Two novel trinuclear cluster-based coordination polymers with 2,6-Di-imidazol-1-yl-pyridine: solvothermal syntheses,crystal structures,properties and Hirshfeld surface analysis

Two novel trinuclear cluster-based coordination polymers {[M₃(dip)(AcO)₆]·(X)}_n (1, M = Cu, X = CH₃OH; 2, M = Co, X = 2H₂O) (dip is 2,6-Di-imidazol-1-yl-pyridine), have been synthesised and structurally determined by single crystal X-ray diffraction, element analysis. Crystallographic unit of 1 consists of three Cu(II), six acetic ions, one dip ligand and one methanol molecule, which formed 1D chain through acetic bridges. The 1D chain further constructed 2-D network through dip ligand bridge which formed 3-D network through π···π interaction. Crystallographic unit of 2 consists of three Co(II), six acetic ions, one dip ligand and two water molecules. The trinuclear unit further formed a dimmer through dip ligand bridge which constructed 1-D through dip ligand bridge. The 1D chain further constructed 2-D network through π···π interaction. IR and UV–vis spectrum properties of 1 and 2 were studied. In addition, Hirshfeld surface analysis was also studied for 1.     

两个salen型卤代希夫碱Ni(Ⅱ)配合物的合成、晶体结构及Hirshfeld表面分析

通过硝酸镍与卤代希夫碱在甲醇溶液中反应,合成了2个Ni（Ⅱ）希夫碱配合物[Ni（3,5-Cl-salcy）]（1）和[Ni（3-Cl-salcy）]（2）,（3,5-Cl-salcyH₂=N,N′-（±）-双（3,5-二氯水杨基）-1,2-环己二胺; 3-Cl-salcyH₂=N,N′-（±）-双（3-氯水杨基）-1,2-环己二胺）。通过X射线衍射测定了2个配合物的结构。结构分析表明2个配合物的基本单元均为Ni（Ⅱ）离子通过与希夫碱配体的[N₂O₂]原子配位构成相似的平面型单核配合物。Platon软件分析表明配合物1中并不存在任何氢键,配合物2也仅存在非经典氢键。通过Hirshfeld表面分析法对2个配合物晶体结构中弱交换作用的分析结果表明,虽然卤原子构成的氢键相对较弱,但是C-H…X在稳定三维超分子晶体结构中起着非常重要的作用;此外,通过2个配合物的对比发现,配体中卤原子数量的不同对于晶体中弱交换作用的占比可以起到非常重要的影响。     

Organostannate derivatives of dicyclohexylammonium hydrogen 2,6-pyridinedicarboxylate: solution/solid-state 13C,119Sn NMR and in vitro antitumour activity of bis(dicyclohexylammonium) bis(2,6-pyridinedicarboxylato)dibutylstannate,and the crystal structure of its monohydrate

Bis(dicyclohexylammonium) bis(2,6-pyridinedicarboxylato)dibutylstannate is assigned seven-fold coordination at tin on the basis of its ¹¹⁹Sn CP/MAS NMR chemical shift (δ=−424.9 ppm). The assignment has been corroborated by a crystal structure determination of its monohydrate, whose tin atom has the trans -C₂SnNO₄ pentagonal bipyramidal [Sn–C=2.040(9), 2.067(8) Å; C–Sn–C =168.9(5)°] geometry. One 2,6-pyridine- dicarboxylato group chelates to the tin atom (Sn–O=2.234(4), 2.260(4); Sn–N =2.279(5) Å) whereas the other binds through only one carboxyl –CO₂ end (Sn–O=2.416(5), 2.441(5) Å). Hydrogen bonds link the cation and the stannate into a linear chain parallel to the b -axis. The lattice water molecule is hydrogen-bonded to the free carboxyl end. The anhydrous compound showed higher in vitro antitumor activity than those of carboplatin and cisplatin when screened against breast (MCF-7, EVSAT), colonic (WiDr), ovarian (IGROV) and renal (A498) carcinoma, and melanoma (M19 MEL) cell lines. © 1997 by John Wiley & Sons, Ltd.     

