Vapour pressure of 4-methylpyridine (MePy) over [Ni(MePy)4(NCS)2]·y(MePy) and [Cu(MePy)4(NCS)2]·2/3(MePy) clathrates during their dissociation

Strain measurement and quasiequilibrium thermogravimetry were used to study the dissociation processes of two clathrates, [Ni(MePy)₄(NCS)₂]·(MePy) and [Cu(MePy)₄(NCS)₂]·2/3(MePy), accompanied by the liberation of MePy into the gaseous phase. In the Ni clathrate dissociation process in the temperature range 298–368 K the liberated MePy was redistributed between the solid clathrate and gaseous phases; the MePy vapour pressure over the clathrate is a function of temperature and the guest contenty, which agrees with the presence in the MePy-[Ni(MePy)₄(NCS)₂] system of a wide range of -clathrate solutions, [Ni(MePy)₄(NCS)₂]·y(MePy). The same methods used to study the Cu clathrate dissociation resulted in conclusions different from those obtained for the dissociation process of the above clathrate: the process is described by the equation [Cu(MePy)₄(NCS)₂]·2/3(MePy)_solid =[Cu(MePy)₂(NCS)₂]_solid+22/3(MePy)_gas; the temperature dependence of the Mepy vapour pressure over the solid sample does not depend on its composition, which points to the absence from the system of solid solutions based on the clathrate. Standard changes of the enthalpy, entropy, and isobaric-isothermal reaction potential for the temperature range 292–325 K are equal to 178.6±1.7 kJ (mole of clathrate)^–1, 463±5.6 J (mole of clathrate)^–1 K^–1, and 40.4±2.4 kJ (mole of clathrate)^–1, respectively.     

[Ni(cien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

硫氰酸根的结构为N三C-S-,其两端的N原子和S原子分别有一对和三对孤对电子,因此,硫氰酸根可采用多种不同的配位模式与金属离子发生配位.硫氰酸根可作为单齿配体与一个金属离子配位,形成M-SCN或M-NCS的单核配合物,也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物[1-3];另一方面,硫氰酸根是一个具有一定共轭性的偶极子,可传递磁相作用.因此,选择硫氰酸根作为桥联配体,将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子,并研究它们的磁性已成为分子磁学的一个研究领域[4-6].本文仅报道标题配合物的合成与晶体结构.     

The Structure–Properties Relations in Werner β-[Ni(NCS)2(4-MePy)4] Clathrates. Part 1. Sorption Equilibria and Guest to Host Influence in Solid β-[Ni(NCS)2(4-MePy)4] Clathrate – Gaseous Guest Systems

Sorption equilibria have been studied in the systems solid -[Ni(NCS)2(4-MePy)4] clathrate – gaseous guest (benzene, furan,tetrahydrofuran, propane, CH2Cl2, CH2Br2, methanol). Analysis of theexperimental data shows that the solid–gas equilibrium in this systemcannot be regarded as simple physical sorption by a rigid host lattice. Itwas found that the isosteric heats of guest sorption decrease withincreasing guest uptake in all systems studied. The observed phenomena areinterpreted as the result of a guest to host influence and guest–guest repulsion. The molecular model of guest sorption by the-[Ni(NCS)2(4-MePy)4] host was suggested on the basis of combinedanalysis of sorption isotherms and the dependence of the isosteric heat ofsorption on clathrate composition.     

[Ni(dien)_2]_2[Mn(NCS)_6]·H_2O的合成、晶体结构

硫氰酸根的结构为N≡C－S－，其两端的N原子和S原子分别有一对和三对孤对电子，因此，硫氰酸根可采用多种不同的配位模式与金属离子发生配位。硫氰酸根可作为单齿配体与一个金属离子配位，形成M－SCN或M－NCS的单核配合物，也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物犤１～３犦；另一方面，硫氰酸根是一个具有一定共轭性的偶极子，可传递磁相作用。因此，选择硫氰酸根作为桥联配体，将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子，并研究它们的磁性已成为分子磁学的一个研究领域…     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

X-ray diffraction study of K3[UO2(C2O4)2(NCS)] · 3H2O

The single crystals of K₃[UO₂(C₂O₄)₂(NCS)] · 3H₂O were studied by X-ray diffraction. The compound crystallizes in the monoclinic system, space group P2₁/n, Z = 4, a = 10.673 Å, b = 12.041 Å, c = 13.856 Å, β = 110.18°, R = 0.0290. The basic structural units of the crystals of I are the island complex groups [UO₂(C₂O₄)₂NCS]^3? corresponding to the crystal-chemical group AB⁰¹ ₂M¹ (A = UO ₂ ²⁺ , B⁰¹ = C₂O ₄ ^2? , M¹ = NCS^?) of uranyl complexes and connected into a three-dimensional framework through electrostatic interactions and through hydrogen bonds involving potassium ions and water molecules.     

