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1.
Complexes [Ca(H2O)2(Dmf@CB[6])(Bdc)] · DMF · 4H2O (I) and [Ca(H2O)3(Dmf@CB[6])]Cl2 · 2H2O (II) are synthesized by the heating (95°C) of a mixture of calcium chloride and cucurbit[6]uril (CB[6]) in a mixture of dimethylformamide (DMF) and water with the addition of terephthalic acid (H2Bdc) in the case of complex I or triethylamine for complex II. The compounds are characterized by X-ray diffraction analysis, IR spectroscopy, and thermogravimetric and elemental analyses. The luminescence spectra are also recorded. According to the X-ray diffraction data, the calcium atom is coordinated by the oxygen atoms of the cucurbit[6]uril molecule, water molecules, and terephthalate anion (for I). The internal cavity of the cavitand is occupied by DMF.  相似文献   

2.
《Polyhedron》2003,22(25-26):3383-3387
Three new octahedral rhenium chalcocyanide cluster compounds [CuNH3(trien)]2[Re6S8(CN)6] · 7H2O (1), [CuNH3(trien)]2[Re6Se8(CN)6] (2) and [CuNH3(trien)]2[Re6Te8(CN)6] · H2O (3) exhibiting ionic structures have been obtained by the diffusion of an ammonia solution of KCs3[Re6S8(CN)6] (for 1), K4[Re6Se8(CN)6] · 3.5H2O (for 2) or Cs4[Re6Te8(CN)6] · 2H2O (for 3) into a glycerol solution of CuCl2 · 2H2O in the presence of trien (trien=triethylenetetramine). The compounds have been characterized by single-crystal X-ray diffraction. All three compounds contain a cationic complex [CuNH3(trien)]2+ which was not described previously.  相似文献   

3.
Binary complex salts, [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH3, hydrocarbons, and ethylenediamine.  相似文献   

4.

Two ion pair complexes, [Ru(bpy)3]2[Fe(CN)6]I [sdot] 7H3O (1) and [Ru(bpy)3][Fe(CN)5NO](CH3OH) [sdot] H2O (2) (bpy = 2,2-bipyridine) have been synthesized and structurally characterized. X-Ray crystallographic structures of 1 and 2 both show Fe(III) and Ru(II) in distorted octahedral environments. In both complexes, H-bonding interactions between an uncoordinated water molecule and the nitrogen atom of a cyano group exist.  相似文献   

5.
The three title complexes, NH4[HoIII(Edta)(H2O)3] · 1.5H2O (I) (H4Edta = ethylenedianine-N,N,N′,N′-tetraacetic acid), (NH4)4[Ho 2 III (Dtpa)2] · 9H2O (II) (H5Dtpa = diethylenetriamine-N,N,N′,N″,N″-entaacetic acid), and (NH4)3[HoIII(Ttha)] · 5H2O (III) (H6 Ttha = triethylenetetramine-N,N,N′,N″,N?,N?-hexaacetic acid), have been prepared and characterized by FT-IR, elemental analyses, and single-crystal X-ray diffraction technique. Complex I has a nine-coordinate mononuclear structure with distorted monocapped square antiprismatic conformation and its crystal structure belongs to orthorhombic system and Fdd2 space group. The crystal data are as follows: a = 19.343(9), b = 35.125(17), c = 12.364(6) Å, V = 8400(7) Å3, Z = 16, M = 552.26, ρcalcd = 1.747 g cm?3 μ = 3.828 mm?1, and F(000) = 4368. Complex II has a binuclear nine-coordinate pseudomonocapped square antiprismatic conformation and its crystal structure belongs to triclinic system and space P1 group. The crystal data are as follows: a = 9.7637(16), b = 9.9722(16), c = 12.945(2) Å, α= 85.853(2)°, β = 77. 140(2)°, γ = 77.140(2)°, V = 1198.4(3) Å3, Z = 1, M = 1340.80, ρcalcd = 1.858 g cm?3, μ = 3.380 mm?1, and F(000) = 674. As for complex III, it also has nine-coordinate mononuclear structure with distorted tricapped trigonal prism and its crystal structure belongs to monoclinic system andP21/c space group. The crystal data are as follows: a = 10.349(3), b = 12.760(4), c = 23.142(7) Å, β = 91.020(6)°, V = 3055.6(16) Å3, Z = 2, M = 797.55, ρcalcd = 1.734 g cm?3, μ = 2.674 mm?1, and F(000) = 1624. The results showed that although the ligands are different from one another in the shape and the numbers of coordination atoms, they all have nine-coordinate structures. However, one of them has binuclear structure and the other two have mononuclear structures because of the difference of the ligands.  相似文献   

