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1.
Qi Shuai 《Inorganica chimica acta》2007,360(5):1381-1387
Three novel coordination polymers [Ca(5-OH-BDC)(H2O)3] · H2O (1), [Sr(5-OH-BDC)(H2O)4] · H2O (2) and [Ba(5-OH-BDC)(H2O)3] (3) were obtained by self-assembly of the corresponding alkaline earth metal chlorate with a ligand, 5-hydroxyisophthalic acid (5-OH-H2BDC), and their structures were determined by X-ray crystallography. The results revealed that complexes 1, 2 and 3 have two-dimensional network with (6, 3) topology observed in the bc plane. Moreover, the two-dimensional layers can be assembled into three-dimensional supramolecular architectures via intermolecular hydrogen bonds. The two carboxylate groups of 5-OH-BDC2− ligand adopt the same coordination mode in complex 1 as that in 2: a μ3-η2:η1 mode and a chelated mode while in complex 3 they coordinate to Ba(II) ions in a μ3-η2:η1 mode and a monodentate mode, which is not observed in previous reports. The constant-volume combustion energies, ΔcU, of these complexes were determined by a precise rotating-bomb calorimeter at 298.15 K, then their standard enthalpies of combustion, , and the standard enthalpies of formation, , have been calculated. 相似文献
2.
Two novel lanthanide(III) two-dimensional (2D) coordination polymers [Ln2(PDC)2(OH)2(H2O)2] · H2O (Ln = Eu (1) and Tb (2), H2PDC = pyridine-3,4-dicarboxylic acid) have been prepared under hydrothermal conditions and characterized by elemental analysis, IR, TGA and single-crystal X-ray diffraction. Compounds 1 and 2 crystallize in the triclinic system, space group , they are isostructural and exhibit the same two-dimensional topological network constructed by PDC-connected Ln-O-Ln double chains. Photoluminescence properties of the compounds 1 and 2 have been investigated in the solid state at room temperature. 相似文献
3.
Olivier Schott Abdeslem Bentama Salah-Eddine Stiriba Jorge Pasán Marius Andruh Miguel Julve 《Inorganica chimica acta》2011,376(1):358-366
The preparation, crystal structure and variable temperature-magnetic investigation of three 2-(2′-pyridyl)imidazole-containing chromium(III) complexes of formula PPh4[Cr(pyim)(C2O4)2]·H2O (1), AsPh4[Cr(pyim)(C2O4)2]·H2O (2) and [Cr2(pyim)2(C2O4)2(OH2)2]·2pyim · 6H2O (3) [pyim = 2-(2′-pyridyl)imidazole, , and ] are reported herein. The isomorphous compounds are made up of discrete [Cr(pyim)(C2O4)2]− anions, cations [X = P (1) and As (2)] and uncoordinated water molecules. The chromium environment in 1 and 2 is distorted octahedral with Cr-N and Cr-O bond distances varying in the ranges 2.040(3)-2.101(3) and 1.941(3)-1.959(3) Å, respectively. The angle subtended by the chromium(III) ion by the two didentate oxalate ligands cover the range 82.49(12)-82.95(12)°, values which are somewhat greater than those concerning the chelating pyim molecule [77.94(13) (1) and 78.50(13)° (2)]. Complex 3 contains discrete centrosymmetric [Cr2(pyim)2(C2O4)2(OH)2] neutral units where the two chromium(III) ions are joined by a di-μ-hydroxo bridge, the oxalate and pyim groups acting as peripheral didentate ligands. Uncoordinated water and pyim molecules are also present in 3 and they contribute to the stabilization of its structure by extensive hydrogen bonding and π-π type interactions. The values of the intramolecular chromium-chromium separation and angle at the hydroxo bridge in 3 are 2.9908(12) Å and 99.60(16)°, respectively. Magnetic susceptibility measurements of 1-3 in the temperature range 1.9-300 K show the occurrence of weak inter- (1 and 2) and intramolecular (3) antiferromagnetic couplings. The magnetic properties of 3 have been interpreted in terms of a temperature-dependent exchange integral, small changes of the angle at the hydroxo bridge upon cooling being most likely responsible for this peculiar magnetic behavior. 相似文献
4.