簇合物[MoS4Cu4(dppm)4](NCS)2·4(CH3)2CHOH的合成与晶体结构

合成了一个五核簇合物[MoS4CU4(dppm)4](NCS)2·4(CH3)2CHOH,用单晶X-射线衍射方法测得该晶体属于单斜晶系,空间群P21/a,晶胞参数a＝2.0536(2),b＝1.8095(2),c＝3.1951(4)nm,β＝100.220(4)°,V＝11.6846(23)nm3,Z＝4,Dc＝1.349g/cm3,μ＝10.87cm-1,F(000)＝4896,R＝0.085,Rw＝0.089.其二价簇阳离子是一个MoS4单元被一个十六原子环[-Cu-P-C-P-]4包围在中心的"主客体"结构.     

Synthesis and Structural Characterization of a Ni(Ⅱ) Complex [Ni(H_2O)_4(4,4'-bipy)_2](hca)_2

1 INTRODUCTION The rational design and synthesis of new metal- organic frameworks have generated considerable interest in supramolecular chemistry and materials science owing to their intriguing structural diver- sities and potential applications as functional mate- rials[1～6]. Carboxylate-containing ligands have attrac- ted considerable attention because of the various coordination modes of carboxylate group, the ability to form hydrogen bonds and the potential applica- tions as functio…     

Unusual magnetic behavior of the new supramolecular ensemble [Ni2L4]2·[NiCl2(LH)2(MeCN)2]·4MeCN (LH is 2-mercaptobenzimidazole)

The diamagnetic dinuclear complex Ni₂L₄ was synthesized by the reaction of NiCl₂·6H₂O with 2-mercaptobenzimidazole (LH) in ethanol in the presence of Et₃N. The solid-state reaction (reagent ratio Ni: LH = 1: 2) followed by recrystallization of the reaction product from a MeCN-THF mixture afforded crystals of the associate [Ni₂L₄]₂·[NiCl₂(LH)₂(MeCN)₂] containing four acetonitrile solvate molecules. Crystals of 2·4MeCN exhibit ferromagnetic properties at helium temperatures. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2101–2105, December, 2006.     

Synthesis and X-ray diffraction study of cs3[UO2(CH3COO)3]2[UO2(CH3COO)(NCS)2(H2O)] and Cs5[UO2(CH3COO)3]3[UO2(NCS)4(H2O)] · 2H2O

Cs₃[UO₂(CH₃COO)₃]₂[UO₂(CH₃COO)(NCS)₂(H₂O)] (I) and Cs₅[UO₂(CH₃COO)₃]₃[UO₂ (NCS)₄(H₂O)] · 2H₂O (II) have been synthesized via the reaction between uranyl acetate and cesium thiocyanate in aqueous solution. According to single-crystal X-ray diffraction data, both compounds crystallize in monoclinic system with the unit cell parameters a = 18.7036(5) Å, b = 16.7787(3) Å, c = 12.9636(3) Å, β = 92.532(1)°, space group C2/c, Z = 4, R = 0.0434 (I); and a = 21.7843(3) Å, b = 24.6436(5) Å, c = 13.1942(2) Å, β = 126.482(1)°, space group Cc, Z = 4, R = 0.0273 (II). Uranium-containing structural units of compound (I) are mononuclear [UO₂(CH₃COO)₃]^? and [UO₂(CH₃COO)(NCS)₂(H₂O)]^? moieties, which correspond to the AB ₃ ⁰¹ and AB⁰¹M ₃ ¹ crystallochemical groups (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?, M¹ = NCS^? and H₂O). The structure of compound II is built of [UO₂(CH₃COO)₃]^? and [UO₂(NCS)₄(H₂O)]^2? complexes, which belong to the AB ₃ ⁰¹ and AM ₅ ¹ crystallochemical groups, respectively. Uranium-containing complexes in both structures are linked into a framework by hydrogen bonds and electrostatic interactions with cesium cations. The IR spectra of compounds I and II agree well with X-ray diffraction data.     

