Crystal and moleclar structures of 5-allyl-25-methoxy-26,27,28-tribenzoylcalix[4]arene

The crystal and molecular structures of 5-allyl-25-methoxy-26,27,28-tribenzoylcalix[4]arene, an unsymmetrically substituted macrocycle, are reported. The space group is orthorhombic,P2₁2₁2₁, witha=13.4181(6),b=16.6652(10) andc=18.9936(14) Å andZ=4. Refinement by least-squares calculations converged with aR=0.060 for 4018 observed reflections. The molecule assumes a 1,3 alternate conformation with 2 benzoate rings and the disordered allyl side chain on one side and the third benzoate ring and the methoxy group on the opposite side of the mean plane of the methylene bridging groups. The four phenyl rings that comprise the macrocycle are approximately parallel in pairs; the members of a pair are 5.6 Å apart. The carbonyl oxygen atoms of the 3 benzoate groups are oriented away from the center of the cavity while the ester oxygen atoms and the methoxy oxygen atom are oriented toward the cavity center. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82033 (26 pages).     

Inclusion of water by a crown amide. First crystal structure of a respective host-guest combination

Crown amide (1) forms a stoicheiometric 1:1 inclusion complex with water, the X-ray crystal structure of which is reported. Crystals of1 · H₂O are triclinic, space groupP1, witha=7.503(1),b=11.394(3),c=13.443(2) Å, =107.066(18), =96.627(10), =106.377(14)°, andZ=2.R _F =0.039 for 1697 MoK reflections [I>3(I)] measured at 24°C. The structure features a hydrogen bonded hostguest relationship with concrete1 · H₂O units. Hydrogen bonds are between the water oxygen and O(4), N(4), respectively. The crystal packing shows a cavity arrangement of four ligands around each water molecule. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82055 (16 pages).     

Über die Struktur der Acrylnitril-Guanidin-Kondensate Über Heterocyclen, 78. Mitt.

Repetition of the work ofSugino andTamaka ¹ showed that acrylonitrile and guanidine react inDMF to yield not only 3,4,6,7-tetrahydro-2H-pyrimido[1,2—a]pyrimidine-2,8(1H)-diimine (1), but a mixture (F) of1 (as a main product) and 2-amino-4-imino-1,4,5,6-tetrahydropyrimidine-1-propionitrile (7) besides one or two bases not identified so far.1 and7 were isolated as picrates. For the prove of their structures,1- and7-picrate were also prepared by an unequivocal synthesis starting from iminodipropionitrile hydrochloride8 · HCl: The latter on reaction with cyanamide gave9 which cyclized to afford a mixture of1,7 and 2-amino-4-oxo-1,4,5,6-tetrahydropyrimidine-1-propionitrile (10). The picrates of1 and7 were identical with those prepared from the acrylonitrileguanidine-condensateF. This result supports the prior proposed¹ structures of pyrimidopyrimidine1 and of4,5 and6, obtained by hydrolysis of1. Nmr-, ir-and some of the mass spectra of1,4,7–10 (and their salts) are reported.

     

Crystal structures of ethylenediaminecadmium(II) tetracyanocadmate(II)-benzene(1/2) and ethylenediaminecadmium(II) tetracyanocadmate(II)

The crystal structure of ethylenediaminecadmium(II) tetracyanocadmate(II)-benzene(1/2),I, has been redetermined based on 1632 reflections collected anew for the crystal coated with epoxy resin, with a final conventionalR=0.038;I crystallizes in space groupP4₂22, witha=b=8.265(1) andc=15.512(3) Å, andZ=2. Ethylenediaminecadmium(II) tetracyanocadmate(II),II, is concluded to be identical with the residual metal complex host ofI, remaining after the liberation of the guest benzene molecules;II crystallizes from an aqueous solution containing bis- or tris-ethylenediaminecadmium(II) tetracyanocadmate(II) in space groupI4₁/acd, witha=b=14.366(1) andc=23.771(4) Å, andZ=16; refinement led to a conventionalR=0.043 for 1181 reflections. The bridging ethylenediamine ligand inI turns to a chelating one inII; dissociation and recombination should occur in the coordination sphere of the six-coordinate cadmium atom, whenII is derived fromI by the liberation of the guest molecules. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82018 (30 pages).Dedicated to Professor H. M. Powell.     

