Synthesis and Characterization of the Isocyanide Ligated Centered Zirconium Halide Cluster [(Zr6Be)Cl12(CNXyl)6]

The first isocyanide ligated hexanuclear zirconium halide cluster is reported. The unoxidized [(Zr₆Be)Cl₁₂(CNXyl)₆] (CNXyl = 2,6-dimethylphenyl isocyanide) was obtained from the solid state precursor K₃Zr₆Cl₁₅Be by dissolution in CH₃CN in the presence of CNXyl. The CNXyl ligands occupy all the axial positions on the cluster. The compound was recrystallized from CH₂Cl₂ and Et₂O. [(Zr₆Be)Cl₁₂(CNXyl)₆].2CH₂Cl₂ crystallizes in the space group (#2) with a = 12.092(5) Å, b=12.728(5) Å, c = 14.102(8) Å, = 104.98(4)°, =107.11°, = 100.94°, V = 1919(2) ų, Z = l, R = 11.3% and R _W = 27.0%. For the bound isocyanide ligands, v _CN increases to 2140 cm^–1.     

Syntheses and structural characterizations of Fe4S4 cubane-like cluster compounds containing cycloalkylthiolate ligands

In a reaction system consisting of FeCl₂, tetrathiometallate and cycloalkylthiolate, two Fe₄S₄ cubanelike cluster compounds were obtained with the following crystallographic data: (PhCH₂NMe₃)₂ [ Fe₄S₄ (SC₅H₉)₄] (I), monoclinic space groupP2₁/c,a = 1.632 7(4),b=1.122 9(3),c = 2. 802 5(10) nm, β= 94.63(2)°, Z=4, andR= 0.074; (Et₄N)₂[F₄S4(SC₆H_lI)₄] (II), tetragod space group ,a = l.167 05(9),b = 1.167 06(2),c = 2.063 26(5) nm,Z = 2, D_obs = 1. 28 g/cm³, andR = 0. 078. The participation of cycloalkylthiolate ligand does not obviously arouse the change of the Fe₄S₄ core structure. Meanwhile, the influence of the cation on the structural symmetry of the Fe₄S₄ cluster dianion is also discussed. Project supported by the National Natural Science Foundation of China and the Climbing Program Foundation of China.     

Li2Br(NH2): Das erste ternäre Alkalimetallamidhalogenid

Li₂Br(NH₂): The First Ternary Alkali Metal Amide Halide The pseudobinary system LiNH₂/LiBr was investigated by X-ray methods. The crystal structure of the compound Li₂Br(NH₂) was solved by single crystal data: Li₂Br(NH₂): Pnma, Z = 8, a = 12.484(2) Å, b = 7.959(1) Å, c = 6.385(1) Å, Z(F_o) with (F_o)² ≧ 3σ(F_o)² = 348, Z (parameter) = 51, R/R_w = 0.019/0.021 Li₂Br(NH₂) crystallizes in a new type of structure. To one another isolated chains of [Li₂Li_4/2(NH₂)₂²⁺] show the motif of closest rod packing. They are connected via bromide ions in a distorted cubic primitive arrangement.     

Molecular structures of benzoylbenzo-12-crown-4 and diphenylacetylbenzo-12-crown-4 and possible reasons for different conformational states of their macrocycles

The molecular structures of (benzoyl)benzo-12-crown-4 (a=22.387,b=4.503,c=16.167 Å,d _calc=1.34 g cm^–3,Z=4, space groupP2₁ nc, DAR-UM, Cu-K,R=0.056) and (diphenylacetyl)benzo-12-crown-4 (a=8.866,b=23.337,c=10.737 Å;d _calc=1.25 g cm^–3,Z=4, space groupP2₁2₁2₁, DAR-UM, Cu-K, R=0.056) have been investigated. The differences in the conformations of the macrocycles and the degree of conjugation between the benzene ring orbitals and the lone pairs on the adjacent oxygen atoms in the macrocycle are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1906–1911, November, 1993.     

Zur Reaktion von Makrozyklen mit Lanthanoiden. I. Die Struktur von [Li(thf)][(C22H22N4)2Ce] · THF

On the Reaction of Macrocycles with Lanthanoids. I. The Crystal Structure of [Li(thf)][(C₂₂H₂₂N₄)₂Ce] · THF In THF CeBr₃ forms with [(TMTAA)Li₂] the paramagnetic doubledecker complex [Li(thf)][(TMTAA)₂Ce]. The complex crystallizes with 1 Mol THF per formula unit. The structure was characterized by X-ray single crystal structure analysis (space group C2 (No. 5), z = 6, a = 1741.8(2) pm, b = 1622.1(2) pm, c = 2540.4(3) pm, β = 104.72(1)°). The sandwich-like arrangement of the heterocyclic ligands leads to a quadratic-prismatic coordination of the Ce³⁺ ion. One macrocyclic ligand is additionally coordinated by a [Li(thf)]⁺ fragment. The coordination of the Li ion is square pyramidal.     

