Synthesis,crystal structure and magnetic properties of Co(NIT4Py)(H2PDA)(H2O)3

A Co(II)-pyridyl substituted nitronyl nitroxide complex Co(NIT4Py)(H₂PDA)(H₂O)₃ has been synthesized and structurally characterized (NIT4Py: 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and H₂PDA: 2,5-pyridine dicarboxylic acid). The compound is in the monoclinic space group P2(1)/c, a = 16.892(5) Å, b = 7.371(2) Å, c = 18.856(5) Å, β = 108.770(5)°, V = 2223.0(11) ų, Z = 4 and F(000) = 1064. The cobalt is in a distorted octahedral environment with one nitrogen from NIT4Py, one oxygen atom from H₂PDA, two oxygens from two water molecules in the basal plane and one nitrogen from H₂PDA and one water in the axial positions. The molecules are connected as a layered structure by intermolecular hydrogen bond interactions. Variable temperature magnetic susceptibility measurements reveal the occurrence of weak antiferromagnetic interactions in the compound.     

Hydrothermal Synthesis and Crystal Structure of a Zinc Complex:[Zn_(2.5)(phen)(BDC)_2(OH)] (phen = 1,10-Phenanthroline, BDC = Benzene-1,4-dicarboxylic Acid)

A metal-organic coordination polymer [Zn2.5(phen)(BDC)2(OH)]2 (phen = 1,10- phenanthroline, BDC = benzene-1,4-dicarboxylic acid) 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The complex crystallizes in the triclinic system, space group P1 with a = 11.199(2), b = 11.593(2), c = 11.865(3) , α = 99.330(1), β = 111.506(1), γ = 104.804(1)°, V = 1328.4(5) 3, Dc = 1.722 g/cm3, Z = 1, Mr = 1377.82, F(000) = 692, μ(MoKα) = 2.306 mm-1, S = 1.093, R = 0.0281 and wR = 0.0756 for 4179 observed reflections (I > 2σ(I)). The coordination polyhedron around Zn(II) can be described as a tetrahedron, trigonal bipyramid and octahedron. It is worth noting that the crystal structure of 1 is composed of tetranuclear zinc clusters linked by {ZnO6} units.     

Synthesis and structural analysis of the polymetallated alkali calixarenes [M4(p-tert-butylcalix[4]arene-4H)(thf)x]2.n THF (M=Li,K; n=6 or 1; x=4 or 5) and [Li2(p-tert-butylcalix[4]arene-2H)(H2O)(mu-H2O)(thf)].3 THF

To study the structures and reactivities of alkali metallated intermediates of calix[4]arenes, three compounds were isolated: [Li(4)(p-tert-butylcalix[4]arene-4H)(thf)(4)](2).6 THF (1), [Li(2)(p-tert-butylcalix[4]arene-2H)(H(2)O)(mu-H(2)O)(thf)].3 THF (2), and [K(4)(p-tert-butylcalix[4]arene-4H)(thf)(5)](2).THF (3). The structure of 1 is shown to be dependent on the coordinating solvent. Partial hydrolysis of 1 leads to the formation of 2. The potassium compound 3 features a different structure to that of 1, due to a higher coordination number as well as stronger cation-pi-bonding interactions.     

Synthesis and crystal structure of [Co(mpt)_2{P(OCH_3)_3}_2]BF_4 (Hmpt = 2-mercaptothiazoline)

The monomeric cobalt-phosphite-thiolato complex [ Co (mpt)2 {P (OCH3 )3 }2 ] BF4 (Hmpt = 2-mercaptothiazoline) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the monoclinic space group C2/c with a= 0.8078(5), b=2.6020(18), c=1.2191(7) nm, β= 99.38 (1)°, V= 2.528(3) nm3, and Z = 4. The structure comprises discrete cations [Co(mpt)2{P(OCH3)3}2.] and anions BF4- , in which the cobalt (Ⅲ) atom is coordinated to two chelate mpt- and two as-oriented monodentate P(OCH3)3 ligands in a highly distorted octahedral geometry. The most distorted angles are S(2)-Co(1)-S(2a) of 162.23(10)° and N(1)-Co(1)-S(2) of 71. 47 (13)°, the latter is caused by the geometric constraint of the bidentate ligand mpt- . Cyclic voltammetry has been used to study the electrochemical behavior of the title complex on the R electrode in MeCN solution with 0.1 mol·L-1 of Bun4NBF4 as electrolyte. The results indicate that the title complex is unstable in MeCN.     

