Small-ring inclusion hosts. 4. X-ray crystal structures oftrans-3,3-Bis(4-methylphenyl)cyclopropane-1,2-dicarboxylic acid and of its inclusion complex with Dimethyl Sulphoxide (1:2)

The crystal structures of the unsolvatedtrans-3,3-bis(4-methylphenyl)cyclopropane-1,2-dicarboxylic acid (1) and of its inclusion compound with dimethyl sulphoxide,1·DMSO (1:2), have been studied by X-ray diffraction. Crystals of1 show triclinic symmetry (P ) withZ = 4 and the unit cell dimensionsa = 7.617(2),b = 15.321(4),c = 15.297(3) Å, = 109.76(2), = 103.47(1), = 89.87(2)°. FinalR = 0.037 for 3601 reflections collected atT = 153(1) K. Crystals of1·DMSO (1: 2) are monoclinic (P2₁/n) withZ = 4 and cell dimensionsa = 10.744(1),b = 10.806(1),c = 21.302(2) Å, = 101.68(1)°. The clathrate structure was refined toR = 0.034 for 1671 reflections obtained atT = 173(1) K. In the unsolvated host compound cyclic pairs of O-H ... bonds, commonly observed in carboxylic acids, couple the carboxylic functions two by two, thus giving rise to endless chains due to the bifunctionality and thetrans position of the acid groups of1. The complex with DMSO as guest, however, consists of distinct hydrogen-bonded 1:2 host-guest associates, held together by weak intermolecular interactions.Supplementary Data relating to this article have been deposited with the British Library at Boston Spa, Wetherby, West Yorkshire, U.K., as Supplementary Publication No. SUP 82139 (32 pages).For Part 3, see Reference [1].     

1,3-Bis(triphenylphosphonium-ylidyl)cyclotetraphosphane

1,3-Bis(triphenylphosphonium-ylidyl)cyclotetraphosphines The title compounds 3a , b result from the condensation of the ylidyldichlorophosphines Ph₃PCR? PCl₂ 1a , b (R = Me, 3-Tol) with phenyl bis(trimethylsilyl)phosphine 2 . Analysis of the ³¹P-NMR spectra and the X-ray structure investigation of 3a demonstrate a folding of the four-membered ring and an all-trans orientation of the substituents.     

6,6′-Bis(1,5-diazabicyclo[3.1.0]hexane)

The interaction of 1,3-diaminopropane with glyoxal and NaOCl in water at pH 9.5–10.5 afforded the previously unknown 6,6′-bis(1,5-diazabicyclo[3.1.0]hexane). According to X-ray diffraction data, both bicyclic fragments of the title compound adopt a boat conformation. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 623–625, March, 1999.     

Pentamethylcyclopentadienylselenium derivatives VI: Synthesis and characterisation of ferrocenyl(pentamethylcyclopentadienyl)selenium

The novel mono(cyclopentadienyl)selenium derivatives, Se(C₅Me₄R)Fc (Fc = ferrocenyl, [Fe(η⁵-C₅H₅)(η⁵-C₅H₄)]; R = H or Me) have been prepared by treatment of diferrocenyl diselenide with LiC₅Me₄R, and characterised by NMR spectroscopy and mass spectrometry. The structure of Se(C₅Me₅)Fc has been confirmed by X-ray crystallography, and its redox properties have been examined by cyclic voltammetry. It reacts with [W(CO)₅(THF)] to form [W₂(μ-SeFc)₂(CO)₈] via C-Se bond cleavage.     

Syntheses and Structures of Blue Luminescent Zinc(Ⅱ) Complexes with 2,6-Bis(imino)pyridyl Ligands

Luminescent coordination compounds with nitrogen-containing ligands have attracted much attention due to their good performance in sensor and electroluminescent device techniques[1-17]. To develop new luminescent materials, a large number of d10 metal complexes, especially zinc complexes, with the nitrogen-containing ligands have been synthesized and their luminescence behaviour have been studied[1-11]. It has been found that for a given complex, the size of the π-conjugated system of the ligand and the electronic effect of substituents at the ligand are important factors for modulating its luminescent properties[5,8,9].     