[Mn(H_2O)_4(NCS)_2)(18C6)和(Co(H_2O)_4(NCS)_2)(18C6)单晶的培养及物性表征

用凝胶法和蒸发法分别培养出配合物[Mn(H_2O)_4(NCS)_2]18C6)和[Co(H_2O)_4(NCS)_2](18C6)的单晶。对两个配合物进行了溶解性能的测试、元素分析、电导测量、红外光谱分析、热分析和质谱分析。表征的指派为晶体结构分析结果所证实。 。。     

Synthesis, Structure, Magnetism and Electrochemical Properties of Linear Pentanuclear Complex: Ni5(μ-dmpzda)4(NCS)2

吡啶修饰的线性五核金属化合物[Ni5(μ-dmpzda)4(NCS)2][ dmpzda-H2=N,N’-Di(4-methyl pyrydin-2-yl)pyrazine-2,6-diamine]被合成并表征,其电化学和磁性被报告。 化合物含有接近180º的 Ni-Ni-Ni角,末端含有两个轴配体的Ni5 线性链。这个五核线性金属链被四个顺式的dmpzda2-配体螺旋包裹。化合物中存在两种类型的Ni-Ni键长：末端连接有轴配体的Ni-Ni键长被配体影响,其键长为2.3821 Å;内部的Ni-Ni距离比较短,为2.2959 Å。两末端的Ni(II)离子由于连接轴配体构成四方锥形(NiN4NCS)并存在较长的Ni-N 键长（2.103 Å),这个键长符合高自旋Ni(II)构型。内部的三个Ni-N 距离为1.886-1.906 Å,这样构成正方形平面(NiN4)并呈低自旋的顺磁构型。化合物显示了同[Ni5(μ-tpda)4(NCS)2]类似的磁性,即在化合物中两末端Ni(II)仍存在反铁磁性的作用。     

[Mn(H2O)4(NCS)2](18-冠-6)的分子和晶体结构

报导了[Mn(H2O)4(NCS)2](18-冠-6)单晶的X射线结构分析.它的晶体正交晶系.锰(II)与两个硫氰酸根,四个水分子配合形成顺式八面体的配位分子,并通过其中的水分子与18-冠-6以氢键结合.     

Synthesis and X-ray diffraction study of K4[(UO2)2(C2O4)3(NCS)2] · 4H2O

Single crystals of K₄[(UO₂)₂(C₂O₄)₃(NCS)₂] · 4H₂O(I) have been synthesized and studied by X-ray diffraction. The crystals are monoclinic with the unit cell parameters a = 8.0226(7) Å, b = 14.9493(11) Å, c = 11.1670(9) Å, β = 98.299(3)°, space group P2₁/n, Z = 2, V = 1325.26(19) ų, R = 0.0186. The main structural units of the crystals of structure I are discrete binuclear groups [(UO₂)₂(C₂O₄)₃(NCS)₂]^4? belonging to the crystal-chemical group A₂K⁰²B ₂ ⁰¹ M ₂ ¹ (A =UO ₂ ²⁺ , K⁰² =C₂O ₄ ^2? , B⁰¹ =C₂O ₄ ^2? , M¹ = NCS^?) of the uranyl complexes. The uranium-containing complexes are linked into a three-dimensional framework through the potassium ions and a system of hydrogen bonds involving the outer-sphere water molecules.     

[Zn(NCS)4]2−-Selective electrodes based on higher quaternary ammonium salts (QAS)

We have studied analytical parameters of tetrarhodanozincate-selective film electrodes based on high-lipophilic quaternary ammonium salts: trinonyloctadecylammonium iodide, R-trioctadecylammonium bromide, R-trimethylammonium nitrate, R-tricetylammonium bromide, R-triethylammonium bromide, R-tributylammonium bromide, R-trilaurylammonium bromide, where R is 3,4,5-tris(dodecyloxy)benzyl. A procedure has been developed for the study of the molecular extraction of zinc rhodanide with membrane plasticizers. The applicability of these electrode to zinc determination in solid wastes has been demonstrated.     

Synthesis and Crystal Structure of an Ion-Pair Compound:[HL]2[Ni(CN)4]·4H2O(L=4-(2-Hydroxyphenyl)-1,5,9-triazacyclododecan-2-one)

An ion-pair compound,[HL]2[Ni(CN)4]·4H2O 1 has been obtained as an unexpected product when we attempt to prepare a heterometallic cyano-bridged complex by the reaction of GdCl3·nH2O,K2Ni(CN)4 and L (L=4-(2-hydroxyphenyl)-1,5,9-triazacyclododecan-2-one) in aqueous solution,and characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/n with a=12.380(1),b=9.9637(8),c=17.087(1)A,β=105.947(2)°,V=2026.6(3) A3,Rint=0.0509,Z=2,Dc=1.297g/cm3,C34H56O8N10Ni,Mr=791.60,F(000)=844,μ(MoKα)=0.538 mm-1,S=1.030,the final R=0.0644 and wR=0.1299 for 2023 observed reflections with I≥2σ(I).The title compound 1 contains one anion of [Ni(CN)4]2-,two cations of [HL]+and four packing water molecules,which are held together by the N-H…O and O-H…O hydrogen bonds to form a three-dimensional framework.     