Synthesis and structure of a novel MoFe4S4 cubane-like cluster (Me3PhCH2N)2 [MoFe4S4 (SC6H11)7]

A novel (Me₃PhCH₂N)₂[MoFe₄S₄(SC₆H₁₁)₇] cubane-like cluster was obtained from a reaction system including (NH₄)₂MoS₄, FeCl₂ and NaSC₆H₁₁ in methanol, and characterized by X-ray crystallography. The title compound crystallizes in triclinic space group witha = 1.523 1(3), b =1.610 5(3),c = 1.838 3(4) nm, α = 77.18 (3)°, β = 75.17(3)°, γ = 64.60(3)°, and Z = 2. Also included in this paper are the discussions on the variation of the reaction products obtained from the participation of cyclohexylthiolate and on the changes of the structural features of the products. Project supported by the National Natural Science Foundation of China and the Climbing Program—State Key Project for Fundamental Research in China, and Hong Kong Research Grants Council (Earmarked Grant No. CUHK. 311/94p).     

Contributions to the Chemistry of Silicon—Sulphur Compounds. 66. Synthesis,crystal and molecular structure of bis(tri-tert-butoxysilanethiolato)(acetonitrile)cobalt(II)[(t-C4H9O)3SiS]2Co(NCCH3)

The title compound [(t-C₄H₉O)₃SiS]₂Co(NCCH₃)] 1 was obtained by reaction of anhydrous cobalt(II) chloride with tri-tert-butoxysilanethiol and triethylamine in acetonitrile as a solvent. The compound crystallizes as deep-blue orthorhombic plates with a = 17.779(4), b = 45.363(9), c = 9.096(2) Å, space group Fdd2 and Z = 8. The structure was solved by Patterson synthesis and refined to the R value of 0.0343. The crystal consists of mononuclear complexes in which the cobalt atom is five-fold coordinated to two sulphurs, two oxygens and one nitrogen in a distorted trigonal bipyramidal arrangement. The relevant bond distances and angles are: Co? S, 2.2680(7); Co? N, 2.065(4); Co? O1, 2.283(2); S? Si, 2.0666(8) Å; S? Co? S′, 119.14(4); N? Co? S, 120.43(2); O1? Co? O1′, 178.81(10)°.     

Synthesis and properties of [Ru(2)(acac)(4)(bptz)](n+) (n=0,1) and crystal structure of [Ru(2)(acac)(4)(bptz)

The neutral complex [Ru(2)(acac)(4)(bptz)] (I) has been prepared by the reaction of Ru(acac)(2)(CH(3)CN)(2) with bptz (bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) in acetone. The diruthenium(II,II) complex (I) is green and exhibits an intense metal-ligand charge-transfer band at 700 nm. Complex I is diamagnetic and has been characterized by NMR, optical spectroscopy, IR, and single-crystal X-ray diffraction. Crystal structure data for I are as follows: triclinic, P1, a = 11.709(2) A, b = 13.487(3) A, c = 15.151(3) A, alpha = 65.701(14) degrees, beta = 70.610(14) degrees, gamma = 75.50(2) degrees, V = 2038.8(6) A(3), Z = 2, R = 0.0610, for 4397 reflections with F(o) > 4sigmaF(o). Complex I shows reversible Ru(2)(II,II)-Ru(2)(II,III) and Ru(2)(II,III)-Ru(2)(III,III) couples at 0.17 and 0.97 V, respectively; the 800 mV separation indicates considerable stabilization of the mixed-valence species (K(com) > 10(13)). The diruthenium(II,III) complex, [Ru(2)(acac)(4)(bptz)](PF(6)) (II) is prepared quantitatively by one-electron oxidation of I with cerium(IV) ammonium nitrate in methanol followed by precipitation with NH(4)PF(6). Complex II is blue and shows an intense MLCT band at 575 nm and a weak band at 1220 nm in CHCl(3), which is assigned as the intervalence CT band. The mixed valence complex is paramagnetic, and an isotropic EPR signal at g = 2.17 is observed at 77 and 4 K. The solvent independence and narrowness of the 1200 nm band show that complex II is a Robin and Day class III mixed-valence complex.     

