Crystal structures of the clathrate inclusion compounds formed by the host bis(isothiocyanato) tetrakis (4-methylpyridine) iron (II) with benzene,m-xylene andp-xylene as guests

Single crystal X-ray structures of three 1 : 1 (guest: host) compounds in which the Fe(NCS)₂ (4-methylpyridine)₄ complex is the host component and benzene,m-xylene andp-xylene are the respective guest components, are reported. The crystals of the inclusion compounds are tetragonalI4₁/a, with:a = 17.08(1),c = 23.66(3) Å (benzene clathrate);a = 17.17(1),c = 24.02(2) Å (m-xylene clathrate) anda = 17.12(1),c = 23.93(3) Å (p-xylene clathrate);Z = 8. The host complex molecule has the octahedral type of coordination of the N₆ donor system. The isothiocyanate ligands are intrans positions and related by twofold axial symmetry. The symmetry axis runs diagonally between the neighbouring, equatorial 4-methylpyridine (MePy) ligands. The two symmetrically independent McPy ligands form angles ofca. 45 and 55° with the equatorial Fe-N₄ plane. The absorption sites for guest molecules lie on centres of symmetry. Non-centrosymmetricm-xylene molecules occupy these sites randomly distributed over two orientations related by symmetry. The structures belong to the class oforganic zeolites since the cavities occupied by the guest molecules are interconnected to form a three-dimensional network.     

Crystal structure of theβ-clathrate form of 4-p-hydroxyphenyl-2,2,4-trimethylselenachroman

In contrast top-hydroxyphenyl-2,2,4-trimethylchroman, Dianin's compound (1), or itsthia analogue2, the title seleno-ether has been found to form two crystallographically distinct types of clathrate. In the first-discovered form, the -modification of as yet undefined structure, the rhombohedral unit cell (R , a = 57.42(1) Å, c = 10.817(1) Å, [from EtOH]) has approximately four times the volume of that found in the clathrates of1 or2 and contains 72 host molecules. Recrystallisation of the selena-host fromn-hexane, however, produces another type of rhombohedral crystal: the-modification has space group R , witha=28.225(2)Å,c=10.859(1)Å, and 18 host molecules in the unit cell. A detailed X-ray study of this latter inclusion compound (host-guest ratio 6:1) has established its true clathrate nature; the disorderedn-hexane guest, showing electron density consistent with an extended planar zig-zag conformation, is found threading the hour glass-shaped cavity's central constriction. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82045 (25 pages).     

DUAL BEHAVIOR OF ACETONITRILE IN A NEW CADMIUM CYANIDE CLATHRATE: CRYSTAL STRUCTURE OF Cd(CH3CN)2Cd(CN)4·2CH3CN

Abstract

We report a new crystal structure of the title clathrate containing tetrahedral and octahedral Cd atoms in a ratio of 1:1. The preparation of the compound is similar to that of the cristobalite-like clathrate Cd(CN)₂·G, where all Cd atoms are tetrahedral. The new inclusion compound crystallizes in the monoclinic space group C2/c, a = 12.337(4), b = 11.964(3), c = 13.594(3) Å, β = 108.60(2)°, Z = 4, R = 0.034 for 1631 reflections. The three-dimensional host framework is built of alternate linkages between the tetrahedral Cd atom of the tetracyanocadmate and the octahedral Cd atom similar to that of the Hofmann-Td and the en-Td types. In the new clathrate dual behavior of acetonitrile, one as a unidentate ligand in the three-dimensional host framework and the other as the guest in the cage-like cavity, has been demonstrated.     

Synthesis and Inclusion Properties of Macrocyclic Polyethers Containing Phosphonic Groups

Abstract

Three novel polyether macrocycles II-IV bearing phosphonic groups have been synthesised in satisfactory yields. Macrocycle II was found to form a 1:1 inclusion compound with cyclohexane and thus was easily isolated from the reaction mixture as a clathrate. The crystal and molecular structure of the cyclohexane solvate has been determined by single crystal X-ray analyses and refined to an R of 0.028 for 3199 reflection. The compound is monoclinic, space group P2₁n with a = 15.886(6) Å, b = 11.657(5) Å, c = 18.621 (6) Å, β = 90.12(3)°, Z = 2. The whole molecule exhibits a great deal of disorder and the different conformations were modelled as consisting of two different primary conformers with population approximately 60:40.     