三例基于5-(二甲基氨基)间苯二甲酸的锌(Ⅱ)/铜(Ⅱ)配合物的合成、晶体结构、Hirshfeld表面分析和荧光性质

利用配体 5-(二甲基氨基)间苯二甲酸(H₂dia)和咪唑(mdz)分别与锌(Ⅱ)和铜(Ⅱ)金属盐反应,制备了 3 例过渡金属配合物[Zn(dia)(mdz)₂]·2H₂O (1)、[Cu(dia)(mdz)₂(DMF)] (2)和[Cu(dia)(mdz)₂]·H₂O (3)。利用单晶 X射线衍射、元素分析、红外光谱、热重和Hirshfeld表面分析对其进行了结构表征。结果表明配合物1和2为一维线状链,1中每个四配位的Zn(Ⅱ)处于变形四面体中心,2中Cu(Ⅱ)中心拥有五配位的三角双锥几何构型。改变合成溶剂条件得到锯齿形一维链状配合物3,其四配位Cu(Ⅱ)中心展现出对称平面四边形构型。上述结果说明,金属离子几何构型以及合成溶剂可能对配合物结构具有重要影响。丰富的分子间氢键帮助3例配合物形成稳定的三维超分子结构。热重分析表明,3例配合物均具有良好的热稳定性。固体荧光分析表明配合物1具有较强荧光性,而配合物2和3荧光强度均远低于配体。     

三例基于5-(二甲基氨基)间苯二甲酸的锌(Ⅱ)/铜(Ⅱ)配合物的合成、晶体结构、Hirshfeld表面分析和荧光性质

利用配体 5-(二甲基氨基)间苯二甲酸(H₂dia)和咪唑(mdz)分别与锌(Ⅱ)和铜(Ⅱ)金属盐反应,制备了 3 例过渡金属配合物[Zn(dia)(mdz)₂]·2H₂O (1)、[Cu(dia)(mdz)₂(DMF)] (2)和[Cu(dia)(mdz)₂]·H₂O (3)。利用单晶 X射线衍射、元素分析、红外光谱、热重和Hirshfeld表面分析对其进行了结构表征。结果表明配合物1和2为一维线状链,1中每个四配位的Zn(Ⅱ)处于变形四面体中心,2中Cu(Ⅱ)中心拥有五配位的三角双锥几何构型。改变合成溶剂条件得到锯齿形一维链状配合物3,其四配位Cu(Ⅱ)中心展现出对称平面四边形构型。上述结果说明,金属离子几何构型以及合成溶剂可能对配合物结构具有重要影响。丰富的分子间氢键帮助3例配合物形成稳定的三维超分子结构。热重分析表明,3例配合物均具有良好的热稳定性。固体荧光分析表明配合物1具有较强荧光性,而配合物2和3荧光强度均远低于配体。     

Crystal growth,structural, spectral,optical, DFT analysis and Z-scan analysis of pyridine-1-ium-2-carboxylatehydrogenbromide (PHBr) for optoelectronic and nonlinear optical applications

A single crystal of Pyridine-1-ium-2-carboxylatehydrogenbromide (PHBr) was grown using the Slow Evaporation Solution Technique. Using Single Crystal X-Ray Diffraction analysis, the crystal lattice characteristics and molecular structure of the grown crystal of PHBr were found and it corresponds to the Triclinic crystal system with space group Pī. Intra and intermolecular interactions were visualized using Hirshfeld surface analysis. The theoretical calculation conducted by Density Functional Theory (DFT) and it is well agreed with the experimental results. The Molecular optimized geometry, FT-IR and HOMO-LUMO energy gap were computed using the B3LYP level of theory with a 6-31 + G (d,p) basis set. The FT-IR spectrum studies are given here to look at the modes of vibration of numerous functional groups found in the PHBr crystal. The measurements of UV–visible NIR transmittance show that the crystal has a high transmittance over the whole visible spectrum. The Z-scan approach is used to perform third-order nonlinear optical (NLO) investigations on a PHBr crystal and optical properties such as linear and nonlinear refractive index are computed.     