Synthesis and Crystal Structure of 2,3-Bis(dinitrofluoromethyl)-1,4-dioxane

For the first time the dinitromethyl group was modified to dinitrofluoromethyl group in the series of aliphatic polynitro compounds in the case of the reaction of 1,1,4,4-tetranitro-2,3-butanediol diacetate with ammonium fluoroxysulfate in the presence of sodium bicarbonate and ethylene glycol. Previously unknown 2,3-bis(dinitrofluoromethyl)-1,4-dioxane was synthesized. Its structure was determined by X-ray diffraction analysis.     

Synthesis and Crystal Structure of 2,5—Bis（morpholino）—3,4—bis（p—chlorophenyl）thiophene

1 INTRODUCTION -Thiocarbonylthioformamide synthesized in 1980[1, 2] is a class of stable and almost unexplored compounds[3]. We have reported the reaction of - thiocarbonylthioformamides in our previous paper[4]. Here, we will report a novel synthesis of 2 by the reaction of 1 and trimethyl phosphite in refluxing xylene. In order to determine the structure of 2, X- ray crystallographic study was carried out. 2 EXPERIMENTAL 2. 1 Preparation of the title compound Trimethyl phosph…     

Liquid structure of benzene and its derivatives as studied by means of X-ray scattering

The liquid structures of benzene, toluene, aniline, benzaldehyde and nitrobenzene were investigated by the X-ray scattering method. The X-ray scattering data were analysed by a method without constructing any structure models. The obtained liquid structure of benzene is different from the previous X-ray scattering results which were derived from the quasi-lattice structure for the liquid based on the crystal structure of benzene. This is because a molecular arrangement which is not found in the crystal structure is left out of consideration. In liquid toluene, benzaldehyde and nitrobenzene, two molecules are associated with the dipole–dipole interaction in the antiparallel fashion. Two aniline molecules are hydrogen-bonded in liquid aniline. The third molecule weakly interacts with the other two in liquid toluene, aniline and benzaldehyde. In liquid nitrobenzene, the parallel dipole–dipole interaction of the third molecule with another one is present in the coplanar form. The substituent effect on the liquid structures is discussed.     

1,3-Bis(alkylimino)isoindolinates of rare earth metals: Synthesis,molecular structure and photoluminescence

The rare earth metal isoindolinates Ln(ⁱPrL)₃ (Ln = Sc (1), Y (2), Eu (3), Dy (4), Yb (5); ⁱPrL = 1,3-bis(isopropylimino)isoindolinate anion) and [(MeL)Ce]₂(μ-MeL)₄ (6) (MeL = 1,3-bis(methylimino)isoindolinate anion) were synthesized by reactions of the amides Ln[N(SiMe₃)₂]₃ with 1,3-bis(isopropylimino)isoindoline (ⁱPrLH) or 1,3-bis(methylimino)isoindoline (MeLH), respectively. The X-ray diffraction study revealed that in monomeric molecules of the isopropyl-substituted compounds 2 and 4 the cations Ln³⁺ are η²-coordinated by three isoindolinate ligands. The methyl-substituted 6 exists in a crystal as a dimer containing two terminal η²-coordinated ligands and four bridging isoindolinate ligands two of which are bonded to Ce atoms in η³ fashion (η:η:η-N,N,N) but two others in η⁴ manner (η:η²:η-N,N,N). All the obtained complexes in solutions exhibited ligand-centered photoluminescence, the spectra of which consist of one broadened band with a maximum at 400–450 nm.     