Crystal structures of heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin complexes with (R)- and (S)-Flurbiprofen

Hepatakis(2,3,6-tri-O-methyl)--cyclodextrin (TM--CDx) forms crystalline complexes with (R)-Flubiprofen (R-FP), C₆₃H₁₁₂O₃₅C₁₅H₁₃O₂F·H₂O, and (S)-Flurbiprofen (S-FP), C₆₃H₁₁₂O₃₅C₁₅H₁₃O₂F. The crystal structures were determined by X-ray analysis. Crystals of both compounds are orthorhombic and the space group isP2₁2₁2₁ with cell dimensions:a=15.092(2),b=21.714(3), andc=28.269(4) Å for theR-FP complex, anda=15.271(2),b=21.451(3) andc=27.895(3) Å for theS-FP complex. The macrocyclic ring of TM--CDx is markedly distorted because of the inability to form intramolecular hydrogen bonds and the steric hindrance involving methyl groups. In both complexes, the phenyl group is inserted into the host cavity from the O(2), O(3) side, which is wider than the O(6) side. The biphenyl moiety ofR-FP is fixed in theR-configuration within the host cavity. The phenyl group ofS-FP is disordered, andR-andS-configurations are statistically distributed with equal probability. TM--CDx molecules are stacked along theb axis to form a column structure. The TM--CDx molecule is laterally shifted with respect to the column axis, and a half of the guest molecule protrudes outside from the crevis of the column. The carboxyl group ofR-FP forms a hydrogen bond with water located outside the host cavity, while the carboxyl group ofS-FP is hydrogen-bonded to an oxygen atom of an adjacent TM--CDx. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82064 (24 pages).     

Indium-based liquid clathrates. II. Inclusion compounds derived from salts of the tetrachloroindate anion,InCl 4 − , and the crystal structure of [Li·15-c-5] [In(CH3)3Cl] (15-c-5=15-crown-5)

Indium(III) chloride reacts with 12-c-4 to give the 1:1 adduct [InCl₃·12-c-4]. This complex is a convenient In precursor to liquid clathrates. [InCl₃·12-c-4] reacts with LiCl to form [Li·12-c-4] [InCl₄]. When the reaction is carried out in the presence of an aromatic solvent such as toluene, a liquid inclusion complex forms readily. It has been determined that the C₆H₅CH₃:[Li·12-c-4] [InCl₄] ratio is 2. Alkylation of the 15-c-5 adduct of InCl₃ with methyllithium yields [Li·15-c-5] [In(CH₃)₃Cl]. The salt fails to form inclusion complexes with aromatic molecules. This compound has been characterized using single crystal X-ray diffraction. The molecule belongs to the monoclinic space groupP2₁/n, witha=7.515(2),b=18.952(6), andc=13.938(7) Å, =95.12(3)° andD _calc=1.43 g cm^–3 for Z=4. Least squares refinement based upon 2348 observed reflections led to a finalR=0.039. Supplementary Data relevant to this paper have been deposited with the British Library under number SUP82054 (20 pages).     

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.     

Inclusion of multi-ring compounds byp-tert-butylcalix[5]arene

The inclusion complex ofp-tert-butylcalix[5]arene with tetralin has been characterized in the solid state by a single crystal X-ray diffraction study and by¹³C CP/MAS NMR experiments. A crystallographic mirror plane bisects the calix[5]arene and contains the tetralin molecule (which is dynamically disordered). The guest penetrates the upper rim of the calixarene and the experimental results indicate the saturated ring is imbedded most deeply.p-tert-Butylcalix[5]arene (tetralin) · 2 EtOH belongs to the monoclinic space group C2/m witha = 22.187(6),b = 15.823(6),c = 18.168(5) Å, = 99.70(2)°, andD _c = 1.09 g cm^–3 forZ = 4. Refinement based on 1652 observed reflections led to a finalR value of 0.081. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82/82129 (19 pages).     

