Azine bridged silver coordination polymers: Powder X-ray diffraction route to crystal structure determination of silver benzotriazole

In continuation of our interest in solid-state structures of silver complexes of photographic importance, the structure for silver benzotriazole (AgBZT), has now been obtained. The preferred method for solving crystal structures is via single-crystal X-ray diffraction (XRD). However, for some materials, growing single crystals of appropriate size and quality is often difficult or even impossible. AgBZT is an example of such a silver complex with poor solubility. The usual routes to preparing single crystals using recrystallization from a cooperating solvent resulted in polycrystalline powder samples. We propose a crystal structure for AgBZT, solved from synchrotron X-ray powder diffraction data, using a direct-space Monte Carlo simulated annealing approach. AgBZT crystals are monoclinic, (P2₁/c), with unit cell dimensions, a=14.8052(3) Å, b=3.7498(4) Å, c=12.3495(12) Å, and β=114.200(6)°. The AgBZT complex is constructed from all three of the Benzotriazole (BZT) nitrogens bonding to a separate silver atom. As a consequence of this bonding mode, the structure is a highly cross-linked, coordination polymer.     

UV stabilizers bonded to transition metals: Synthesis and X-ray structure of 2-(2′-hydroxyphenyl)benzotriazole-oxovanadium(IV) and -dioxomolybdenum(VI) complexes

The UV-stabilizer 2-(2′-hydroxy-5′-methylphenyl)benzotriazole (Tinuvin P, LH) has been used as a monoanionic bidentate ligand for complexing oxocations. Displacement of acacH from [VO(acac)₂] and [MoO₂(acac)₂] gave [*VO(acac)₂*(μ-L)] (2) and [cis-O₂Mo(acac)L] (3) respectively, as crystalline compounds. Their structure has been determined by an X-ray analysis showing the structural changes occurring upon coordination. The UV spectrum of Tinuvin P is significantly affected by complexation.     

苯并三氮唑及其羧酸酯衍生物对铜缓蚀机理的分子动力学模拟研究

用分子动力学(MD)方法, 模拟计算了5种铜缓蚀剂[苯并三氮唑(BTA)、苯并三氮唑-5-羧酸甲酯(MBTC)、苯并三氮唑-5-羧酸丁酯(BBTC)、苯并三氮唑-5-羧酸己酯(HBTC)、苯并三氮唑-5-羧酸辛酯(OBTC)]与Cu₂O晶体的相互作用. 结果发现, 中性条件下缓蚀剂分子与Cu₂O晶体的结合能均大于酸性条件下的数值, 但两种条件下结合能的大小排序均为OBTC＞HBTC＞BBTC＞MBTC＞BTA. 对体系各种相互作用以及对关联函数g(r)的分析表明, 体系结合能主要由库仑作用提供, Cu₂O晶体中的Cu原子与缓蚀剂分子中的N原子之间形成了配位键. 在与Cu₂O(001)晶面结合过程中, BTA及其衍生物分子发生了扭曲变形, 但形变能远小于体系的非键相互作用能.     

Synthesis of N-（α-Alkoxyalkyl）benzotriazoles Catalyzed by Acidic Ionic Liquid at Room Temperature

N-（α-Alkoxyalkyl）benzotriazoles were synthesized via the condensation of benzotriazole with various aldehydes and alcohols catalyzed by acidic ionic liquid [hmim]HSO4 at room temperature. The yield was up to 99%. This novel method was effective when triethoxymethane was utilized instead of alcohols. Moreover, acidic ionic liquid could be reused easily with no significant degradation of its catalytic activity.     

Crystal structure and characterization of the bis(n-benzyl-benzotriazole-n3)-dichloro Co(II) complex: CoCl2(C6H4N3CH2Ph)2

The structure of [CoCl₂(C₆H₄N₃CH₂Ph)₂] has been determined by X-ray crystallography. It is also characterized by elemental analysis, IR and electronic spectroscopy, and by thermogravimetric differential thermal analysis. It crystallizes in the monoclinic system, space group C2/c, with lattice parameters a = 16.133(3) , b = 11.355(2) , c = 15.637(3) , = 117.22(3)°, and Z = 8. The crystal structure of the title compound consists of monomeric molecules of [CoCl₂(C₆H₄N₃CH₂Ph)₂] with slightly distorted tetrahedron geometry for the CoCl₂N₂ chromophore. The thermal gravimetry (TG) data indicate that there are four decomposition steps with five endothermic peaks. The final product of the thermal decomposition is CoCl₂. Elemental analysis and the electronic and IR spectra are in agreement with the structural data.Original Russian Text Copyright © 2004 by F. Jian, H. Wang, and H. XiaoTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 723–728, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Preparation ,Structural Characterization and Luminescent Property of Binucleasr Silver（Ⅰ）Complex Formed by Benzotriazole and 1—Hydroxymethyl Benzotriazole