Eric Burkholder 《Inorganica chimica acta》2005,358(1):116-122
The hydrothermal reactions of MoO3, tetra-2-pyridylpyrazine (tpyprz) and M(CH3CO2)2 · 2H2O (M = Co, Ni) yielded the two-dimensional oxides [M2(tpyprz)(H2O)2Mo8O26] · xH2O [M = Co, x = 1.8 (1); M = Ni, x = 0.6 (2)]. However, the reaction of (NH4)6Mo7O24 · 4H2O, tpyprz and Cu(CH3CO2)2 · H2O produced [{Cu2(tpyprz)}2Mo8O26] · 2H2O (3 · 2H2O). The isomorphous structures of 1 and 2 are constructed from clusters linked through {M2(tpyprz)(H2O)2}4+ subunits into two-dimensional networks. While the structure of 3 is also two-dimensional, the molybdate building block is present as the δ-isomer and the secondary-metal/ligand component consists of a one-dimensional chain. The structure of 3 is compared to that of the previously reported three-dimensional material [{Cu2(tpyprz)}2Mo8O26] · 7H2O which contains clusters and structurally distinct chains. 相似文献
5.
Two cyano-bridged cadmium(II) and copper(II)-copper(I) mixed-valence polymer compounds 1 and [CuII(en)2]0.5[CdCuI(CN)3] · Cl · H2O 2 (en = 1,2-ethanediamine) through systematically varying the solution environment have been synthesized and structurally characterized by single crystal X-ray diffraction analysis. The cyano anions connected the copper and cadmium centres with bidentate or tridentate bridging modes resulting in two complicated 3D networks for 1 and 2. Compound 1 has a rare 5,6-connected network, while compound 2 can be reduced to a 6-connected α-Po net. The magnetic and thermal properties of 1 and 2 are also studied. 相似文献
6.
Hydrothermal synthesis has afforded a family of three structurally related metal phthalate (pht) 1-D coordination polymers incorporating the kinked dipodal organodiimine 4,4′-dipyridylamine (dpa), with a general formulation of [L2M(dpa)2M(H2O)4] · H2O (L = pht, M = Co, 1, M = Ni, 2; L = 4-methylphthalate (4-mpht), M = Co, 3). Single crystal X-ray diffraction of 1 and 2 revealed the presence of one-dimensional (1-D) polymeric chains consisting of [M(H2O)4]2+ and [M(pht)2]2− subunits linked through dpa tethers. These chains in turn conjoin into pseudo 2-D layers and 3-D networks via extensive supramolecular hydrogen bonding pathways. An extremely similar structure is observed for 3 despite the presence of the bulkier methyl group substituent. 1-3 were further characterized via infrared spectroscopy and elemental and thermogravimetric analysis. 1-3 represent the first dicarboxylate coordination polymers incorporating dpa tethering ligands. 相似文献
7.
Five cadmium halides with N-donor ligands were synthesized under the hydrothermal conditions and characterized by X-ray single-crystal diffraction. The isostructural [CdX2(2,2′-bpy)] (X = I 1, Br 2, bpy = bipyridine) (1) possess 3-D supramolecular network structures based on 1-D zigzag-type CdX2 chains extended by bpy molecules via non-covalent C-H?X hydrogen-bonded interactions. The 3-D porous [CdBr2(pip)] (pip = piperazine) (3) is formed through a linkage of 1-D zigzag-type CdBr2 chains by pip bridges. The heteronuclear dimetal-iodo cluster [Cu(phen)2CdI4] (phen = phenanthroline) (4) consists of a trigonal bipyramidal Cu(II) center and a tetrahedral Cd(II) center linked by a μ2-I bridge. The ionic [Co(dien)2][CdI4] (dien = diethylenetriamine) (5) comprises an octahedral cation and a tetrahedral anion. 相似文献
8.