Synthesis and Crystal structure of Poly{[Co(4,4''-bpy)(H2O)4]SO4((4-abaH)2(3H2O}

The title complex has been obtained by the reaction of cobalt sulfate heptahydrate with 4,4'-bpy and 4-abaH (4,4'-bpy = 4,4'-bipyridine, 4-abaH = 4-aminobenzonic acid) in ethanol solution, and its structure was determined by X-ray crystallography with the following data: tetragonal, space group P42/n, Mr = 5692.46, Co8C192H288N32O120S8, a = b = 16.402(5), c = 22.750(5) (A), Z = 1, V = 6120(2) (A)3, F(000) = 2968, Dc = 1.544 g/cm3,μ = 0.707 mm- 1, the final R = 0.0786 and wR = 0.1935 for 2673 observed reflections (I ＞ 2σ(I)). The title complex consists of polymeric [Co(4,4'-bipy)(H2O)4]2+ cation chains, SO42- anions, lattice 4-abaH and water mole cules. The center CoⅡ ions are connected by bridging 4,4'-bpy ligands exhibiting one-dimensional chains, and coordinated by four water molecules into a distorted octahedral geometry. These chains are further extended by hydrogen bonds among SO42- anions, coordinated and lattice water molecules as well as lattice 4-abaH molecules into a three-dimensional network.     

三维无机-有机杂化骨架微孔材料──[Co3(BTC)(HBTC)(H2BTC)(C2H4O2)3]·3(DMF)·6(H3O)的合成与结构

沸石和分子筛微孔晶体材料是指以硅酸盐、硅铝酸盐、磷铝酸盐和无机金属磷酸盐为骨架的晶体材料[1,2 ] .最近 ,Yaghi,Williams,Zaworotko,Kitagawa和游效曾等 [3～ 11] 利用刚性和热稳定性较好的有机分子 (如芳香多酸和多碱 )和金属离子作为结构单元 ,制备出了新型无机 -有机杂     

Syntheses and Structural Characterization of Two Nitrilotriacetate Cobalt Complexes: [{CoK2(NTA)(Hmta)(H2O)3}NO3]n and [{Co(4,4′‐bpy)2(H2O)4}{Co2(NTA)2(4,4′‐bpy)(H2O)2}]

Two nitrilotriacetate cobalt complexes {[CoK₂(NTA)(Hmta)(H₂O)₃]NO₃}_n ( 1 ) and [{Co(4,4′‐bpy)₂(H₂O)₄}{Co₂(NTA)₂(4,4′‐bpy)(H₂O)₂}] ( 2 ) (NTA = nitrilotriacetate anion, Hmta = hexamethylenetetramine and 4,4′‐bpy = 4,4′‐bipyridine) were prepared and characterized by IR, elemental analysis and single crystal X‐ray diffraction study. The influence of the neutral ancillary ligands on the formation of the complexes with different structures in the Co‐NTA system was discussed. The coordination of NTA and Hmta to Co²⁺ ions only resulted in the formation of mononuclear [Co(NTA)(Hmta)]^? ions which are further connected by K⁺ ions and water molecules to form a three‐dimensional network. The use of 4,4′‐bpy as ancillary ligand in 2 led to the formation of separate mononuclear [Co(4,4′‐bpy)₂(H₂O)₄]²⁺ and dinuclear [Co₂(NTA)₂(4,4′‐bpy)(H₂O)₂]^2? which are further connected by hydrogen bonds to form a supramolecular three‐dimensional network. In these cases it seems to suggest that the addition of neutral ancillary ligand into the Co‐NTA system leads to the formation of lower dimensional structures when the contribution of alkali ions to the structural dimensionality is neglected.     