Proximally functionalized cavitands and synthesis of a flexible hemicarcerand

A general study on the synthesis of partly bridged octols3a-d and4c-d is described. Tri-bridged diol3c can be prepared in 54% yield in DMSO at 70°C with excess CH₂BrCl or in 52% yield in DMF at 70°C with only 4 equiv. of CH₂BrCl. 1,3-Di-bridged tetrol4a, one of the two possible di-bridged isomers formed in preference to the other, was obtained in 30% yield. Tri-bridged diols3c andd can be selectively debrominated in one step by treatment with 5 equiv. ofn-BuLi in THF to afford the corresponding dibromo derivatives8a andb in 77% and 76% yields, respectively. After incorporation of the fourth bridge, the remaining two bromines can be replaced by C(O)OMe to give9c (60%), by OH to give9d (62%) or by CN to give9f (>95%). When the lithiated derivatives of3c andd are quenched with electrophiles other thanH ⁺, a selectively functionalized tri-bridged diol with hydroxyl (8c, 47%) and selectively functionalized cavitands with thiomethyl (9g, 25%) or iodo (9h, 20%) groups can be synthesized. Two molecules of9d were coupled with CH₂BrCl in DMSO/THF under high dilution conditions to give the flexible hemicarcerand10 in 71% yield. Supplementary Data. A list of observed and calculated structure factors have been deposited with the British Document Supply Centre as Supplementary Publication No. SUP 82170 (50 pages)This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Studies in werner clathrates. Part 2. Structures of bis (isothiocyanato) tetra (4-phenylpyridine) nickel (II)· 4-dimethylsulphoxide,bis (isothiocyanato) tetra (3-methylpyridine) nickel (II)· chloroform and bis (isothiocyanato) tetra (3,5-dimethylpyridine) nickel (II)

The structures of Ni(NCS)₂(4-PhPy)₄·4DMSO and Ni(NCS)₂(3-MePy)₄·CHCl₃ have been elucidated. Movement of guest molecules through channels in the host structure was simulated by potential energy calculations. Ni(NCS)₂(3,5-diMePy)₄ does not form inclusion compounds. An intra-molecular potential energy study shows that theortho-hydrogens on the 3,5-dimethylpyridine ligands control the conformation of the molecule. The same result is obtained with the 4-methylpyridine ligand, which suggests that the extent of rotation of substituted pyridines about the Ni–N bounds is not a factor governing clathrate formation. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82030 (43 pages).     

Synthesis and thermal transformations of molecular complexes of bis[tris(trifluoromethyl)germyl]mercury(ii witho-quinones

Stable molecular complexes of bis[tris(trifluoromethyl)germyl]mercury(II) Hg[(CF₃)₃Ge]₂ (1) witho-quinones (3,6-di-tert-butylbenzoquinone-1,2 (2), 3,6-di-tert-butyl-4,5-dimethoxybenzoquinone-1,2 (3), and 1,4,5,7-tetra-tert-butyldibenzo[1,4]dioxin-2,3-dione (4)) have been synthesized and characterized by elemental analysis and IR and electronic absorption spectroscopies. Depending on the ratio between the starting reactants, the reactions ofo-quinones with1 gave complexes of the composition R₂Hg · Q (5,7,9) or R₂Hg · Q₂ (6,8,10), where Q=2 (5,6),3 (7,8),4 (9,10); R=Ge(CF₃)₃. According to the spectral data, the molecule ofo-quinone in R₂Hg · Q acts as a neutral ligand, whereas the second molecule ofo-quinone in R₂Hg · Q₂ is not coordinated to1. It has been found by ESR that thermolysis of polycrystalline samples of complexes6 and10 involves intermediate formation of radical pairs and finally yields paramagnetico-semiquinone complexes, SQGe(CF₃)₃, which are typical products of one-electron oxidation of Organometallic compounds byo-quinones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1568–1573, August, 1995.The authors wish to thank M. A. Lopatin for his help in recording the electronic absorption spectra.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-18369).     

Clathrates of organic onium halides,V: preparation of new clathrates and structure of the 1-propanol inclusion of a bis-quinuclidinium salt

Organic onium salts (3–15) are prepared and their inclusion capacity towards solvent molecules is investigated. The crystal structure of the1·propanol·H₂O clathrate ofN,N-[5-tert-butyl-1,3-phenylenebis(methylene)]bis(quinuclidinium)dibromide (4) is reported and compared with the X-ray structures of related clathrates described earlier. Supplementary Data: Details of the crystal structure are available on request from the Fachinformationszentrum Energie-Physik-Mathematik, D-7517 Eggenstein, Leopoldshafen 2, by quoting the depository number CSD 50883, the names of the authors, and the journal citation.     

f-Element/crown ether complexes, 11. Preparation and structural characterization of [UO2(OH2)5] [ClO4]2·3(15-crown-5)·CH3CN and [UO2(OH2)5] [ClO4]2·2(18-crown-6)·2 CH3CN·H2O