The combination of transition metal ions with mixed ligands resulted in the formation of three new coordination polymers, {[Co(C4H4O5)(bpe)(H2O)2] · (0.5bpe)(H2O)}n (1), {[Cu(C4H4O6)(bipy)] · 5H2O}n (2) and {[Cu(C4H4O5)(bpa)] · 2.5H2O}n (3) (, , bpe = 1,2-bis(4-pyridyl)ethene, bipy = 2,2′-bipyridine, bpa = 1,2-bis(4-pyridyl)ethane), which were prepared under solvothermal conditions and characterized by single-crystal X-ray diffraction. 1 and 2 feature 1D chain structures. Interestingly, each pair of chains recognizes each other through aromatic π-π stacking interactions, generating a zipper-like double-stranded chain in 2. Compound 3 shows 2D 63 topology framework with a rectangle-like grid. 相似文献
9.
The reaction of 1,3-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib) ligand with silver(I) nitrate in a 1:1 molar ratio generated a [2 + 2] metallocyclic complex [Ag2(bib)2](NO3)2 · 2H2O, in which bib ligand displayed in cis configuration. When the additional competing ligands/counterions, such as oxlate salt, 1,2-diaminoethene (en), 1,3-diaminopropane (pn), and were introduced, respectively, to the above-mentioned reaction solution, ring-open polymerization of sliver(I) complexes {[Ag(bib)]NO3 · H2O}n (1), {[Ag(bib)2]X}n ( (2), (3)), {[Ag2(bib)2(NO2)](NO2) · 19/8H2O}n (4) and {[Ag2(bib)2](V4O12)0.5 · 3H2O · 2MeCN}n (5) were generated. In compounds 1, 4 and 5, bib ligand adopts trans configuration and twists around the Ag-Ag axis, giving rise to single-stranded helical structure with short adjacent Ag?Ag distances of 3.56, 3.56, 3.50 and 3.63 Å, respectively. Compounds 2 and 3 are 1D coordination polymers fusing the [2 + 2] metallocycle [Ag2(bib)2]2+, in which bib ligand exhibits in cis configuration and the metallocycles have longer Ag?Ag distances of 8.52 Å in 2 and 8.61 Å in 3 along with the strong intracyclicπ-π interactions between phenyl groups. Cis and trans configurations of bib coexist in solution and crystallize in complexes 1 and 2 in the solid state in the presence of en or pn. The solution of 1 and 2 can be converted into 3 via the addition of the bulky counter anion or into 4 through introduction of the competing ligand/conuterion . 相似文献
10.
Chih Yuen Chen 《Inorganica chimica acta》2007,360(1):21-30
The synthesis and characterization of three simple 1:2 silver(I) pyridine adducts of different counter-anions, [Ag(py)2]+ · X− (X = ClO4, 1; BF4, 2; PF6, 3), are reported. The structural studies for 1-3 reveal the presence of strong ligand-unsupported argentophilic interactions between [Ag(py)2]+ ions, forming pairs of . The Ag?Ag contact distances are 2.96-3.00 Å. In 1 and 2, pairs of are further linked into 1-D infinite chains by a combined set of multiple Ag?Ag close contacts (3.34-3.37 Å), offset ‘head to head’ π-π stacking, and anion bridging interactions. Such combined set of interactions is anion-dependant with 1 and 2 containing anions of tetrahedral geometry and , affording essentially the same supramolecular architecture. Metal-anion interactions are crucial in organizing the 1-D chains into 3-D networks. The ES-MS studies of 1 and 2 provide positive evidence for the aggregation of silver(I) ions in solution. In contrast, for 3 with the counter-anion of octahedral , pairs of are organized into a 3-D network via a combined set of Ag?F contacts, C(H)?F hydrogen bonds, and ‘head to tail’ π-π stacking interactions. No extended 1-D polymeric chains of silver ions are present in 3. 相似文献
11.