Inclusion Compounds of Bulky Binaphthyl-type Bis-fluorenol Hosts

Inclusion properties of a new family of clathrate hosts (1–4) containing two 9-hydroxy-9-fluorenyl units or chloro-, bromo- and t-butyl-substituted derivatives of this group attached in the 3,3′-position to a basic 2,2′-binaphthyl construction element are reported (115 examples of clathrates). The crystal structures of six selected clathrates, involving dimethylsulfoxide, cyclopentanol, diethylether, benzylamine, chloroform and acetone as the guest, have been determined by X-ray diffraction, showing varied modes of supramolecular interaction dependent on the host and guest constitutions, while the formation of an intramolecular hydrogen bond between the hydroxy groups of the fluorenol units is a common structural feature (except in 3a) controlling twisted conformation of the host molecules.     

Preparation,Structural Characterization and the Molecular Structure of 2,3,5-Trinitro-<Emphasis Type="Italic">p</Emphasis>-xylene

2,3,5-trinitro-p-xylene (TPX) is synthesized by nitration of p-xylene in mixed acid of nitric and sulfuric acid. Single crystal of TPX is cultured from DMF solution using a slow cooling method. The compound is characterized by FT-IR, ¹H NMR and MS techniques. The crystal structure is determined by X-ray⁴ single-crystal diffraction analysis. The crystal belongs to the monoclinic system with space group P_n. Its unit cell parameters are as follows: a = 0.8271(2), b = 0.6011(1), c = 1.0487(2) nm, β = 105.42(2)^∘, V = 0.50263(2) nm³, D_c = 1.593 g/cm³, Z = 2, F(0 0 0) = 248. The molecular structures of TPX have been calculated at the B3LYP/6-31G^** and B3LYP/6-311G^** levels of theory, and its frequencies analysis have also been accomplished at the same level of theory. The thermal decomposition process of the compound was studied using DSC and TG-DTG techniques. The predicted nitro group vibrations with B3LYP/6-311G^** calculation considerably agree with the observed frequencies. The calculated results propose that the structural parameters from the theory are close to those of the crystal structure from the experiments.     

Prins-Reaktionen mit Arylaldehyden, 5. Mitt.: Zur Umsetzung mit 2-Buten und mit Cyclohexen

By reaction of 2-[(1RS, 2RS)-2-hydroxy-1-methyl-propyl]-2-phenyl-1,3-dithiane (1 a) withcis-2-butene oxide, subsequent reduction and acetalizationc-4,t-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 a) andt-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 b) were synthesized as model compounds. For the same purpose by aldol reaction of cyclohexanone and reduction (1RS, 2SR)-2[(RS)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (7 a), (1RS, 2RS)-2[(SR)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (8 a), and (1RS, 2RS)-2[(RS)-hydroxy-(4-nitrophenyl)methyl]cyclohexanol (8 b) and by acetalization (2 , 4 , 4 a, 8 a)-2,4-bis(4-methoxyphenyl)hexahydro-4H-1,3-benzodioxin (9 a) and (2 , 4 , 4 a, 8 a)-2,4-bis(4-nitrophenyl)hexahydro-4H-1,3-benzodioxin (10 b) were obtained. FromPrins reactions, starting with 2-butene3 a,c-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 c),r-4,t-5-dimethyl-c-6-phenyl-1,3,2-dioxathiane-2,2-dioxide (4), and (2Z, 4E)-1,5-diphenyl-4-methyl-2,4-pentadien-1-on (5), and starting with cyclohexene (E)-3-(4-methoxybenzylidene)cyclohexenyl-4-methoxyphenyl ketone (11) have been isolated in low yields.

4. Mitt.:Griengl, H., Nowak, P., Mh. Chem.109, 11 (1978).     

Host-guest binding in two coordinatoclathrates of 1,1′-binaphthyl-2,2′-dicarboxylic acid. x-ray crystal structures of the inclusion compounds with 1-propanol (2 : 1) andt-butanol (1 : 1)

1,1'-Binaphthyl-2,2'-dicarboxylic acid (1) forms crystalline inclusion compounds with 1-PrOH (2:1) andt-BuOH (1:1). X-ray crystal structures of the two inclusion compounds are reported. Crystals of1·1-PrOH (2: 1) show triclinic ( ) symmetry with the unit cell dimensionsa = 10.160(1),b = 14.050(2),c = 15.167(1) Å = 100.37(1), = 104.40(1), and =94.82(1)°. Crystals of1s·t-BuOH (1: 1) are monoclinic (P2₁/n) with the cell dimensionsa = 10.603(5),b = 14.377(4),c = 15.664(7) Å, = 104.24(4)°. In both structures, H-bonded loops involving host –000H functions and guest –OH groups establish the supramolecular association. They relate these coordinatoclathrates to previous alcohol inclusions of1. Due to the unusual 2:1 (host: guest) stoichiometry, additional dimer-like interactions between –000H groups of host molecules are found in the 1-PrOH inclusion compound. From the point of view of topology these structures can be referred to as channel inclusion compounds.     