Crystal structure and solid state computational (DFT/Hirshfeld surface) study for probing a new efficient and recyclable oxidation reagent, 1,2-ethandiylbis(triphenylphosphonium) peroxodisulfate dihydrate

A new, efficient and recyclable reagent, 1,2-Ethandiylbis(triphenylphosphonium) peroxodisulfate dihydrate, for the oxidation of benzylic alcohols has been synthesized and characterized by IR, NMR spectroscopy, and single crystal X-ray crystallography. Using the title compound, the results indicate that the oxidation reactions are rapid, take place under mild reaction conditions, easily to work-up and high yielding. The Hirshfeld surface and associated finger print plots were derived from the X-ray structure to visualize the significant nonclassical C-H ??? O/π interactions in the crystal packing. The geometry, vibrational spectroscopy and electronic properties of the bis(triphenylphosphonium) dication have also been investigated by various DFT computational methods.     

Hydrothermal Synthesis,Structural Investigation and Characterization of an Organic-inorganic Hybrid, [Co(BⅡM)_3]_2H[BW_(12)O_(40)]·7H_2O

An organic-inorganic hybrid based on α-Keggin-typed [BW12O40]5- anionic cluster, [Co(BⅡM)3]2H[BW12O40]·7H2O(BⅡM = 2,2′-biimidazole), was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a = 12.3490(10), b = 33.270(3), c = 18.9660(16) β = 105.9950(10)°, V = 7490.5(11) 3, C36H50BCo2N24O47W12, Mr = 3905.80, Dc = 3.451g/cm3, μ(MoKα) = 18.886 mm-1, F(000) = 6972, Z = 4, S = 1.004, the final R = 0.0404 and wR = 0.0914 for 14683 observed reflections(I 2σ(I)). The compound consists of two isolated [Co(BⅡM)3]2+ cations and one [BW12O40]5- anion, in which each Co2+ ion is coordinated by six N atoms from three BⅡM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N–H···O(polyoxometalate and water) hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W–Oterminal···πimidazole ring interactions which cooperate with the classical N–H···O hydrogen bonds to stabilize the structural packing.     

Crystal Structure, Hirshfeld Surface Analysis and Quantum Mechanical Study of a Cocrystal Based on 1,3-Di（4-pyridyl）propane and 3-（（4~′-Carboxybenzyl）oxy） Benzoic Acid

A cocrystal based on 1,3-di(4-pyridyl)propane and 3-((4′-carboxybenzyl)oxy)benzoic acid,C13H14N2·C15H12O5,has been synthesized and characterized by single-crystal X-ray diffraction.The compound crystallizes in monoclinic,space group P21 /c with a = 11.639(4),b = 9.808(3),c = 20.854(6),β = 91.242(7)°,V = 2380.0(13)3,C28H26N2O5,Mr = 470.51,Dc = 1.313 g/cm3,μ(MoKα) = 0.091 mm-1,F(000) = 992,Z = 4,the final R = 0.0677 and wR = 0.1477 for 4175 observed reflections(I > 2σ(I)).Intermolecular N H···O hydrogen bonds link two kinds of components into a one-dimensional chain in [10-1] direction and adjacent chains are further arranged into a two-dimensional network by π···π and C H···π interactions.Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that the close contacts are mainly focused on weak interactions.The theoretical investigations with HF/6-31G(d) method were performed,and its stability,frontier molecular orbital composition and Mulliken charge distribution were also discussed.     

Hydrothermal Synthesis,Structural Investigation and Characterization of an Organic-inorganic Hybrid, [Co（BIIM）3]2H[BW12040]·7H2O

An organic-inorganic hybrid based on a-Keggin-typed [BWI2040]5- anionic cluster, [Co（BIIM）3]2H[BWx2040]＇7H20 （BIIM = 2,2＂-biimidazole）, was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a = 12.3490（10）, b = 33.270（3）, c = 18.9660（16） A, β = 105.9950（10）°, V= 7490.5（11） A3, C36HsoBCo2N24047W12, Mr = 3905.80, Dc = 3.45 l g/cm3, μ（MoKa） = 18.886 rnm-1, F（000） = 6972, Z = 4, S = 1.004, the final R = 0.0404 and wR = 0.0914 for 14683 observed reflections （1 〉 2tr（/））. The compound consists of two isolated [Co（BIIM）3]2＋ cations and one [BW12040]5 anion, in which each Co2＋ ion is coordinated by six N atoms from three BIIM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N-H...O（polyoxometalate and wate） hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W--Oterminal···πimidazole ring interactions which cooperate with the classical N-H···O hydrogen bonds to stabilize the structural packing.     