Jun-Feng Lu Qiu-Xuan Zhou Jian-Mei Lu Xue-Wei Xia Yong Zhang 《Inorganica chimica acta》2009,362(10):3401-1003
The influence of coanion on self-assembly of CuSO4 and 4,4′-dipyridyl sulfide (dps) was studied in this paper. During the formation of Cu(II)/dps coordination polymers, coanions Cl−, SCN− and were added in the solution respectively. Three novel coordination polymers were obtained, {[Cu(dps)2 · (SO4)2][Cu(dps) · Cl · (H2O)2]2 · 12H2O}n (1 · 12H2O, a 3D network), {[Cu(SCN)2(dps)(CH3OH)2][Cu(dps)2 · SO4][Cu(dps)(CH3CH2OH)2 · SO4] · 5H2O}n (2 · 5H2O, a 3D network), and {[Cu(dps)2(H2O)2] · (PF6)2 · 3H2O}n (3 · 3H2O, a 2D lattice network). Different coanion shows different influence on framework construction. In 1 and 2, Cl− and SCN− act as terminal ligands and similar 3D frameworks were composed of [Cu(dps)] layer with larger cavity (ca. 400 Å) and sulfate bridge; in 3, replaces entirely and the 3D framework was broken due to the removal of bridging anions. However, a 2D [Cu(dps)]4 undulating grid was preserved in 3. 相似文献
12.
Gui-Lin Wen Ping Liu Chun-Yan Guo Wei-Hong Zhang Qi-Zhen Shi 《Inorganica chimica acta》2009,362(6):1730-2521
Six new coordination polymers based on V-shaped linkage 2,5-bis(4-pyridyl)-1,3,4-thiadiazole (bpt) and transition metal ions, [Co(bpt)(pm)0.5(H2O)]n · 3nH2O (1), [Cu2(bpt)(pm)(H2O)4]n (2), [Co(bpt)(pydc)]n · 2nCHCl3 · nH2O (3), [Cu2(bpt)(pydc)2(H2O)2]n (4), [Cu2(bpt)(pydco)2(H2O)2]n · nH2O (5) and [Cd(bpt)(pydco)]n (6) (H4pm = pyromellitic acid, H2pydc = pyridine-2,6-dicarboxylic acid, H2pydco = pyridine-2,6-dicarboxylic acid N-oxide), have been synthesized under the intervention of various polycarboxylate ligands. Complex 1 exhibits a 3-D 4-connected structure with 1-D nanosized open channels encapsulated lots of water molecules. Complex 2 represents a 2-D grid containing two types of rectangular windows. When pydc and pydco instead of pm, complexes 3 and 6 were obtained with highly undulated 2-D layers. The interlayers of 3 are filled with two kinds of solvent molecules, whereas 6 is a double-layered framework without free molecules. Complexes 4 and 5 consist of two distinct 1-D infinite chains held together to form different 2-D supramolecular networks. Importantly, bpt spacer shows changeful conformational geometries and generates complicated crystalline architectures with the introduction of polycarboxylate ligands. Additionally, thermal stability of complexes 1, 3 and 5, fluorescent properties of 6 and X-ray powder diffraction of 1 have also been investigated. 相似文献
13.
David P. Martin 《Inorganica chimica acta》2007,360(2):599-606
Hydrothermal synthesis has afforded a family of four coordination polymers containing divalent nickel or cobalt and pendant-arm pyridylcarboxylate ligands. Utilizing 3-pyridylacetic acid and appropriate metal precursors produced [M(3-pyrac)2(H2O)2] phases (M = Co (1); M = Ni (2)), while 3-pyridylpropionic acid generated [M(3-pyrprop)2(H2O)2] coordination polymers (M = Co (3); M = Ni (4)). Single crystal X-ray diffraction revealed that 1-4 all display discrete 2-D layers with (4,4)-topology, anchored via bridging 3-pyridylcarboxylate ligands bearing monodentate carboxylate termini. Intralamellar hydrogen bonding between the aquo ligands and unligated carboxylate oxygen atoms is observed within 1-4. The pseudo 3-D structures of 1-4 are further assembled via stacking of individual neutral layers by interlayer hydrogen bonding. Thermal properties are also discussed. 相似文献
14.
Jessica Chuang 《Inorganica chimica acta》2008,361(8):2357-2364
Hydrothermal chemistry was used to prepare the bimetallic organic-inorganic hybrid oxide [Cu(I)Cu(II)2(trz)2Mo4O13(OH)] · 6H2O (1 · 6H2O). The structure consists of chains linked through into a three-dimensional framework. The structures of the simple metal-triazole phases [MoO3(Htrz)0.5] (2) and [Cu(trz)] (3) are also reported. Compound 2 is two-dimensional, constructed from corner-sharing {MoO5N} octahedra. Compound 3 consists of {Cu(trz)}n chains linked through weak Cu?Cu contacts into a virtual layer. 相似文献
15.