Calixarenes: Structure of an acetonitrile inclusion complex and some transition metal rimmed derivatives

The hostt-butylcalix[4]arene,1a, forms a 11 inclusion compound with acetonitrile as guest. The inclusion compound has been isolated and characterised by X-ray analysis of a twinned crystal at 123 K. The acetonitrile guest lies on a crystallographic four-fold symmetry axis passing through the centre of the bowl of1a which adopts a regular cone conformation. A known tetradentate and a new tridentate phosphinitocalix[4]arene derivative,2a and2c respectively, have been synthesized from1a and Ph₂Cl. Both2a and2c show a strong ability to coordinate with late transition metals and new complexes of gold(I), palladium(II) and platinum(II) are reported. Supplementary Data relating to this paper have been deposited with the British Library as Supplementary Publication No. SUP 92171 (5 pp.)This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Solid-state binding of dimethyl sulphoxide involving carboxylic host molecules. X-ray crystal structures of four inclusion species

The crystal structures of four dimethyl sulphoxide (DMSO) inclusion compounds with different carboxylic acid hosts,1–4, have been studied by single crystal X-ray analysis. Crystals of thetrans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid inclusion compound (1a), [1 · DMSO (1: 1)] show monoclinic (P2₁/n) symmetry with the unit cell dimensionsa = 11.522(4),b = 18.658(2),c = 8.709(1) Å and = 98.92(2)°. The clathrate of the 9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid (2a), [2 · DMSO (1: 2)] is triclinic (P) with the cell dimensionsa = 15.043(7),b =9.657(4),c = 8.118(7) Å, = 101.81(5), = 96.05(4) and = 100.04(4)°. Triclinic (P) symmetry is shown also by the inclusion compound of 9,10-dihydro-9,10-ethanoanthracene-11-monocarboxylic acid (3a) [3 · DMSO (1:1)] with the cell dimensionsa=6.3132(1),b=7.9846(2),c=17.5314(4) Å, = 96.46(2), = 87.08(2) and = 106.02(2)°. The 9,9-bianthryl-2-monocarboxylic acid clathrate (4a) [4 · DMSO (1:1)] is monoclinic (P2₁/n) and the cell dimensions area = 19.625(18),b = 8.817(1),c = 14.076(8) Å and = 97.92(6)°. In all these structures, the hosts show the same basic recognition pattern for the DMSO guest, involving a strong O-H ... O bond from the COON to the S=O group, and a possible C-H ... O type interaction between the carbonyl O atom of the host and a CH₃ group of the guest. The crystals consist of discrete host-guest aggregates which are mainly held together by weak intermolecular interactions of the Van der Waals' type. The stoichiometries of the aggregates are, however, different.     

Infrared Spectroscopic Study on the Hofmann-dadn-type and the Td-dahxn-type clathrates

Infrared spectra of M(1,10-diaminodecane)Ni(CN)₄ · 1,5 G (M=Co, Ni or Cd; G=o-xylene, m-xylene, p-xylene) and Cd(l,6-diaminohexane)M(CN)₄ · C₆H₆ (M=Cd or Hg) clathrates are reported. The 1,10-diaminodecane and 1,6-diaminohexane molecules in the host permit the inclusion of bulky guest molecules. The spectral data of clathrates were compared with those of the corresponding host. The spectral features suggest that these compounds are similar in structure to other Hofmann-type and Hofmann-T_d type clathrates, respectively.     

Supramolecular behaviour of bulky arylboranes in the crystalline state

The aromatic monoboranes 1, 2 and bisboranes 3, 4 of which 4 is a newly synthesised compound have been studied with reference to their supramolecular behaviour in the crystalline state. While the monoboranes crystallise purely, the bisboranes form channel-type solvent inclusions with m-xylene (3a) and nitrobenzene (4a) in the crystals, showing their potential as clathrate hosts in the realm of optically and electronically interesting compounds.     

Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphan-Azodicarbonsäureester, 5. Mitt.: Transformationen an Glykonolactonen

Reaction ofD-glucono-1,5-lactone1 with two equivalents oft-butyldimethylchlorosilane yields via a ringcontraction 2,6-bis-O-(t-BDMSi)-D-glucono-1,4-lactone2a as main product and a small amount of 5,6-bis-O-(t-BDMSi)-D-glucono-1,4-lactone2c. Under the same conditionsL-mannono-1,4-lactone3 is transformed to the derivatives 2,6-bis-O-(t-BDMSi)-L-mannono-1,4-lactone3a and 3,6-bis-O-(t-BDMSi)-L-mannono-1,4-lactone3c as the minor product. 2,6-bis-O-(t-BDMSi)-D-galactono-1,4-lactone4a and 2,6-bis-O-(t-BDMSi)-D-gulono-1,4-lactone5a are also prepared from the corresponding glyconolactones4 and5. Whereas the compounds2a, 2c, 4a and5a withAc ₂O-pyridine give the bisacetylderivatives2b, 2d, 4b and5b, 3c is converted by an accompanying migration of one silylgroup to the 5,6-bis-O-(t-BDMSi)-2,3-bis-O-acetyl-L-mannono-1,4-lactone3d. The gluconolactone derivative2a reacts easily withTPP/DEAD/HX to the 5-X-L-idono-1,4-lactone derivatives6a (X=N₃),6b (X=p-NO₂-C₆H₄COO) and6c (3-O-acetylderivative of6a). Treating6b with a second equivalentTPP/DEAD/HX leads to the unsaturated sugarlacton7b. Without an external nucleophile2a affords withTPP the mixture of 2,6-bis-O-(t-BDMSi)-3,5-carbonato-D-glucono-1,4-lactone2c, 3,5-anhydro-L-idono-1,4-lactone8 and 3,6-anhydro-D-glucono-1,4-lactone9. Analogous procedures applied to4a yield theL-altronolactonoderivatives10a, 10b and10c, the unsaturated sugarlactone11b on the one and the 3,5-carbonatogalactonolactone4c and the 2,6-bis-O-(t-BDMSi)-3-desoxy-5-ethoxycarbonyl-D-threo-hex-2-en-1,4-lactone12 on the other hand.Whereas the bis-silyletherderivative3a is transformed by the title system exclusively by an elimination process to13, the derivative5a affords withTPP/DEAD without any elimination the 3,6-anhydrosugar14. Partial desilylation of14 followed by acetylation gives the derivatives14a and14b.Structural elucidations were achieved by¹H-NMR-analysis. In some cases also CD-measurements allowed suitable correlations.

Mark, E., Zbiral, E., Brandstetter, H. H., 4. Mitt., Mh. Chem.111, 289 (1980).     

Synthesis of some schiff bases of 3-aroyl-6-aryl-4-hydroxy-2H-pyran-2-ones

Summary The reaction of 3-aroyl-6-aryl-4-hydroxy-2H-pyran-2-ones (Ar=p-tolyl, 1,1-biphenyl-4-yl or thienyl) with aniline and substitutedo-phenylenediamine (R=H, CH₃ or Cl) yields a series of new Schiff bases2a–f in 51–72% yield. Bromination of1a gave the 5-bromo derivative1c, while the compounds1a,1b,2b,2e, and2f were converted into 2,6-diaryl-4H-pyran-4-ones3a–c. All products have been fully characterized.

---

Synthese von Schiff'schen Basen von 3-Aroyl-6-aryl-4-hydroxy-2H-pyran-2-onen

Zusammenfassung Die Reaktion von 3-Aroyl-6-aryl-4-hydroxy-2H-pyran-2-onen (Ar=p-Tolyl, 1,1-Biphenyl-4-yl oder Thienyl) mit Anilin und substituierteno-Phenylendiaminen liefert neue Schiff'sche Basen2a–f/bd in 51–72% Ausbeute. Bromierung von1a gab das 5-Bromderivate1c, während die Verbindungen1a,1b,2b,2e und2f in 2,6-Diaryl-4H-pyran-4-onen3a–c übergeführt wurden. Alle Produkte wurden voll charakterisiert.

     

The easy hydrolysis of hexacyanocyclopropane, ethyl 1,2,2,3,3-pentacyanocyclopropane-1-carboxylate, 1,2,2,3,3-pentacyanocyclopropane-1-carboxamide, andN,N-dimethyl-1,2,2,3,3-pentacyanocyclopropane-1-carboxamide tor-1,c-2,c-3-tricyanocyclopropane-t-carboxamide

Hydrolysis of hexacyanocyclopropane (1a), ethyl 1,2,2,3,3-pentacyanocyclopropane-1-carboxylate (1b), 1,2,2,3,3-pentacyanocylopropane-1-carboxamide (1c), andN,N-dimethyl-1,2,2,3,3-pentacyanocylopropane-1-carboxamide (1d) in 95% acetic acid yieldsr-1,c-2,c-3-tricyanocyclopropane-t-1-carboxamide (3). The structure of3 was proved by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 454–456, March, 1998.     