6.
Two new banana-shaped tungstophosphates [M6(H2O)2(PW9O34)2(PW6O26)]17 ? (MII?=?NiII, CoII) incorporating two types of lacunary polyoxometalate units have been synthesized in aqueous solution and characterized by elemental analyses, IR, and UV spectra, and single-crystal X-ray diffraction. Structural analyses show that Na6H11[Ni6(H2O)2(PW9O34)2(PW6O26)]?·?32H2O (1) and Na7H10[Co6(H2O)2(PW9O34)2(PW6O26)]?· 31H2O (2) are generated from two tri-MII substituted B-α-[(MOH2)M2PW9O34] Keggin units connected by a hexavacant [PW6O26]11? Keggin fragment, leading to the MII-containing banana-shaped tungstophosphates. Magnetic properties of 2 show decrease of the molar magnetic susceptibility at higher temperatures results from spin-orbit coupling of CoII and antiferromagnetic interactions whereas the maximum at the lower temperatures is indicative of the ferromagnetic interactions within the trinuclear CoII spin cluster in the sandwich belt.  相似文献   

7.
8.
[Ni(bpy)(mal)(H2O)3]·H2O and [Ni(4,4′-dmbpy)(mal)(H2O)3]·1.5H2O (mal = maleato; bpy = 2,2′-bipyridine; 4,4′-dmbpy = 4,4′-dimethyl-2,2′-bipyridine) exhibit molecular crystal structures. The Ni(II) central ions in both complexes are six-coordinate by one chelate bonded L–L ligand, three aqua ligands, and one position is occupied by a maleato oxygen donor atom. Hydrogen bonded ribbon-like supramolecular structural motifs are present in both studied complexes; these are linked by weaker C–H?O hydrogen bonds in [Ni(bpy)(mal)(H2O)3]·H2O, whereas in [Ni(4,4′-dmbpy)(mal)(H2O)3]·1,5H2O the hydrogen bonded ribbons are linked by O?H-O-H?O hydrogen bonds with the participation of the additional water solvate molecule positioned on the twofold axis. In both structures, ππ stacking interactions with different patterns in respective structures were found. The role of dispersion energy and many-body effects in the stabilization of bpy and 4,4′-dmbpy stacking interactions were investigated using methods of computational chemistry. Those confirm the dispersion-dominated stabilization of the 4,4′-dmbpy supramolecular chain-like structure, with only marginal impact of cooperativity effects. Thermal decompositions of both complexes start with dehydration. Magnetic susceptibility studies performed from 2 to 300 K revealed a dominant effect of the zero-field splitting of the Ni(II) ion, governing the low-temperature magnetic properties of both compounds.  相似文献   

9.
Two new hybrid Dawson-based polyoxotungstates, [Mn(2,2′-bipy)3]H2[Mn(2,2′-bipy)2][P2W18O62] (1) and [Co(H2biim)3)]2H2[P2W18O62] · 8H2O (2) (2,2′-bipy = 2,2′-bipyridine, H2biim = 2,2′-biimdazole), have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses (TGA), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectra. Compound 1 is a 1-D zigzag chain constructed from alternate Dawson-type heteropolyanions [α-P2W18O62]6? and metal coordination cations [Mn(2,2′-bipy)2]2+, in which the 1-D chains are extended into a 3-D framework through C–H ··· π and π–π stacking interactions. Compound 2 is a discrete structure consisting of [α-P2W18O62]6? and two [Co(H2biim)3)]2+ cations, forming a 3-D supramolecular framework via N–H ··· O hydrogen bonds and C–H ··· π interactions. Photoluminescence properties of 1 and 2 have been investigated at room temperature.  相似文献   

10.
11.
The binuclear complexes [Cu2L2(H2O)4] · 5H2O (1) and [Ni2L2(H2O)4] · 2H2O (2) (where L = C11H11NO5S, H 2 L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P21/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) Å3; Z = 4; D Calcd = 1.729 g cm?3; F(000) = 1712; μ = 1.554 mm?1; R 1 = 0.0519, wR 2 = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) Å3; Z = 2; D Calcd = 1.604 g cm?3; F(000) = 800; μ = 1.388 mm?1; R 1 = 0.1859, wR 2 = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H2O)4 water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.  相似文献   