Dinuclear silver (I) six‐membered ring complex [Ag₂ (bta)₂ ‐(hmbta)₂] (ClO₄)₂ (3) has been synthesized by the reaction of benzotriazole (bta) (1) and 1‐hydroxymethyl benzotriazole (hmbta) (2) with Ag (CH₃CN)₄ClO₄. The structures of compound 2 and Complex 3 have been studied by single crystal X‐ray diffraction analysis. The change of luminescent intensity of 1, 2 and 3 was reported. Compound 2 crystallizes in the monoclinic system with space group P2 (1)/c, a = 0.7655 (10) nm, b = 1.0126 (14) nm, c =0.9502 (13) nm, β = 95.07 (2)°, V = 0.7337 (17) nm³ and Z = 4. Complex 3 crystallizes in the triclinic system with space group P1, a = 0.73611 (18) nm, b = 0.9152 (2) nm, c = 1.2277 (3) nm, β = 87.170 (5)°, V = 0.8221 (3) nm³ and Z = 1. The main structural feature of complex 3 is a symmetric dinuclear six‐membered ring formed by two silver (I) atoms and four N‐atoms from two benzotriazoles. The second structural feature of complex 3 is the τ‐τ stacking interaction between two adjacent molecular planes, which forms the two‐dimentional layer structure. Besides, compared with 2, the luminescent intensity of complex 3 shows a remarkable enhancement.     

α, α'-二胺基二苄基硒醚的合成

本文以苯骈三氮唑、胺和苯甲基醛为原料,发现Mannich反应,生成胺烷基化的苯骈三氮唑衍生物。在此衍生物中,苯骈三氮唑基是亲核取代反应的良好离去基团,易被强亲核试剂的硒负离子取代,生成对称α,α'-二胺基二苄基硒醚。反应易进行,产率较高,产物均为固体,易提纯。这是合成含氮原子的对称硒醚的较好方法。     

Crystal and molecular structure of 1-(trimethylsilylmethyl)benzotriazole

The crystal and molecular structure of 1-(trimethylsilylmethyl)benzotriazole has been established by X-ray diffraction (XRD) analysis. The coordination polyhedron of the silicon atom in this molecule is a tetrahedron. The bond lengths and angles of the 1-(trimethylsilylmethyl)benzotriazole molecule were compared with those of related crystal structures.     

Theoretical investigation into coordination and selectivity of uranyl-unilateral benzotriazole salophens (X = O/S) for R/S-triadimefons

The design of new uranyl-ligands (uranyl-Ls) is of great significance for the separation and utilization of uranium. In this paper, the triazole group was introduced into uranyl-salophen (uranyl-S) to form new asymmetric uranyl-unilateral benzotriazole salophen (uranyl-UBS); we further replaced two oxygen atoms of uranyl-UBS with two sulfur atoms to generate uranyl-unilateral benzotriazole thio-salophen (uranyl-UBTS) as a new receptor. Then, we comprehensively explored coordination models of uranyl-UBS and uranyl-UBTS with R/S-triadimefons (R/S-TDFs) enantiomers as the guests using density functional theory calculations at the B3LYP//RECP/6-311G** level; we then investigated enantioselectivity recognition of the new receptors to the guests R/S-TDFs. The results indicated that the uranium atoms of the receptors uranyl-S, uranyl-UBS and uranyl-UBTS could coordinate with the carbonyl oxygens in guests R/S-TDFs to form complexes of guest-receptors R/S-TDFs-uranyl-Ls that exhibited two stable V-shaped structures with quite different properties. It was found that the coordination ability to the guests R/S-TDFs is uranyl-UBTS > uranyl-UBS > uranyl-S, while the enantioselectivity for the guests is uranyl-UBTS > uranyl-S > uranyl-UBS and, when the receptor is the same, R-TDF has stronger coordination ability than S-TDF. These results provide information and theoretical supports for the experiments of asymmetric uranyl-UBS with R/S-TDFs, and produce a reference for further exploring the coordination characteristics of asymmetric uranyl-salophen with the triazole derivatives.     

2-十二烷基二硫代-4-苯基-1,3,4-噻二唑-5-硫酮的合成及其对铜的缓蚀性能

合成了2-十二烷基二硫代-4-苯基-1,3,4-噻二唑-5-硫酮(DPTT),用元素分析、IR1、H NMR等技术对化合物进行了结构表征.采用动态旋转挂片法考察了DPTT和苯并三唑(BTA)复配时对铜的缓蚀作用.结果表明,单一DPTT在浓度为3.0 mg/L时缓蚀效果最佳;DPTT与BTA复配使用时显示出较好的协同效应,1.0 mg/L DPTT和1.0 mg/L BTA复配时缓蚀效果最好.