Synthesis and crystal structure of [Ln(4-Pyta)3(H2O)2] n (Ln = Nd,Ce, Eu,Gd; 4-Pyta = 4-pyridylthioacetate)

Four new lanthanide complexes, [Nd(4-Pyta)₃(H₂O)₂] _n (1), [Ce(4-Pyta)₃(H₂O)₂] _n (2), [Eu(4-Pyta)₃(H₂O)₂] _n (3) and [Gd(4-Pyta)₃(H₂O)₂] _n (4), have been obtained from reaction of lanthanide(III) nitrate with 4-Pyta (4-pyridylthioacetate) in water. Their structures were characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The crystals belong to triclinic, space group P 1 and all complexes exhibit one-dimensional chains that arrange to form a three-dimensional supramolecular architecture by hydrogen bonds between the chains.     

Synthesis,Crystal Structure and Properties of a Novel Nickel Citrate Ni（H_2cit）（phen）（H_2O）·3H_2O（H_4cit = Citrate Acid,phen=1,10-Phenanthroline）

A new nickel citrate compound Ni(H2cit)(phen)(H2O).3H2O(H4cit = citrate acid,phen = 1,10-phenanthroline) has been synthesized and characterized by single-crystal X-ray diffraction.It crystallizes in the trigonal system,space group P31 with a = 13.8319(13),c = 10.425(2),V = 1727.3(4)3,Dc = 1.445 g/cm3,Mr = 501.09,F(000) = 780,μ = 0.901 mm-1,Z = 3,R = 0.0760 and wR = 0.1730 for 3859 observed reflections(I > 2σ(I)).In this compound,Ni2+ cation is chelated by a phen molecule,one H2cit2-anion and one H2O molecule.The citric acid coordinates to the Ni2+ center through three functional groups:α-hydroxyl,α-carboxylate and β-carboxylate while another α-carboxylate forms hydrogen bond with surrounding H2O molecule.And the citric acid is doubly protonated.The temperature-dependent magnetic susceptibility data revealed that the compound is a paramagnetic material.     

Reaktionen von Cyclostibanen (RSb)n [R = (Me3Si)2CH,n = 3; Me3CCH2, n = 4, 5] mit den Übergangsmetallcarbonyl‐Komplexen [W(CO)5(thf)], [CpxMn(CO)2(thf)], [CpxCr(CO)3]2 und [Co2(CO)8]; Cpx = MeC5H4

Reactions of Cyclostibanes, (RSb)_n [R = (Me₃Si)₂CH, n = 3; Me₃CCH₂, n = 4, 5] with the Transition Metal Carbonyl Complexes [W(CO)₅(thf)], [Cp^xMn(CO)₂(thf)], [Cp^xCr(CO)₃]₂, and [Co₂(CO)₈]; Cp^x = MeC₅H₄ (RSb)₃ [R = (Me₃Si)₂CH] reacts with [W(CO)₅(thf)], [Cp^xMn(CO)₂(thf)], or [Co₂(CO)₈] to give [(RSb)₃W(CO)₅] ( 1 ), [RSb{Mn(CO)₂Cp^x}₂] ( 2 ) or [RSbCo(CO)₃]₂ ( 3 ). The reaction of (R′Sb)_n (n = 4, 5; R′ = Me₃CCH₂) with [Cp^xCr(CO)₃]₂ leads to [(R′Sb)₄{Cr(CO)₂Cp^x}₂] ( 4 ); Cp^x = MeC₅H₄, thf = Tetrahydrofuran.     

Synthesis,molecular and electronic structure of [ReCl2(N2COPh)(C4N2H4)(PPh3)2]

A new organodiazenido rhenium complex, [ReCl₂(N₂COPh)(C₄N₂H₄)(PPh₃)₂] has been obtained from the direct reaction of [ReCl₂(η²–N₂COPh–N′,O)(PPh₃)₂] with pyrazine in acetone. The complex has been characterized by spectroscopic methods and its structure determined using single-crystal X-ray diffraction techniques.     