12.
The crystal and molecular structures of K3[TbIII(nta)2(H2O)](5.5H2O (nta = nitrilotriacetic acid) and K3[YbIII(nta)2](5H2O complexes have been determined by single-crystal Xray structural analyses. Because TbIII and YbIII have different ionic radii and electronic configura- tions, they take nine- and eight-coordinate structures with two nta ligands, respectively. The crystal of K3[TbIII(nta)2(H2O)](5.5H2O belongs to orthorhombic, space group Pccn with a = 1.6374(7), b = 1.9913(8), c = 1.5068(6) nm, V = 4.913(3) nm3, Z = 8, Mr = 769.54, Dc = 2.081 g/cm3, μ= 3.476 mm-1 and F(000) = 3048. The final R and wR are 0.0432 and 0.0916 for 4961 observed reflections (I > 2.0(σI)), and 0.0814 and 0.1042 for all 21921 reflections, respectively. The [TbIII(nta)2(H2O)]3- complex anion has a nine-coordinate pseudo-monocapped square anti-prismatic structure, in which two N and six O coordinated atoms are from two nta ligands and the left ninth O atom from one water molecule. The crystal of K3[YbIII(nta)2]·5H2O is of monoclinic, space group P21/c with a = 1.5579(5), b = 0.9981(3), c = 1.5956(5) nm, β = 109.776(5), V = 2.3348(13) nm3, Z = 4, Mr = 756.62, Dc = 2.153 g/cm3, μ= 4.624 mm-1 and F(000) = 1484. The final R and wR are 0.0253 and 0.0657 for 4123 observed reflections (I > 2.0(σI)), and 0.0320 and 0.0731 for all 9414 reflections, respectively. The [YbIII(nta)2]3- complex anion has an eight-coordination structure with a distorted square antiprismatic prism, in which each nta acts as a tetradentate ligand with one N atom from the amino group and three O atoms from the carboxylic groups.  相似文献   

13.
Compounds p-HOOCC6F4COOH · H2O (H2L · H2O), [Tb2(H2O)4(L)3 · 2H2O] n (I), and Tb2(Phen)2(L)3 · 2H2O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H2L · H2O is built of centrosymmetric molecules H2L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb2(H2O)4(L)3] n and molecules of water of crystallization. The ligands are the L2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO9 is a distorted three-capped trigonal prism. Acid H2L manifests photoluminescence in the UV region (??max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb3+ ions, and the band with ??max = 545 nm (transition 5 D 4?? 7 F 5) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.  相似文献   

14.
Synthesis, structure characterization, and magnetic properties of three novel cyano-bridged complexes {[MnII(bpy)(DMF)2]2[MoIV(CN)8]·1.5H2O} n (1), [CuII(L)]2[MoIV(CN)8]·6.75H2O (2), and [MnII(bpy)2]4[MoIV(CN)8]2·4MeOH·4H2O (3) (where DMF = N,N′-dimethylformamide; bpy = 2,2-bipyridine and L = 1,3,6,8,11,14-hexaazatricyclo[12.2.1.18,11]octadecane) have been studied. The X-ray single-crystal structure reveals that 1 is a cyanide-bridged 1D infinite chain with the alternating of MnII(bpy)(DMF)2 and MoIV(CN)8 moieties. The neighboring chains interact with each other by hydrogen bonding to form a sheet-like network, and the layers further extend to a 3D network due to the face-to-face π···π stack interactions. For 2, the MoIV center adopts a distorted square antiprism coordination environment, while the CuII center adopts a distorted square pyramidal geometry. The weak Mo–CN···Cu interactions between neighboring molecules lead to a 2D network structure of 2. For 3, basic structural unit is centrosymmetric and contains four MnII centers bridged by two octacyanomolybdate(IV). Here, their magnetic properties have also been studied. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