New acenaphthene-1,2-diimine and its reduction to the tetraanion. Molecular structures of 1,2-bis[(trimethylsilyl)imino]acenaphthene and its lithium derivatives

1,2-Bis[(trimethylsilyl)imino]acenaphthene (1) was synthesized by the reaction of acenaphthenequinone with (Me₃Si)₂NLi in toluene followed by treatment of the reaction product with trimethylchlorosilane. The dianionic derivative [(tms-BIAN)Li₂]₂ (3) was obtained as the final product by reduction of compound 1 with lithium in toluene, whereas reduction in diethyl ether afforded the tetraanion [(tms-BIAN)Li₄(Et₂O)₃]₂ (5). The formation of the paramagnetic mono-and trianions in solution was confirmed by ESR spectroscopy. Compounds 3 and 5 were isolated in the crystalline state and characterized by elemental analysis, IR spectroscopy, and NMR spectroscopy. The crystal structures of 1, 3, and 5 were established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 697–705, April, 2006.     

Synthesis and Crystal Structure Determination of 6-(N-Isopropyl)Amidino-2-Methylbenzothiazole Hydrochloride Monohydrate and 2-Amino-6-(N-Isopropyl)Amidinobenzothiazole Hydrochloride

Two novel substituted amidino-benzothiazoles 6-(N-isopropyl)amidino-2-methylbenzothiazole 4 and 2-amino-6-(N-isopropyl)amidinobenzothiazole 6 were prepared in multistep synthesis in form of hydrochloride salts. They were characterized by means of IR, ¹H, and ¹³C-NMR spectroscopy and elemental analysis. The crystal structures have been also determined by X-ray analysis. Both compounds crystallize as colorless prisms in the triclinic crystal system, space group P . Crystal data: (4) a = 8.741(4) Å, b = 9.602(7) Å, c = 9.946(2) Å, = 63.94(3)°, = 79.18(2)°, = 79.68(3)°, V = 732.1(6) ų, Z = R = 0.0396; a = 8.106(1) Å, b = 9.148(2) Å, c = 9.291(2) Å, = 104.83(1)°, = 103.36(2)°, = 90.62(1)°, V = 646.2(2) ų , Z = 2, R = 0.0376. The bond distances and angles in both structures are almost similar. Between these two structures was found the difference in the orientation of the 6-(N-isopropyl)amidino moiety with respect to the benzothiazole ring. In the crystal structures of the both compounds the intermolecular hydrogen bonds form three-dimensional networks.     

The Synthesis and Structure of (1-(Diphenylphosphino)-1 - (Phenylthio)Ferrocene)Tricarbonyliron(O) (ptppf)Fe(CO)3

The complex (ptppf)Fe(CO)₃ has been prepared in high yield by the reaction of ptppf, l-(diphenyl-phosphino)-l'-(phenylthio)ferrocene, with (cis-cyclooctene)₂-Fe(CO)₃ in THF at ?60°C. The complex has been characterized by IR, ³¹P NMR, mass spectrometry and single-crystal X-ray diffraction. This compound is the first example of a ferrocenyl ligand having both sulfur and phosphorus donor atoms bound to a Fe(CO)₃ moiety. X-ray crystallography shows that the two cyclopentadienyl rings are approximately eclipsed, a rotation of 13° from exactly eclipsed conformation. The tricarbonyl iron center has a trigonal bipyramidal geometry with sulfur occupying the equatorial site and phosphorus the axial site. Crystals of (ptppf)Fe(CO)₃ are monoclinic, with a = 11.645(2), b = 14.304(1), c = 17.075(2) Å,β = 109.23(3)°, Z = 4, and space group P 2₁/n. The structure was solved according to the heavy-atom method and refined by full-matrix least-squares procedures to R = 0.037 for 2098 reflections with I ≥ 2.5σ(I).     

