[Ni(bpy)(mal)(H2O)3]·H2O and [Ni(4,4′-dmbpy)(mal)(H2O)3]·1.5H2O: syntheses,crystal structures,magnetic properties,and computational study of stacking interactions

[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, π–π 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.     

Synthesis,crystal structure and magnetic properties of a 1D coordination polymer[Ni(phth)(phen)(H2O)] n · n H2O

A new one-dimensional coordination polymer [Ni(phth)(phen)(H₂O)] _n ?·?nH₂O was synthesized. The structure was determined by X-ray crystallography revealing that each nickel atom is five-coordinate bridged via phthalate ion to form a zigzag chain. The chains are further linked together via hydrogen-bonding interactions to construct a three dimensional supramolecular network. The magnetic properties of the complex show that there are weak antiferromagnetic interactions between Ni(II) centers.     

Synthesis,crystal structures and magnetic properties of a series of new cyano-bridged complexes derived from templates [Ni(CN)4]2− and [Co(III)(CN)6]3−

Three new cyano-bridged complexes 1 [Ni(tn)₂Ni(CN)₄] (tn?=?1,3-diaminopropane), 2 [Cu^II(dipn)Ni^II(CN)₄], and 3 [Cu(dipn)]₆[Co(CN)₆]₄?·?4H₂O (dipn?=?dipropylenetriamine) have been assembled by the templates [Ni(CN)₄]^2? and [Co(CN)₆]^3?. 1 consists of a one-dimensional linear chain–Ni(tn)₂–NC–Ni(CN)₂–CN–Ni(tn)_2? in which the Ni(II) centers are linked by two CN groups. One 1-D zigzag chain of 2 is formed with–Ni(2)–C–N–Cu(1)–N–C–linkages. A 2D structure of 3 is formed by an alternate array of [Co(CN)₆]^3? and [Co][Cu₆] units. For 1, there is an overall weak antiferromagnetic interaction between Ni(II) ions through the–NC–Ni–CN–bridges of the diamagnetic [Ni(CN)₄]^2? anions. 2 exhibits a weak antiferromagnetic exchange interaction between copper(II) ions mediated by [Ni(CN)₄]^2? diamagnetic bridges. Complex 3 exhibits a weak ferromagnetic interaction between nearest Cu^II and Cu^II atoms through–NC–Co–CN–bridges.     

Synthesis, crystal structures, and properties of [Ca(H2O)2(Dmf@CB[6])(Bdc)] · DMF · 4H2O and [Ca(H2O)3(Dmf@CB[6])]Cl2 · 2H2O

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.     

Synthesis and properties of Na6[Pb(S2O3)4] · 6H2O

Conditions for the synthesis of the water-soluble lead thiosulfate complex Na₆[Pb(S₂O₃)₄] · 6H₂O were determined. The complex synthesized was characterized by UV and IR spectroscopy and X-ray phase and thermal analyses. Thermolysis schemes were proposed on the basis of the IR and mass spectra of the thermal decomposition products.     

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.     

Synthesis and structure of [UO2(SeO4)(C2H4N4)2] · 0.5H2O

The single-crystal X-ray diffraction analysis of [UO₂(SeO₄)(C₂H₄N₄)₂] · 0.5H₂O (I) is performed. The crystals are monoclinic: space group C2/c, Z = 8, a = 19.035(2), b = 7.1326(8), c = 21.477(2) Å, β = 109.683(4)°. The main structural units of the crystal are chains of [UO₂(SeO₄)(C₂H₄N₄)₂]. Compound I belongs to the crystal-chemical group AT³M ₂ ¹ (A = UO ₂ ²⁺ , T³ = SeO ₄ ^2? , M¹ is a cyanoguanidine molecule) of the uranyl complexes. The chains are united into three-dimensional framework through hydrogen bonds involving the oxygen atoms of the selenate and uranyl groups, the nitrogen atoms of cyanoguanidine, and the hydrogen atoms of the cyanoguanidine or water molecules.     