咪唑-金属配合物的合成、性质及其与DNA的作用机理

Three hexakis（imidazole）metallo complexes of Co, Cd and Ni were synthesized and spectroscopically characterized. The crystal and molecular structures have been determined by X-ray crystallography analysis. The metal ions have an octahedral geometry with the MN6 chromophore. The electrochemical experimental results indicate that both [Co（Im）6]C12·2HCl·2H2O （1） and [Ni（Im）6]C12·4H2O （3） [Im=imidazole] could interact with DNA mainly by intercalation.     

Synthesis and crystallographic studies of two new 1,3,5‐triazines

The synthesis and characterization of two new 1,3,5‐triazines containing 2‐(aminomethyl)‐1H‐benzimidazole hydrochloride as a substituent are reported, namely, 2‐{[(4,6‐dichloro‐1,3,5‐triazin‐2‐yl)amino]methyl}‐1H‐benzimidazol‐3‐ium chloride, C₁₁H₉Cl₂N₆⁺·Cl^? ( 1 ), and bis(2,2′‐{[(6‐chloro‐1,3,5‐triazine‐2,4‐diyl)bis(azanediyl)]bis(methylene)}bis(1H‐benzimidazol‐3‐ium)) tetrachloride heptahydrate, 2C₁₉H₁₈ClN₉²⁺·4Cl^?·7H₂O ( 2 ). Both salts were characterized using single‐crystal X‐ray diffraction analysis and IR spectroscopy. Moreover, the NMR (¹H and ¹³C) spectra of 1 were obtained. Salts 1 and 2 have triclinic symmetry (space group P) and their supramolecular structures are stabilized by hydrogen bonding and offset π–π interactions. In hydrated salt 2 , the noncovalent interactions yield pseudo‐nanotubes filled with chloride anions and water molecules, which were modelled in the refinement with substitutional and positional disorder.     

Three polymorphs of 3‐(3‐phenyl‐1H‐1,2,4‐triazol‐5‐yl)‐2H‐1‐benzopyran‐2‐one formed from different solvents

The polymorphic study of 3‐(3‐phenyl‐1H‐1,2,4‐triazol‐5‐yl)‐2H‐1‐benzopyran‐2‐one, C₁₇H₁₁N₃O₂, was performed due to its potential biological activity and revealed three polymorphic modifications in the triclinic space group P, the monoclinic space group P2₁ and the orthorhombic space group Pbca. These polymorphs have a one‐column layered type of crystal organization. The strongest interactions between the molecules of the studied structures is stacking between π‐systems, while N—H…N and C—H…O hydrogen bonds link stacked columns forming layers as a secondary basic structural motif. C—H…π hydrogen bonds were observed between neighbouring layers and their role is the least significant in the formation of the crystal structure. Packing differences between the polymorphic modifications are minor and can be identified only using an analysis based on a comparison of the pairwise interaction energies.     

[Bi6O4.5(OH)3.5]2(NO3)11: a new anhydrous bismuth basic nitrate. Synthesis and structure determination from twinned crystals

The bismuth basic nitrate [Bi₆O_4.5(OH)_3.5]₂(NO₃)₁₁ crystallizes in the monoclinic space group P2₁ with , , , β=107.329(17)° and . Its structure has been determined from , twinned crystal X-ray data (16 781 reflections, 683 parameters, R=0.0703). It is built upon [Bi₆O_x(OH)_8−x]^(10−x)+, x=4 and x=5 hexanuclear complexes and nitrate groups. The polycationic entities are linked to the nitrate anions either by hydrogen bonds or through bismuth-oxygen coordination. Even at , the [Bi₆O₄(OH)₄]⁶⁺ and [Bi₆O₅(OH)₃]⁵⁺ polycations could not be observed as such, the crystal structure refinement only detecting an average [Bi₆O_4.5(OH)_3.5]^5.5+ polycation. To prove the presence of both hexanuclear complexes in the structure, we report the existence of a correlation between the bismuth-linked oxygen bond-valence parameters and the presence, or not, of hydroxyl groups. Moreover, the Raman spectrum of the new anhydrous bismuth basic nitrate is compared to those of [Bi₆O₅(OH)₃](NO₃)₅·3H₂O, [Bi₆O₄(OH)₄](NO₃)₆·4H₂O, and two yet uncharacterized bismuth nitrates.