group P1¯, a = 8.053(1) Å, b = 10.247(2) Å, c = 8.918(2) Å, = 113.03(1)°, = 107.14(2)°, = 95.15(1)°, Z = 2; [NH₂(CH₂)₄NH₂]_0.5NH₂SO₃ (II), space group P2₁/a, a = 8.468(7) Å, b = 5.92(1) Å, c = 10.890(9) Å, = 100.40(9)°, Z = 4; {[C₃H₅NH(CH₂)₄NHC₃H₅][NH₂(CH₂)₄NH₂]}_0.5[Cu(NH₂SO₃)₃] · H₂O (III), space group P1¯, a = 11.729(3) Å, b = 8.266(2) Å, c = 10.611(3) Å, = 82.13(2)°, = 65.73(2)°, = 74.86(2)°, Z = 2. Structure III is a hybrid of elements of structures I and II and contains the -coordinated Cu(I) atom surrounded by three -donor sulfamate nitrogen atoms, which was found for the first time.     

Octanuclear Rare-Earth Clusters

The polyoxo rare-earth core (Ln = Y, Gd, and Yb) has been synthesized from the appropriate rare-earth chloride hydrate and K₂Se and Se in dmf (dimethylformamide). The cluster core is ligated with a variety of polyselenido chains in addition to a number of dmf molecules. The structure of the Gd₈(dmf)₁₃(₄-O)(₃-OH)₁₂(Se₃)(Se₄)₂(Se₅)₂ cluster, 1, was determined by X-ray diffraction methods. It is similar to an Eu cluster previously characterized. Two new clusters, Yb₈(dmf)₁₁(₄-O)(₃-OH)₁₂(Se₄)₂(Se₅)₂Cl₂·dmf, 2, and Y₈(dmf)₁₂(₄-O)(₃-OH)₁₂(Se₄)₄Cl₂·6 dmf, 3, have also been synthesized and characterized. Clusters 2 and 3 have the same octanuclear core of rare-earth atoms as the Gd cluster but contain two chloro ligands in two isomeric conformations in place of the Se ₃ ^2- ring in the Gd cluster. The geometry of the Ln ₈ core is described as a triangulated dodecahedron with ₃-OH groups capping the 12 faces. A ₄-O atom centers the cluster with close contacts to four Ln atoms in an approximate tetrahedral arrangement. Pertinent crystallographic data are: Compound 1, monoclinic, , a= 14.410(3) Å, b = 24.439(5) Å, c = 28.927(6) Å, = 101.05(3)°, V = 9998(3) ų, T = 106(2) K, Z = 4; Compound 2, orthorhombic, , a = 17.049(9) Å, b = 24.68(1) Å, c = 45.03(2)Å, V = 18,945(16) ų, T = 153(2) K, Z = 8; Compound 3, monoclinic, C _2h ⁵ -P2₁/c, a =18.728(l) Å, b = 29.263( 1) Å, c = 20.548(1) Å, = 90.144(1)°, V = 11,261(1) ų, T = 153(2) K, Z = 4.     

Mechanisms of 5'-O-Benzoyl-2,3'-anhydrothymidine Reactions with Nucleophiles: II. Kinetics of the Reaction with Triethylammonium Tetrazolide in DMF

The reaction of 5'-O-benzoyl-2,3'-anhydrothymidine with triethylammonium tetrazolide in DMF at 100-120°C is described by a second-order kinetic equation, following the first-order kinetics in each of the reactants. On the basis of the experimental activatin parameters, H298 = 80 kJ/mol, S = -116 J× mol^{- 1} K^{- 1}, a mechanism was proposed, according to which in the rate-determining stage of S_N2 reaction triethylammonium tetrazolide attacks the C^{3 '} atom of 5'-O-benzoyl-2,3'-anhydrothymidine with simultaneous loosening of the C^{3 '}ÄO² anhydro bond.