Synthesis, crystal structure, and photophysical properties of acid (H3O)2[{W6Br8}Br6] · 4H2O

Compound (H₃O)₂[{W₆Br₈}Br₆] · 4H₂O is synthesized by the reaction of polymeric tungsten bromide W₆Br₁₂ with hydrobromic acid in an ethanolic solution. The structure of the compound is a packing of counterions H₃O⁺ and [{W₆Br₈}Br₆]^2? and crystallization water molecules joined with each other by an extended system of hydrogen bonds. The finely crystalline sample of the complex exhibits luminescence, whose spectrum has a broad profile from ??500 nm to more than 950 nm with a maximum at ??715 nm, with an absolute quantum yield of ??0.225. The emission is characterized by the biexponential decay with lifetimes of ??2.2 and ??8.4 ??s.     

Synthesis,structure, and properties of a new trinuclear iron cluster, [(MeOH)(H2O)2Fe3(μ3-O)(μ-OOCC6H4OCH2C5H4NH)6] (ClO4)7 · · 8MeOH · 3.5H2O

Reactions of iron(m) salts with a new bidentate ligand, which is potentially capable of forming binuclear iron complexes upon complexation, were studied. Under various conditions, we succeeded in isolating only the trinuclear cationic complex (Fe^III ₃(O₂CR)6(₃-)17+ (1), where RCO₂ is 2-(pyrid-2-ylmethoxy)benzoic acid protonated at the pyridyl moiety. The structure of 1 was established by spectral, magnetic, and X-ray structural studies. Cyclic voltammetry in McCN in the temperature range from -35 to 20 °C demonstrated that 1 undergoes successive Fe^IIIFe^II reduction in three one-electron stages, which is indicative of the electronic interaction between iron atoms in the complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2086–2092, August, 1996.     

Synthesis, crystal structure and magnetic properties of bimetallic complex of Ni2Co(TTHA)·12H2O

The bimetallic complex of Ni₂Co(TTHA)·12H₂O (TTHA = triethylene tetraminehexaacetic acid) was synthesized and characterized structurally and magnetically. The title complex crystallizes in the triclinic space group P ī with a = 0.7316(2), b = 0.8624(2), c = 1.5041(4) nm; α = 73.38(2), β = 83.97(2), γ = 70.50(2)°. The crystal structure is built up of [Ni₂(TTHA)(H₂O)₂]²⁻, Co(H₂O)₆²⁺ and water molecules. The variable magnetic measurement shows that there is strong antiferromagnetic interaction between two Ni(II) ions in [Ni₂(TTHA) (H₂O)₂]²⁻ with J _Ni−Ni = −141.64 cm⁻¹, g _Ni = 2.21 and that the constant of spin-orbit coupling of Co(II) ion is −134.8 cm⁻¹. __________ Translated from Acta Scientiarum Naturalium Universitatis Nankaiensis, 2007, 40(1): 6–10 [译自: 南开大学学报(自然科学版)]     

Syntheses and structures of nine-coordinate NH4[HoIII(Edta)(H2O)3] · 1.5H2O, (NH4)4[Ho 2 III (Dtpa)2] · 9H2O, and (NH4)3[HoIII(Ttha)] · 5H2O complexes

The three title complexes, NH₄[Ho^III(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[Ho^III(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) ų, Z = 16, M = 552.26, ρ_calcd = 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) ų, Z = 1, M = 1340.80, ρ_calcd = 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) ų, Z = 2, M = 797.55, ρ_calcd = 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.     

Synthesis and Study of Tetraamminenickel 9-Molybdomanganate [Ni(NH3)4] · H4[MnMo9O32] · 6H2O

Tetraamminenickel 9-molybdomanganate [Ni(NH₃)₄] · H₄[MnMo₉O₃₂] · 6H₂O (zbdI) has been synthesized and studied by thermogravimetry, IR spectroscopy, and X-ray powder diffraction analysis. The crystals of compound I are monoclinic: a = 11.5961 Å, b = 11.1609 Å, c = 8.7200 Å, β = 109.23°, V = 1065.59 ų, ρ_calcd = 3.067 g/cm³, Z = 1.     