Synthesis and Crystal Structure of [Sm（4-Pyta）3（H2O）2]n （4-Pyta = 4-Pyridylthioacetate）

A novel coordination polymer [Sm（4-Pyta）3（H2O）2]n has been synthesized by the hydrothermal reaction between 4-Pyta （4-Pyta = 4-pyridylthioacetate） and Sm（NO3）3. The structure was characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space groupP1, with a = 9.100（2）, b = 11.842（3）, c = 12.183（3） A, α= 79.781（4）, β= 74.124（4）, γ = 841882（5）^o, V = 1241.6（5） A^3, Z = 2, Mr = 690.95, Dc = 1.84806 g/cm^3, F（000） = 686,μ = 2.669 mm^-1, the final R = 0.0388 and wR = 0.0808 for 4149 observed reflections with I 〉 2σ（I）. The structural analysis shows that the complex exhibits a one-dimensional architecture. Intermolecular hydrogen bonding interactions are found in the complex molecules.     

配位聚合物{[Co(4,4''''-bpy)(H2O)4](Fum)·4H2O}n的合成和晶体结构

0引言近年来,利用晶体工程方法设计、裁剪和组装具有一维、二维和三维有序超分子结构的配位聚合物引起了人们极大的兴趣,并成为材料科学和化学学科中最活跃的研究领域之一[1~3]。在超分子结构设计方面,利用过渡金属借助配体配位作用引导的自组装已成为一个热点。其中多联吡啶类     

Hydrothermal Synthesis and Crystal Structure of a Zinc Complex： [Zn2.5（phen）（BDC）2（OH）] （phen = 1,10-Phenanthroline,BDC = Benzene-1,4-dicarboxylic Acid）^①

A metal-organic coordination polymer [ZnE.s（phen）（BDC）2（OH）]2 （phen = 1,10- phenanthroline, BDC = benzene-1,4-dicarboxylic acid） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The complex crystallizes in the triclinic system, space group PI with a = 11.199（2）, b = 11.593（2）, c = 11.865（3）/A, α= 99.330（1）, β = 111.506（1）, γ = 104.804（1）^o, V= 1328.4（5）A^3, Dc= 1.722 g/cm^3, Z = 1, Mr = 1377.82, F（000） = 692,μ（MoKa） = 2.306 mm^-1, S = 1.093, R= 0.0281 and wR = 0.0756 for 4179 observed reflections （I 〉 2σ（/））. The coordination polyhedron around Zn（II） can be described as a tetrahedron, trigonal bipyramid and octahedron. It is worth noting that the crystal structure of 1 is composed of tetranuclear zinc clusters linked by {ZnO6} units.     

Synthesis, molecular structure and properties of the [H6-nNi30C4(CO)34(CdCl)2]n- (n=3-6) bimetallic carbide carbonyl cluster: a model for the growth of noncompact interstitial metal carbides