Reactions of 1,1′-(1,4-butanediyl)bis-1H-benzimidazole (bbbm) with Cd(II), Ni(II), or Co(II) afford three organic-metal polymers: {[Cd(bbbm)(SO4)(H2O)2]CH3OH}n (1), {[Ni(bbbm)2(H2O)2](NO3)2 · 2CH3OH · 6H2O}n (2) and {[Co(bbbm)2(H2O)2](NO3)2 · 2CH3OH · 6H2O}n (3). In 1, bbbm and coordinate to Cd(II) simultaneously leading to a 3-D structure. In 2 and 3, each bridging bbbm ligand links two Ni(II) or Co(II) ions forming the 2-D layered structure with (4, 4) grid units. Each (4, 4) grid unit is a 44-membered ring and constructed by four bbbm ligands acting as four sides and four Ni(II) or Co(II) ions representing four corners. Their third-order nonlinear optical (NLO) properties in DMF solution have been studied by Z-scan technique. The results show that the DMF solution of 2 possesses both the large third-order NLO absorptive and strong refractive behaviors; and 3’s shows large NLO absorptive effect and weak NLO refractive behavior. A reasonably good fit between the experimental data and the theoretical curve suggests that the experimentally obtained NLO effects are effective third-order in nature. 相似文献
16.
Three new iron(III) citrate complexes [Fe2(cit)2(H2O)2](H2bpa) (1), [Fe2(cit)2(H2O)2](H2bpe) (2) and [Fe4(cit)4(H2O)4](H2bpp)2(H2O) (3) (cit = C(O−)(COO−)(CH2COO−)2, bpa = 1,3-bis(4-pyridyl)ethane, bpe = 1,3-bis(4-pyridyl)ethene, bpp = 1,3-bis(4-pyridyl)propane) were synthesized and characterized by elemental analysis, spectroscopic techniques and magnetic properties. Single X-ray diffraction analyses in the 1-3 complexes reveal that the iron ion is six-coordinated and is bound by two deprotonated citrates and a pair of aqua ligands in a distorted octahedral fashion. The anionic complex contains a centro-symmetrical planar of four-membered Fe2O2 ring. There are significant contributions to the stabilities of the assembled lattices in 1-3 arising from the protonated pyridine analogue counterions neutralizing the anionic charges of the complexes. The units in the complexes are connected together via hydrogen bonding to form 3D supramolecular networks. The supramolecular structures of 1-2 show alternating and motif linking the anionic moieties which are in turn interwoven with cationic moieties, while 3 shows alternating and motif. The magnetic properties of 1-3 are investigated and discussed in detail. 相似文献
17.
Adrian E. Ion 《Inorganica chimica acta》2007,360(13):3925-3931
The synthesis of two nickel(II) complexes based on a central bridging triaminoguanidine scaffold and a capping ligand per metal ion is reported. When 2,2′-bipyridine (bipy) is utilized as co-ligand the complex [Ni3LBr(bipy)3(H2O)3]NO3 · 9H2O · 1.5DMF (1) is obtained which crystallizes in the hexagonal space group P63/m. Complex 1 shows an interesting supramolecular structure pattern with alternating hydrophilic and hydrophobic layers characterized by extensive hydrogen-bonding and π-π-stacking, respectively. With 2,4,6-(2-pyridyl)-1,3,5-triazine (tptz) as capping ligand, complex [Ni3LBr(tptz)3]ClO4 · 7H2O · 1.5DMF (2) is obtained. The magnetic susceptibility data can be fitted using an equilateral triangle model () with an isotropic coupling constant of J=-31.0±0.6 for 1 and for 2. 相似文献
18.