Competitive clathration ofp-xylene andp-dibromobenzene by the [Ni(NCS)2(4-Methylpyridine)4] host

The selectivity of inclusion ofp-xylene andp-dibromobenzene from their liquid mixtures by the host [Ni(NCS)₂(4-methylpyridine)₄] and the enthalpy of clathration were determined.p-Dibromobenzene is clathrated significantly more thanp-xylene. The heats of clathration show a linear dependence upon the composition of the enclathrated mixture and are considered to be indicative of the conclusion that the guest-guest interactions are negligible from the thermochëmical point of view. By comparing data presented herein with some literature data on competitive clathration an attempt to derive the entropy of guest exchange in the clathrate was performed.Presented at the International Seminar on Inclusion Compounds, Jaszowiec, Poland, 24–26 September, 1987.     

Synthesis and Cation-Binding Properties of (1→6)-2,5-Anhydro-D-glucitol with 3,4-Di-O-Pentyl and Decyl Groups by Cyclopolymerization of 1,2:5,6-Dianhydro-D-mannitols

Abstract

The cyclopolymerizations of 1,2:5,6-dianhydro-3,4-di-O-pentyl-D-mannitol (1b) and 1,2:5,6-dianhydro-3,4-di-O-decyl-D-mannitol (1c) were carried out using BF₃OEt₂ and t-BuOK. All the resulting polymers consisted of cyclic constitutional units, i.e., the extent of cyclization was 100%. The polymer structures for the polymerization with t-BuOK were (1→6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol (2b) and (1→6)-2,5-anhydro-3,4-di-O-decyl-D-glucitol (2c), whereas those with BF₃O-decyl₂ comprised 2,5-anhydro-D-glucitols as major units along with other cyclic ones. These polymers were soluble in n-hexane, CHCl₃, and THF, but insoluble in water, which differs from the amphiphilic solubility of (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol (2a). The cation-binding properties of 2b and 2c were examined using alkali-metal picrates in order to compare them with those of 2a. The extraction yields for each cation decreased in the order of 2c < 2b < 2a. Every polymer exhibited a similar cation-binding selectivity in the order Cs⁺ > Rb⁺ > K⁺ ? Na⁺ > Li⁺. The ratio of K⁺ and Na⁺, K⁺/Na⁺, was 4.6 for 2a, 5.1 for 2b, and 7.1 for 2c in the increasing order 2a < 2b > 2c.     

Kinetics of the dimerization of silylenes to disilenes

The activation parameters of the dimerization of t-butylmesitylsilylene (2a), dimesitylsilylene (2b) and bis(2,4,6-triisopropylphenyl)silylene (2c) to the corresponding disilenes were estimated by monitoring the time-dependent changes in their UV-Vis absorption spectra. The activation energy increased in the order: 2a < 2b < 2c. This article is part of a Special Issue dedicated to M. Kira.     

Synthesis of Acid-Resistant P-Quinone Monoketals and Thermally Stable 4,4-Dialkoxycyclohexa-2,5-Dien-1-OLS

Preparation and high resistance to acid hydrolysis of sterically hindered p-quinone monoketals 1a, 1b and 1c are described. Thermal stability of ketal alcohols 2a and 2b derived from 1a and 1c, respectively, is also mentioned.     

Triol Crystalline Hosts Derived from Malic Acid. Synthesis,Inclusion Formation and X-ray Crystal Structures of a Free Host and its Inclusion Compound with Ethanol (1:1)

Abstract

Four new host compounds 1–3 (a, b) derived from malic acid as different optical species and having particular lateral substituents were synthesized. Their properties in crystalline inclusion formation were studied and discussed. Crystal structures of a free host compound 1 and its ethanol inclusion complex [1·EtOH (1:1)] have been determined by X-ray analysis [1: orthorhombic, P2₁2₁2₁, a = 9.304(3), b = 14.950(3), c = 15.712(3) Å, Dc = 1.248 Mg·m^?3, Z = 4, R = 0.039 for 2474 reflexions; 1·EtOH (1:1): triclinic, P 1; a = 11.945(3), b = 14.080(3), c = 16.029(4) Å, α = 106.82(2), β = 97.74(2), γ = 89.93(2)°, D_c = 1.187 Mg·m³, Z = 4, R = 0.096 for 10404 data]. Spontaneous resolution occurs during crystallization in crystals of 1. An interesting H-bonding pattern develops that probably is responsible for the inclusion formation with ethanol in the associate crystal.