The reaction of UO₂(ClO₄)·nH₂O with 15-crown-5 and 18-crown-6 in acetonitrile yielded the title complexes. [UO₂(OH₂)₅] [ClO₄]₂·3(15-crown-5)·CH₃CN crystallizes in the triclinic space groupPT with (at–150°C)a=8.288(6),b=12.874(7),c=24.678(7) Å, =82.62(4), =76.06(5), =81.06(5)°, andD _calc=1.67 g cm^–3 forZ=2 formula units. Least-squares refinement using 6248 independent observed reflections [F _o5(F _o)] led toR=0.111. [UO₂(OH₂)₅] [ClO₄]₂·2(18-crown-6)·2CH₃CN·H₂O is orthorhombicP2₁2₁2₁ with (at–150 °C)a=12.280(2),b=17.311(7),c=22.056(3) Å,D _calc=1.68 g cm^–3,Z=4, andR=0.032 (3777 observed reflections). In each complex the crown ether molecules are hydrogen bonded to the water molecules of the pentagonal bipyramidal [UO₂(OH₂)₅]²⁺ ions, each crown ether having exclusive use of two hydrogen atoms from one water molecule and one hydrogen from another water molecule. In the 15-crown-5 complex the remaining hydrogen bonding interaction is between one of the water molecules and one of the perchlorate anions. The solvent molecule has a close contact between the methyl group and a perchlorate anion suggesting a weak interaction. There are a total of three U-OH...OClO₃ hydrogen bonds to the two perchlorate anions in [UO₂(OH₂)₅] [ClO₄]₂·(18-crown-6)·2CH₃CN ·H₂O. The remaining coordinated water hydrogen bond is to the uncoordinated 2H₂O molecule, which in turn is hydrogen bonded to a perchlorate oxygen atom and an acetonitrile nitrogen atom. One solvent methyl group interacts with an anion, the other with one of the 18-crown-6 molecules. Unlike the 15-crown-5 structure, the hydrogen bonding in this complex results in a polymeric network with formula units joined by hydrogen bonds from one of the solvent molecules and the uncoordinated water molecule. Supplementary data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82051 (37 pages).For Part 10, see reference [1].     

p-t-Butylcalix[4]arene tetra-acetamide: a new strong receptor for alkali cations [1]

From the reaction ofp-t-butylcalix[4]arene with -chloro-N,N-diethyl acetamide a new lipophilic ether-amide ligand (2) has been obtained in high yield. Solution studies show (2) to be a very strong cation receptor for alkali cations, especially sodium and potassium. The X-ray crystal structure determination of the free ligand (2) and two potassium complexes (KI and KSCN) shows the calix[4]arene in a fixed cone structure and the cation completely encapsulated in a polar cavity of eight oxygen atoms. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82059 (57 pages).Presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986.     

Reaction of trimethylaluminum with calixarenes. I. Synthesis and structure of [Calix[8]arene methyl ether] [AlMe3]6·2 toluene and of [p-tert-butylcalix[8]arene methyl ether] [AlMe3]6·4 benzene

Reaction of the methyl ether of calix[8]arene with AlMe₃ yields [calix[8]arene methyl ether] [AlMe₃]₆·2 toluene,1, while that ofp-tert-butylcalix[8]arene gives [p-tert-butylcalix[8]arene methyl ether] [AlMe₃]₆·4 benzene,2. Both compounds1 and2 fail to react with alkali metal salts, MX. In1, the absence of a butylpara-substituent affords greater flexibility than is the case for thetert-butyl compound2. Thus, all six of the AlMe₃ groups are located on the outside of the macrocyclic ring (in projection) in1, but two AlMe₃ units are found on the inside in2. Colorless, air-sensitive crystals of1 belong to the triclinic space group witha=13.690(8),b=14.317(4),c=14.738(6) Å, =76.11(3), =62.36(4), =82.41(4)^o, andD _c =1.06 g cm^–3 forZ=1. Refinement led toR=0.101 for 1154 observed reflections.2 crystallizes in with =12.400(6),b=16.229(8),c=19.251(5) Å, =96.17(3), =107.25(3), =101.54(3)^o, andD _c =1.01 g cm^–3 forZ=1. Refinement of2 gaveR=0.128 for 4351 observed reflections. The macrocyclic array in both1 and2 lies about a crystallographic center of inversion. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82049 (48 pages).     