生物活性配体喹啉-2-羧酸根锰(Ⅱ)配位聚合物的晶体结构及生物活性

合成了一个喹啉-2-羧酸根锰配位聚合物{[Mn(Qina)_2(Bpp)]·2/3H_2O}_n,(Qina=2-quinolinecarboxylic-carboxylate,Bpp=4,4′-trimethylenedipyridine)并制得其单晶。运用元素分析、红外光谱和X射线单晶衍射等方式表征了配合物结构。晶体结构分析表明,每一个Mn(Ⅱ)被2个Qina分子螯合并通过Bpp配体桥联而形成一维线性结构;一维分子链通过分子链间的C-H…π及π…π作用构筑得配合物三维超分子结构。分别利用溴化乙锭荧光光谱法、琼脂糖凝胶电泳法研究了配合物对小牛胸腺DNA及质粒DNA的结合活性及切割活性。配合物表现出了一定的DNA结合力与切割活性。并利用MMT比色法,测试了配合物对Hela,MCF-7肿瘤细胞株的体外毒性,配合物表现出了一定的体外细胞毒性。     

Structural,Hirshfeld surface and in vitro cytotoxicity evaluation of five new N-aryl-N’-alkoxycarbonyl thiocarbamide derivatives

Abstract

Five new compounds, N-(2, 4-dichlorophenyl)-N’-(methoxycarbonyl) thiocarbamide (1), N-(2, 4-dichlorophenyl)-N’-(ethoxycarbonyl) thiocarbamide (2), N-(2, 4-dichlorophenyl)-N’-(2, 2, 2-trichloroethoxycarbonyl) thiocarbamide (3), N-(2,4-dichlrophenyl)-N’-(pentoxycarbonyl) thiocarbamide (4) and N-(4-nitrophenyl)-N’-(pentoxycarbonyl) thiocarbamide (5), have been synthesized by the reaction of various alkoxy chloroformates with 2, 4-dichloroaniline/4-nitroaniline.The molecular structures of the compounds were elucidated by using spectroscopic methods (FT-IR, ¹H and ¹³C NMR) and single-crystal X-ray structure analysis of compounds 2 and 5. Antiperiplanar orientation of C?=?O and C?=?S group across C–N bonds of thiocarbamide core may be due to the presence of intramolecular (N–H···O–C) hydrogen bond in the crystal structure of both the compounds. The presence of intermolecular interactions (C–H···S, C–H···O and N–H···S) in the molecular structure of the compounds has been studied in detail using Hirshfeld surfaces and their associated two-dimensional fingerprint plots. In vitro cytotoxicity screening of the synthesized compounds evaluated on a panel of seven human cancer cell lines (cervical carcinoma (2008, C13*), colorectal (HT29 and HCT116) and ovarian carcinoma (A2780, A2780/CP and IGROV-1)) demonstrated significant inhibitory properties.     

Structural Investigation, Quantum Mechanical Study and Hirshfeld Surface Analysis of One Novel Adduct Based on Aminopyridinium and Biphenyl-2,4'-dicarboxylate

One novel adduct based on aminopyridinium and biphenyl-2,4′-dicarboxylate, C5H7N2+·C14H9O4-, has been synthesized and characterized by X-ray structural study. The compound crystallizes in trigonal, space group P32 with a = 9.2886(16), b = 9.2886(16), c = 16.746(6) , γ = 120°, V = 1251.2(5) 3, C19H16N2O4, Mr = 336.34, Dc = 1.339 g/cm3, μ(MoKα) = 0.095 mm-1, F(000) = 528, Z = 3, the final R = 0.0438 and wR = 0.1119 for 3097 observed reflections (Ⅰ > 2σ(Ⅰ)). Its electronic structure was calculated at the RHF/6-31G(d) level and a detailed analysis of intermolecular interactions was used by Hirshfeld surface and fingerprint plot. Intermolecular N-H…O hydrogen bonds link two components generating R22(8) rings which are linked into three one-dimensional chains in the [100], [010] and [110] directions, and these chains are finally arranged into a three-dimensional framework by hydrogen bonds. Investigation of intermolecular interactions via Hirshfeld surface analysis reveals that the close contacts are mainly associated with the classical hydrogen bonding interactions. The HOMO-LUMO energy gap of the compound indicates a higher kinetic stability.