Danielle Cangussu Humberto O. Stumpf Jim A. Thomas Miguel Julve 《Inorganica chimica acta》2005,358(7):2292-2302
The preparation and magnetic properties of three copper(II) compounds of formulae [Cu2(bpcam)2(H2O)2(C2O4)] (1), [Cu2(bpcam)2(H2O)4(C4O4)] · 10 H2O (2) and Cu2(bpcam)2(C5O5)(H2O)3 (3) [bpcam = bis(2-pyrimidyl)amidate, and are reported. The structures of two of them (1 and 2) have been solved by single crystal X-ray diffraction and consists of centrosymmetric discrete copper(II) dinuclear units bridged by bis-bidentate oxalate (1) and bis-monodentate squarate (2), with the bpcam group acting as a terminal tridentate ligand. Each copper atom in 1 exhibits a distorted elongated octahedral coordination geometry. Three bpcam nitrogen atoms and one oxalate oxygen define the basal plane while the other oxalate oxygen and a water molecule take up the axial positions. Each copper atom in 2 is in an elongated octahedral surrounding with three bpcam nitrogen atoms and one squarate oxygen in the equatorial plane and two water molecules in the axial positions. The intramolecular copper-copper separations are 5.677(1) (1) and 7.819(53) Å (2). Magnetic susceptibility measurements for 1-3 in the temperature range 1.9-290 K show the occurrence of weak ferromagnetic interactions through oxalato (J = +0.75 cm−1) and squarato (J = +1.26 cm−1), the Hamiltonian being defined by . These values are analyzed and discussed in the light of the available magneto-structural data for analogous systems. The quasi-Curie law observed in 3 (θ = −1.15 K) contrasts with the significant antiferromagnetic interaction through bis-chelating croconate in other structurally characterized croconate-bridged copper(II) complexes and rules out the presence of bridging croconate in this compound. 相似文献
19.
Five new supramolecular lanthanide coordination polymers with three different structures, {[La2(IA)3(phen)2] · 2H2O}n (1), {[Ln(IA)1.5(phen)] · xH2O}n [x = 1, Ln = Eu (2); x = 0.25, Ln = Dy (3)], and [Ln(IA)1.5(phen)]n [Ln = Er (4); Yb (5)], were prepared by hydro- and solvothermal reactions of lanthanide chlorides with itaconic acid (H2IA) and 1,10-phenanthroline (phen), and structurally characterized by single crystal X-ray diffraction. 1 Comprises 1-D double-chains that are further assembled to a 3-D supramolecular structure via hydrogen bonds and π-π stacks between phen molecules. 2 and 3 have 2-D infinite networks which are further constructed to form 3-D supramolecular architectures with 1-D channels by π-π aromatic interactions. 4 and 5 have 2-D layer structures consisting of three types of rings which are further architectured to form 3-D supramolecular structures by C-H?O hydrogen bonds. The H2IA ligands are all completely deprotonated and exhibit tetra-, penta-, and hexadentate coordination modes in the titled complexes. The high-resolution emission spectrum of 2 shows only one Eu3+ ion site in 2, which is in agreement with the result of X-ray diffraction. And the magnetic property and the thermal stability of 2 were also investigated. 相似文献
20.
Bellam Sreenivasulu 《Inorganica chimica acta》2009,362(8):2735-281
Complexes [Cu(HSas)(H2O)] · 2H2O (H3Sas = N-(2-hydroxybenzyl)-l-aspartic acid) (1), [Cu(HMeSglu)(H2O)] · 2H2O (H3MeSglu = (N-(2-hydroxy-5-methylbenzyl)-l-glutamic acid) (2), [Cu2(Smet)2] (H2Smet = (N-(2-hydroxybenzyl)-l-methionine) (3), [Ni(HSas)(H2O)] (4), [Ni2(Smet)2(H2O)2] (5), and [Ni(HSapg)2] (H2Sapg = (N-(2-hydroxybenzyl)-l-aspargine) (6) have been synthesized and characterized by chemical and spectroscopic methods. Structural determination by single crystal X-ray diffraction studies revealed 1D coordination polymeric structures in 2 and 4, and hydrogen-bonded network structure in 5 and 6. In contrast to previously reported coordination compounds with similar ligands, the phenol remains protonated and bonded to the metal ions in 2 and 4, and also probably in 1. However, the phenolic group is non-bonded in 6. 相似文献