15.
Qualitative single crystals of ??-complexes Cu(H+L)(ClO4)]ClO4 · H2O (I), Cu(H+L)(BF4)]BF4 · H2O (II), and [Cu(H+L)(H2O)]SiF6 · H2O (III) are synthesized from solutions of 3-(diallylamino)propanenitrile (L) in propanol, ethanol, and methanol-water acidified with the corresponding acid to pH 3.5?C5 and from the copper(II) salts (Cu(ClO4)2 · 6H2O, Cu(BF4)2 · 6H2O, and CuSiF6 · 4H2O) using the alternating-current electrochemical method on copper wire electrodes. The crystal structures of the complexes are determined. All compounds crystallize in the monoclinic crystal system: complexes I and II are isostructural, space group P21/n, Z = 4. For compound III, space group P21/c, Z = 8. Unit cell parameters: for I a =7.8153(3), b = 16.7824(7), c = 12.4426(5) ?, ?? = 93.410(2)°, V = 1629.1(1) ?3; for II, a = 7.6755(4), b = 16.7119(7), c = 12.3784(6) ?, ?? = 94.354(2)°, V = 1583.2(1); and for III a = 9.826(2), b = 24.009(3), c = 12.061(2) ?, ?? = 91.820(6)°, V = 2843.9(7) ?3. The trigonal pyramidal coordination of the copper atom in complexes I-III is formed by two C=C bonds of the allyl groups of H+L, the nitrile N atom of the adjacent cation of the ligand, and the O or F atom of the ClO 4 ? or BF 4 ? anions. In structure III, the apical position of the pyramid is occupied by the O atom of the water molecule, since the SiF 6 2? anion is considerably remote from the copper(I) atom. However, this anion is bound to the organic cation by hydrogen bonds F??H (2.05?C2.51 ?).  相似文献   

16.
Two lanthanide complexes, (mnH)2[EuIII(egta)]2·6H2O (1) (H4egta = ethyleneglycol-bis-(2aminoethylether)-N,N,N,N′-tetraacetic acid) and (mnH)4[EuIII2(dtpa)2]·6H2O (2) (H5dtpa = diethylenetriamine-N,N,N,N″,N″-pentaacetic acid), have been synthesized and characterized by FT-IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction. X-ray diffraction reveals that 1 is multinuclear nine-coordinate and crystallizes in the monoclinic crystal system with space group C2/c. The obtained cell dimensions are a = 38.513(3)?Å, b = 13.5877(8)?Å, c = 8.7051(5)?Å, β = 99.6780(10)°, and 4490.6(5)?Å3. Each methylamine (mnH+) cation in 1, through hydrogen bonds, connects three adjacent [EuIII(egta)]? anions. The [EuIII(egta)]? anions connect one another forming a 1-D multinuclear zigzag chain structure along the c-axis. Complex 2 is nine-coordinate binuclear structure with tricapped trigonal prismatic conformation and crystallizing in the monoclinic crystal system, but with space group P21/n. The obtained cell dimensions are a = 9.9132(8)?Å, b = 24.1027(18)?Å, c = 10.7120(10)?Å, β = 109.1220(10)°, and 2418.2(3)?Å3. For 2, there are two kinds of methylamine cations (mnH+) connecting [EuIII2(dtpa)2]4? complex anions and lattice waters through hydrogen bonds, leading to formation of a 2-D ladder-like layer structure.  相似文献   

17.
The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.  相似文献   

18.
The X-ray crystal structure and properties of the [Mo(CN)2O(acetam)] · 2.5H2O {acetam = N-[1-(pyridin-2-yl)-ethylidene]diethanetriamine} complex are described. The complex was prepared by the in situ reaction of [Mo(CN)4O(H2O)]2–, 2-acetylpyridine and diethylenetriamine in aqueous solution. The complex is seven coordinated. The Mo atom having a distorted pentagonal bipyramid arrangement with a tetradentate 'half-unit' Schiff base and oxygen ligand in a plane. The properties of the salt, i.r., u.v.–vis. spectra and cyclic voltammetry measurements are described and compared with those of [Mo(CN)2O(diaceen)] · H2O {diaceen = N,N-bis[1-(pyridin-2-yl)ethylidene]ethane-1,2-diamine) having the same coordination number for the metal.  相似文献   

19.
The salt Rb[C6H3(COO)2()] · [C6H3(COOH)3] · 2H2O (I) of trimesic acid was synthesized and its thermal stability and conductivity (10–11 ohm–1 cm–1 at 298 K) were measured. Molecular and crystal structures of I were established by X-ray diffraction analysis. Hydrogen bonding system in complex I was detected by IR and Raman spectroscopies. X-ray diffraction data agree with vibration spectroscopy data.  相似文献   

20.
Two new Cd(II) coordination polymers, [Cd(C4H6N2)2(C4H2O4)(H2O)2] n (1) (where C4H6N2?=?2-methylimidazole, C4H2O4?=?fumarate), and [Cd(C4H6N2)(H2O)(C4H4O4)] n ?·?nH2O (2), (where C4H4O4?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.  相似文献   

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