Synthesis and Crystal Structure of a New Coordination Polymer: {[AgL]ClO_4}_n(L = 2,5-Bis(3-pyridinylmethylthio)-l,3,4-thiadiazole)

The title complex {[AgL]ClO4}n(L=2,5-bis(3-pyridinylmethylthio)-1,3,4-thiadiazole) was synthesized by the reaction of Ag(I) salt and a novel flexible ligand L.Its structure was determined by X-ray crystallography with the following data:monoclinic,space group P21/n,a=16.5068(13),b=7.6548(4),c=16.5521(13),β=115.119(3)o,V=1893.7(2)3,Z=4,Dc=1.893 g/cm3,μ=1.565 mm-1,F(000)=1072,C14H12AgClN4O4S3,Mr=539.78,T=293(2) K,S=1.067,the final R=0.0342 and wR=0.0870.The silver ion in the complex is in a trigonal coordin...     

Crystal and molecular structures of tris (p-methoxyphenyl)- and tris(2,4, 6-trimethylphenyl)tin(IV) acetates

The crystal and molecular structures of tris(p-anisyl)tin acetate (1) (p-anisyl = p-methoxyphenyl) and trimesityltin acetate (2) (mesityl = 2,4,6-trimethylphenyl) have been determined. Both have monomeric structures with the acetate group acting as an asymmetric bidentate ligand. Bond valence analysis of (1) and (2) and other Ph₃SnO₂CR suggest however that the carboxylate ligand effectively occupies a single bonding position at tin. Thus in (1) and (2) the tin atom is in a chemical environment equivalent to that found in four-coordinate R₃Sn-X systems based on tetrahedral geometry.     

Synthesis and Crystal Structure of a One-dimensional Ladder-like Complex [Cu2(L)(dca)2]n (dca = [N(CN)2]-,L = 1,4-Bis(3-furanyl)-2,3-diaza-1,3-butadiene)

A new Cu(I)-dicyanamide with formula [Cu2(L)(dca)2]n (dca = dicyanamide anion, L = 1,4-bis(3-furanyl)-2,3-diaza-1,3-butadiene) has been synthesized and structurally characterized.The complex crystallizes in the monoclinic system, space group P21/n with a = 9.271(2), b = 7.7355(16), c = 11.967(3) -, β = 102.693(3)°, V = 837.3(3) -3, Z = 4, Mr = 223.68, Dc = 1.775 g/cm3, μ(MoKα) = 2.567 mm-1, F(000) = 444, R = 0.0782 and wR = 0.2582 for 951 observed reflections (I > 2σ(I)).Single-crystal X-ray analysis reveals that the copper atom is three-coordinated by two nitrogen atoms from two dicyanamide anions and another one from the ligand, and each copper atom is connected by two [N(CN)2]- anions to form an infinite double-stranded bridge fashion leading to 1D ladder-like motifs.     

Electronic Structure and Magnetic Properties of a High-Spin MnIII Complex: [Mn(mesacac)3] (mesacac=1,3-Bis(2,4,6-trimethylphenyl)-propane-1,3-dionato)

Metal acetylacetonates of the general formula [M(acac)₃] (M^III=Cr, Mn, Fe, Co) are among the best investigated coordination compounds. Many of these first-row transition metal complexes are known to have unique electronic properties. Independently, photophysical research with different β-diketonate ligands pointed towards the possibility of a special effect of the 2,4,6-trimethylphenyl substituted acetylacetonate (mesacac) on the electron distribution between ligand and metal (MLCT). We therefore synthesized and fully characterized the previously unknown octahedral title complex. Its solid-state structure shows a Jahn-Teller elongation with two Mn−O bonds of 2.12/2.15 Å and four Mn−O bonds of 1.93 Å. Thermogravimetric data show a thermal stability up to 270 °C. High-resolution mass spectroscopy helped to identify the decomposition pathways. The electronic state and spin configuration of manganese were characterized with a focus on its magnetic properties by measurement of the magnetic susceptibility and triple-zeta density functional theory (DFT) calculations. The high-spin state of manganese was confirmed by the determination of an effective magnetic moment of 4.85 μ_B for the manganese center.