Synthesis and Structure of a Novel Compound [Cu2(EDTA)(Py)2(H2O)2]·2H2O

A novel compound [Cu2(EDTA)(Py)2(H2O)2]·2H2O was synthesized by the reaction of CuSO4(5H2O with H4EDTA in pyridine/water (V/V = 1/4) solvent, and characterized by elemental analysis, IR spectrum and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 1.26974(6), b = 0.67949(3), c = 1.48548(3) nm, β = 91.454(2)o, V = 1.28122(9) nm3, Z = 2, Dc = 1.673 g/cm3, Mr = 645.56, F(000) = 664, μ(MoKα) = 1.729 mm-1, the final R = 0.0353 and wR = 0.0832 for 1920 observed reflections (I > 2((I)). The compound is a centrosymmetric binuclear molecule with bridged EDTA group. Each Cu(II) atom is linked to two oxygen atoms and one nitrogen atom of EDTA, one oxygen atom of water and one nitrogen atom of pyridine to form a distorted square pyramidal environment. There exist face-to-face π-π stacking interactions between pyridine rings from neighboring molecule with the interplanar distance of 0.3670 nm and hydrogen bonding between EDTA and water molecules.     

Synthesis, characterization and magnetic investigation of (NH4)0.5Mn1.25(H2O)2[BP2O8]·0.5H2O

A new borophosphate compound with the composition (NH₄) _χ Mn_((3?χ)/2)(H₂O)₂ [BP₂O₈]·(1?x)H₂O was prepared under mild hydrothermal conditions and characterized by X-ray powder diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) methods. The title compound was synthesized from MnCl₂·2H₂O, H₃BO₃, and (NH₄)₂HPO₄ with variable molar ratios by heating at 180 °C for 7 days in an autoclave. The X-ray diffraction data of the water insoluble polycrystalline powder was indexed using the TREOR program in hexagonal system with the unit cell parameters of a = 9.5104, c = 15.7108 Å, Z = 6 and the space group P6₅ (No.176). (NH₄) _χ Mn_((3?χ)/2)(H₂O)₂ [BP₂O₈]·(1?x)H₂O is isostructural with (NH₄) _χ M _((3?χ) ^2)/II (H₂O)₂ [BP₂O₈]·(1?x)H₂O (M^II = Co, Cd, Mg; x = 0.5–1). Its unit cell parameters and hkl values were in good agreement with the other isostructural compounds. This is the first report presenting both the synthetic details and the indexed X-ray powder diffraction pattern of this compound along with the characterization by FTIR, thermal gravimetric analysis, scanning electron microscopy and EPR.      

Synthesis, crystal structure, and fluorescence properties of a novel coordination polymer [Zn(L)(4,4′-bipyridine)(H2O)] n · (H2O)4

In this work, a novel and rare coordination polymer, [Zn(L)(Bipy)(H₂O)] _n · (H₂O)₄ (H₂L??sphenylpropylmalonate acid, Bipy??4,4??-bipyridine), has been synthesized and characterized by elemental analysis, FT-IR spectroscopy, and solid fluorimetry studies. In the crystal, the Zn²⁺ ion of the complex is hexacoordinated in a slightly distorted octahedral configuration forming the unit structure, 2D structure, and 3D framework. The supramolecular architecture was constructed by a unit of (H₂O)₄ discrete water cluster. Besides, the coordination polymer displays strong emission spectra due to the metal-to-ligand charge-transfer transition, having potential applications as fluorescent materials.     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

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) ų; 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) ų; 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.     

Crystal Structure and Interaction with DNA of [Ni(phen)(mal)(H2O)2]·3H2O

A new complex [Ni(phen)(mal)(H2O)2]·3H2O (phen = 1,10-phenanthroline,mal2-= malonic acid) has been synthesized by the reaction of nickel nitrate,phen and malonic acid.EA,IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the title complex.Crystal data:monoclinic system,space group P2/c,a =8.937(3),b = 12.163(5),c = 9.725(3)(A),β = 119.36°,C15H19N2O9Ni,Mr= 430.03,Z = 2,F(000) =446,V = 921.3 (A)3,Dc = 1.550 g/cm3,μ = 1.104 mm-1,-10≤h≤ 10,-12≤k≤ 14,-11 ≤l≤7,R =0.0261 and wR = 0.0609 for 4376 (Rint = 0.0203) independent reflections and 1631 observed ones (I＞ 2σ(I)).Ni(Ⅱ) exhibits an octahedral coordination geometry,with hydrogen bonds and π-π interactions stabilizing the whole structure.UV spectrum of the complex interacting with protamine DNA indicates that the title compound interacts with DNA via insertion mode with bonding constant Kb of 1.11 × 104.     