A New Member of Giant Polyoxomolybdate Containing Bridging Hydroxylamine Moieties: Synthesis and Crystal Structure of (NH4)4Na2[MoVI 36O108(NH2OH)2(OH)6(H2O)12]⋅35H2O

A new member of giant polyoxomolybdate containing bridging hydroxylamine groups has been unexpectedly obtained during the preparation of the material of {Mo₅₇V₆}, (NH₄)₄Na₂[Mo^VI ₃₆O₁₀₈(NH₂OH)₂(OH)₆(H₂O)₁₂]35H₂O. The title compound crystallizes in the monoclinic space group P2(1)/n, a=16.7886(2), b=18.4309(3), c=24.49950(10) Å, =99.58°, V=7475.18(15) ų, Z=2, and D _calc =2.817. Each giant cluster anion [Mo^VI ₃₆O₁₀₈(NH₂OH)₂(OH)₆(H₂O)₁₂]^6– ({Mo ₃₆ (NO) ₂ }) consists of two large [Mo^VI ₁₅O₅₀(MoO)⁴⁺ ₂(-NH₂OH)(-OH)(t-OH)₂(t-OH₂)₆]^5– ({Mo₁₇} units linked together by two {MoO₂}²⁺ centers; these anions {Mo ₃₆ (NO) ₂ } are further connected via distorted mono-capped pentagonal-pyramidal sodium into a three-dimensional structure with channels that filled with lattic water molecules and NH⁺ ₄ ions.     

Syntheses,characterisation and solid state thermal studies of 1-(2-aminoethyl)piperidine (L), 1-(2-aminoethyl)pyrrolidine (L′) and 4-(2-aminoethyl)morpholine (L″) complexes of nickel(II): X-ray single crystal structure analyses of trans-[NiL2(CH3CN)2](ClO4)2, trans-[NiL2(NCS)2] and trans-[NiL″2(NCS)2]

Reactions of nickel(II) salts with substituted ethane-1,2-diamine where one of the amine nitrogens is a part of a flexible cyclic ring, e.g. 1-(2-aminoethyl)piperidine (L), 1-(2-aminoethyl)pyrrolidine (L′) and 4-(2-aminoethyl)morpholine (L″) produce a number of complexes of the type: (i) Ni(AA)₂X₂ (where X=CF₃CO₂ ⁻, SCN⁻ and NO₂ ⁻; AA represents L/L′/L″); (ii) Ni(AA)₂(CH₃CN)₂X₂ (X=ClO₄ ⁻ and NO₃ ⁻); (iii) Ni(AA)₂(H₂O)₂X₂ (X=CF₃SO₃ ⁻, Cl⁻, Br⁻ and I⁻); and (iv) Ni(AA)₂(H₂O)₄X₂ (X=0.5SO₄ ²⁻, 0.5SeO₄ ²⁻ and CF₃SO₃ ⁻). The complexes possess octahedral geometry. The major complexes upon desolvation retain trans-geometry, some of which are cis with respect to the counter-anion and a few of them are square planar. X-ray single crystal structure analyses of trans-[NiL₂(CH₃CN)₂](ClO₄)₂, trans-[NiL₂(NCS)₂] (violet) and trans-[NiL″₂(NCS)₂] (sky-blue) have been done. The violet and sky-blue thiocyanato species have blue and green coloured isomers, respectively, and these pairs of isomers are proposed to be conformational isomers. Solid state thermal investigation of the complexes has been carried out. The complexes show thermochromism due to deaquation–anation/deaquation reaction/change of conformation. Only [NiL₂](ClO₄)₂, [NiL′₂(CF₃CO₂)₂] and [NiL″₂(NO₂)₂] undergo thermally induced phase transition. The effect of flexible ring size on diamine has been discussed.     

大环镍配合物[Ni(teta)(NCS)2]的合成与结构研究

大环配体由于其独特的配位性能已吸引了广泛的注意,用大环化合物模拟生物功能,是当今大环化学发展的方向之一[1]。大环四胺配体5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷(简记为teta)的钴配合物已被用来作为研究维生素B12的模型分子[2],一些teta的配合物也已被陆续报道[3     

CRYSTAL AND MOLECULAR STRUCTURE OF [K(C_(14)H_(20)O_5)_2]_2[Co(NCS)_4]

<正> The title complex (Mr= 1442.6) crystallizes in the monoclinic, space group PC, with a =14.515(7),b =15.773(5), c =16.287(11)51,β=95.13(5)°,Z=2,V=3713.8A3,Dc=1.29 g·cm-3. The structure was solved by Patterson method and the final R=0.068. The potassium atom in the cation lies between the two planes of the oxygen atoms from two benzo-15-crown-5 molecules.