Rearrangement of the crystal structure during solid-phase elimination of solvate acetic acid fromN′-(5-nitrofurfurylidene)isonicotinic hydrazide monohydrate

A new crystal modification ofN-(5-nitrofurfurylidene)isonicotinic hydrazide (1) was studied by IR spectroscopy and X-ray structural analysis. The compound studied is the product of solid-phase desolvation of solvate hydrate1 of the composition [MeCOOH · 1 · H₂O]. Spontaneous elimination of solvate acetic acid results in complex overall rearrangement of the crystal structure and formation of a new system of intermolecular hydrogen bonds. The crystal hydrate of 1 : 1 composition (1c) was formed from compound1. In the crystal structure of1c molecules1 are linked in infinite chains through intermolecular C=O...W...H-N hydrogen bonds. The second hydrogen atom of the molecule of the crystallization water is involved in formation of an intermolecular O-H...N(Py) hydrogen bond with the nitrogen atom of the pyridine ring of the molecule of the adjacent chain.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2501–2505, October, 1996.     

Molecular inclusion in functionalized macrocycles part 10*: Crystal and molecular structure of ap-tert-butylcalix[6]arene hexapodand

Colourless prismatic crystals of (3) were obtained from ethanol/CH₂Cl₂ (1:1) solution, space groupP2₁/c,a=14.581(5),b=22.517(8),c=11.799(5) , =92.13(4)°. Refinement led to a final conventionalR value of 0.074 for 4247 reflections. The conformation of the molecule, which lies on a center of symmetry, is 1,2,3-alternate with one oligoethereal chain pointing inside the molecular cavity. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. 82011 (30 pages).For part 9, see [1]. Results presented in part at the Second International Symposium of Clathrate Compounds and Molecular Inclusion Phenomena, Parma, Italy, 1982.     

Host-guest chemistry. 2. Amine inclusion compounds of 2-[o-(triphenylphosphoranylidenamino)benzyliden]amino-1H-2,3-dihydroindazol-3-one. X-ray structure of its 1∶1∶1 inclusion complex with isopropylamine and water

The crystal and molecular structure is reported for the inclusion compound 2-[o-(triphenylphosphoranylidenamino)benzyliden]amino-1H-2,3-dihydroindazol-3-one/isopropylamine/water3b. The crystal structure consists of discrete dimeric salt-like aggregates joined together by strong N⁺–H...^–O–C hydrogen bonds between pairs of centrosymmetrically-related indazolonate anions and isopropylammonium cations. Six other inclusion compounds have been prepared and characterized by NMR [with propylamine (3a), withtert-butylamine (3c), withsec-butylamine (3d), withtert-pentylamine (3e), with 1-methylbutylamine (3f) and withiso-pentylamine (3g)]. Two different arrangements are found, both with the host being in the anionic form. The guests are either: (i) one protonated amine and one water molecule (3b and3f); or (ii) one protonated amine and the corresponding neutral amine (3a, 3c, 3d, 3e and3g). Supplementary Data relating to this article (structure factors, thermal components, hydrogen parameters and bond distances and angles, and¹³C-NMR shifts) are deposited with the British Library at Boston Spa, Wetherby, West Yorkshire, U.K., as Supplementary Publication No. SUP 82155 (23 pages).For Part 1, see Reference [1].     

Dansyl-Modified γ-Cyclodextrin as a fluorescent sensor for molecular recognition

The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usualF conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C₁₂H₁₇N₄OS⁺·I^– · 1.5 H₂O, monoclinic,P2₁/c, a=12.585(2), b=25.303(5), c=12.030(2) Å, =115.15(1)°,V=3468(1) ų,Z=8,D _c=1.606 g cm^–3,R=0.045 for 3328 observed reflections. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP. 82156 (13 pages).     

Novel tetrapodal molecules and reticular polyamides based on tetraphenylmethane

A series of tetrapodal derivatives of tetraphenylmethane were synthesized and characterized. Crystals obtained from tetrakis(4-acetamidophenyl)methane (1c) and from tetrakis[4-(4-aminobenzamido)phenyl]methane (2b) were analyzed by X-ray diffraction. The analyses pointed to the crystal packing problems faced by molecules of this kind by showing that the crystals, with composition1c·2DMF·2H₂O and2b·2DMSO, respectively, contained cocrystallized solvent molecules. The solvent molecules were found in both cases to be held in place by H bonds; in the case of2b·2DMSO they occupied channels running along theb axis. Tetrakis(4-aminophenyl)methane (1b) was used in polycondensation reactions with terephthalic acid, under modified Yamazaki conditions, to produce rigid aromatic polyamide networks. The networks were obtained as gels encompassing the whole volume of the reaction mixture. The volume of the gels did not vary noticeably upon changing the solvent (1-methyl-2-pyrrolidone) with less polar solvents, but the gels collapsed upon drying. No crystallinity was observed.