Reaction of the [Ni(9)C(CO)(17)](2-) dianion with CdCl(2)2.5 H(2)O in THF affords the novel bimetallic Ni--Cd carbide carbonyl clusters [H(6-n)Ni(30)C(4)(CO)(34)(micro(5)-CdCl)(2)](n-) (n=3-6), which undergo several protonation-deprotonation equilibria in solution depending on the basicity of the solvent or upon addition of acids or bases. Although the occurrence in solution of these equilibria complicates the pertinent electrochemical studies on their electron-transfer activity, they clearly indicate that the clusters [H(6-n)Ni(30)C(4)(CO)(34)(micro(5)-CdCl)(2)](n-) (n=3-6), as well as the structurally related [H(6-n)Ni(34)C(4)(CO)(38)](n-) (n=4-6), undergo reversible or partially reversible redox processes and provide circumstantial and unambiguous evidence for the presence of hydrides for n=3, 4 and 5. Three of the [H(6-n)Ni(30)C(4)(CO)(34)(micro(5)-CdCl)(2)](n-) anions (n=4-6) have been structurally characterized in their [NMe(3)(CH(2)Ph)](4)[H(2)Ni(30)C(4)(CO)(34)(CdCl)(2)]2 COMe(2), [NEt(4)](5)[HNi(30)C(4)(CO)(34)(CdCl)(2)]2 MeCN and [NMe(4)](6)[Ni(30)C(4)(CO)(34)(CdCl)(2)]6 MeCN salts, respectively. All three anions display almost identical geometries and bonding parameters, probably because charge effects are minimized by delocalization over such a large metal carbonyl anion. Moreover, the Ni(30)C(4) core in these Ni-Cd carbide clusters is identical within experimental error to those present in the [HNi(34)C(4)(CO)(38)](5-) and [Ni(35)C(4)(CO)(39)](6-) species, suggesting that the stepwise assembly of their nickel carbide cores may represent a general pathway of growth of nickel polycarbide clusters. The fact that the [H(6-n)Ni(30)C(4)(CO)(34)(micro(5)-CdCl)(2)](n-)(n=4-6) anions display two valence electrons more than the structurally related [H(6-n)Ni(34)C(4)(CO)(38)](n-) (n=4-6) species has been rationalized by extended Hückel molecular orbital (EHMO) analysis.     

Co(C2(COO)2)(H2O)4 · 2 H2O und Co(C2(COO)2)(H2O)2: zwei Koordinationspolymere mit dem Acetylendicarboxylat‐Dianion

Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O and Co(C₂(COO)₂)(H₂O)₂: Two Co‐ordination Polymers of the Acetylenedicarboxylate Dianion By reaction of CoCO₃ with an aqueous solution of acetylenedicarboxylic acid and subsequent crystallisation single‐crystals of Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O were obtained (P2₁/a, Z = 2). In the solid state structure cobalt is octahedrally surrounded by four water molecules and two oxygen atoms of the carboxylate anions. These octahedra are connected to chains by the dicarboxylates. Already at ambient conditions Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O looses four water molecules to give Co(C₂(COO)₂)(H₂O)₂ (isotypic to Mn[C₂(COO)₂] · 2 H₂O, C2/c, Z = 4). The cobalt cation is now octahedrally co‐ordinated by two water molecules and four oxygen atoms of the dicarboxylate ligands, which connect the Co octahedra to a three dimensional network. Thermoanalytical investigations show another mass loss at about 200 °C, which leads to non‐crystalline products. Measurements of the magnetic susceptibilities result in the expected behaviour for Co²⁺ in an octahedral co‐ordination (high spin, ⁴T₁ ground state). The effective magnetic moment at room temperature is n_eff = 5.51 μ_B.     

A new stepped tetranuclear copper(II) complex: synthesis,crystal structure and photoluminescence properties

Binuclear and tetranuclear copper(II) complexes are of interest because of their structural, magnetic and photoluminescence properties. Of the several important configurations of tetranuclear copper(II) complexes, there are limited reports on the crystal structures and solid‐state photoluminescence properties of `stepped' tetranuclear copper(II) complexes. A new Cu^II complex, namely bis{μ₃‐3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolato}bis{μ₂‐3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolato}tetracopper(II), [Cu₄(C₁₁H₁₃NO₃)₄], has been synthesized and characterized using elemental analysis, FT–IR, solid‐state UV–Vis spectroscopy and single‐crystal X‐ray diffraction. The crystal structure determination shows that the complex is a stepped tetranuclear structure consisting of two dinuclear [Cu₂(L )₂] units {L is 3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolate}. The two terminal Cu^II atoms are four‐coordinated in square‐planar environments, while the two central Cu^II atoms are five‐coordinated in square‐pyramidal environments. The solid‐state photoluminescence properties of both the complex and 3‐[(2‐hydroxy‐4‐methoxybenzylidene)amino]propanol (H₂L ) have been investigated at room temperature in the visible region. When the complex and H₂L are excited under UV light at 349 nm, the complex displays a strong blue emission at 469 nm and H₂L displays a green emission at 515 nm.