Synthesis, Structure and Antimicrobial Activity of a Cyclic Compound [Cu(Pmal)(Dadm)(H2O)]2·4H2O

A new copper compound constructed from H2 Pmal (phenylmalonic acid), Dadm (4,4-diaminodiphenylmethane) and Cu(Ⅱ) has been synthesized from H2O-EtOH-DMF solution, and is characterized by X-ray single-crystal diffraction and other measurements. The compound crystallizes in the monoclinic system, space group C2/c with a=13.7866(6), b=10.1557(4), c=30.9036(17), β=101.422(5)o, V=4241.2(3)3 , Z=4, Dc=1.547g/cm3 , Mr=987.94, F(000)=2056, μ(MoKα)=1.078 mm-1 , S=1.007, R=0.0453 and wR=0.987 for 2806 observed reflections (I>2σ (I)). The title compound is characteristic of the cyclic dimeric molecules which further aggregate through hydrogen bonds and π-π interactions to form a 3-D supramolecular network. The microbial activities of the title compound and its reagents are investigated with filter paper discs diffusion method. The results show that the activity of the title compound is slightly better than its precursor reagents.     

Synthesis, Crystal Structure and Luminescence Property of [Co(hmz)2(H2O)4]·2H2O

A new mononuclear Co(Ⅱ) complex, [Co(hmz)2(H2O)4]·2H2O, has been synthesized by the reaction of Co(CH3COO)2·4H2O with 1-(4-hydroxyphenyl)-5-mercaptotetrazole (Hhmz). It crystallizes in the monoclinic system, space group P21/n with a = 13.502(5), b = 6.718(3), c = 13.972(6) (A), β = 117.532(4)°, V = 1123.9(8) (A)3, Z = 2, M r = 553.45, F(000) = 570, Dc = 1.635 g/cm3, μ = 1.008 mm-1, the final R = 0.0272 and wR = 0.0684 for 2194 observed reflections (Ⅰ＞ 2σ(Ⅰ)). The Co(Ⅱ) is six-coordinated by two nitrogen atoms from two hmz-1 ligands and four water molecules, forming an octahedral geometry. The intermolecular hydrogen bonding and offset-panel π-π stacking interactions between the adjacent molecules extend the compound into a three- dimensional supramolecular framework. The title compound emits strong blue fluorescent light (λem(max) = 427 nm) at room temperature and is red-shifted compared with free ligand Hhmz (λem(max) = 342 nm).     

Synthesis and structures of two cobalt complexes [NaCoII(NTA)(H2O)] n and NH4[CoIII(IDA)2] · 2H2O

Two cobalt complexes [NaCo^II(nta)(H₂O)] _n (H₃nta?=?nitrilotriacetic acid) (1) and NH₄[Co^III(ida)₂]?·?2H₂O (H₂ida?=?iminodiacetic acid) (2) have been synthesized and characterized by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the orthorhombic system, space group P2₁2₁2₁ with a?=?7.9770(12)?Å, b?=?9.7613(15)?Å, c?=?12.1945(18)?Å, V?=?949.5(2)?ų, Z?=?4, and R ₁?=?0.0705 for 1597 observed reflections. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c with a?=?5.1801(3)?Å, b?=?11.2073(6)?Å, c?=?12.2891(7)?Å, V?=?707.09(7)?ų, Z?=?2, and R ₁?=?0.0349 for 1143 observed reflections. In compound 1, the Co is coordinated by a nitrogen and five oxygen atoms in a distorted octahedral geometry {CoNO₅}, and the Na is coordinated by one water molecule and four carboxyl oxygen atoms in slightly distorted square pyramidal geometry. The entire structure shows a three-dimensional network. In compound 2, Co atom is equatorially coordinated by two ida ligands in a distorted octahedral geometry {CoN₂O₄}. The discrete [Co(ida)₂]^2? anions are linked by hydrogen bonding to a three-dimensional supramolecular network.