Synthesis and crystal structure of [CuCl(phen)2]3H3V10O28 · 7 H2O

The new compound, [CuCl(phen)₂]₃H₃V₁₀O₂₈ · 7 H₂O, was prepared by reaction of an aqueous KVO₃ solution (pH 3) with an aqueous solution of CuSO₄ · 5 H₂O in which 1,10‐phenanthroline (phen) and KCl were added. The crystal structure of the compound was determined, and the proton position in H₃V₁₀O₂₈^3– were calculated by the bond length/bond number method and also determined from difference electron density map. The protons are bound to colinearly arranged μ–OV₂ and μ–OV₃ groups which is the common protonation type in trihydrogen decavanadates. The structure crystallizes in P1 space group symmetry. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and structure of 2D‐ and 3D‐ inorganic‐organic coordination polymers: based on Ag‐hmt subunit

Two new inorganic‐organic complexes, namely, [Ag₂(hmt)₂]Cr₂O₇·H₂O ( 1 ) and [Ag(hmt)(tar)_0.5]·H₂O ( 2 ), (hmt = hexamethylenetetramine, Tar = tartarate,), have been synthesized in H₂O/CH₃CN solvent at room temperature. Both molecules have the common [Ag₃hmt₃]³⁺ layers. Compound 1 is a two‐dimensional structure, and Complex 2 shows three‐dimensional topology. In complex 2 , the tartarate molecules are connected with adjacent layers to form parallelogram pores of 18.55×7.44 Å, which are occupied by two water molecules. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

1,6‐Hexanediammonium Dihydrogendecavanadate Dihydrate, (H3N—(CH2)6—NH3)2H2V10O28 · 2 H2O

The crystal structure of (H₃N—(CH₂)₆—NH₃)₂H₂V₁₀O₂₈ � 2 H₂O consists of dihydrogendecavanadate anion with C_i symmetry, two 1,6‐hexanediammonium cations and two water molecules. The structure has a P space group symmetry with one of the cations in special position; this cation is disordered. The polyanion of most usual protonation type is similar as formed in other known dihydrogendecavanadates.     

Synthesis and crystal structure of a new inorganic – organic complex: (4‐ClC7H6NH3)9[Nd(P6O18)2]·9H2O

Single crystals of (4‐ClC₇H₆NH₃)₉[Nd(P₆O₁₈)₂]·9H₂O were synthesized in aqueous solution. This compound crystallizes in a triclinic P1 unit‐cell, with a = 14.898(6), b = 18.049(7), c = 20.695(6)Å, α = 102.04(3), β = 100.49(3), γ = 98.82(3)°, V = 5245(4) ų and Z = 2. The crystal structure has been solved and refined to R = 0.043 (Rw = 0.061) for 20420 observed reflections. The atomic arrangement of the title compound can be described as infinite layers built by complex of Neodyme [Nd(P₆O₁₈)₂] and nine water molecules. The organic cations are located in the space delimited by the successive inorganic layers. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth and magnetic properties of the copper coordination polymer [Cu(µ ‐C2O4)(4‐aminopyridine)2(H2O)]n

In this paper, we consider various ways of crystal growth of the polymer [Cu(µ ‐C₂O₄)(4‐aminopyridine)₂(H₂O)]_n. Single crystals of the size of 1.5×1.5×0.2 mm³ have been grown by a slow diffusion technique from solutions of the monoammine copper complex and of the mixture of potassium oxalate and aminopyridine with the stoichiometric ratio. Magnetic susceptibility and ESR measurements have been performed on single crystals large enough for investigating anisotropic properties. The susceptibility can be well described within the model of a Heisenberg antiferromagnetic spin chain. The magnetic measurements reveal a small concentration of paramagnetic moments reflecting the high quality of the single crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,crystal structure and vibrational characterization of bis‐μ‐peroxo‐hexacarbonatodicerate(IV) complexes of rubidium and cesium

The new compounds Rb₈[Ce(O₂)(CO₃)₃]₂ · 12 H₂O (1) and Cs₈[Ce(O₂)(CO₃)₃]₂ · 10 H₂O (2) were obtained from the reaction of hydrogen peroxide and Ce(III) in saturated alkali carbonate solutions. The crystal structures and the unit cell parameters of (1) triclinic, P‐1 with a = 8.973(2) Å, b = 10.815(2) Å, c = 11.130(3) Å, α = 66.992(2)°, β = 68.337(2)°, γ = 74.639(2)°, V_EZ = 914.7(4) ų, Z = 2, and (2) orthorhombic, Pbca, a = 19.3840(16) Å, b = 18.528(2) Å, c = 10.487(3) Å, V_EZ = 3766.4(13) ų, Z = 8, were determined. Both compounds contain the bis‐µ‐peroxo‐hexacarbonatodicerate(IV)‐ion, [(CO₃)₃Ce(O₂)₂Ce(CO₃)₃]^8‐. IR and Raman spectra were measured and discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and crystallographic characterization of a chiral complex of (R)‐2‐(pyridin‐2‐ylmethylene)amino‐2′‐hydroxy‐1,1′‐binaphthyl(L) with hydrated nickel(II) acetate

A chiral complex of (R)‐2‐((pyridin‐2‐ylmethylene)amino)‐2′‐hydroxy‐1,1′‐binaphthyl ( L ) with hydrated nickel (II) acetate has been synthesized and spectroscopically characterized. The crystal structure of [NiL₂(CH₃OH)(CH₃COO)]CH₃COO·CH₃OH has been determined by single‐crystal X‐ray diffraction. The complex crystallizes in the orthorhombic space group P 2(1) 2(1) 2(1) with cell constants a = 15.1035 (19), b = 17.836 (2), c = 18.730 (2)Å, α = β = γ = 90.00°, Z = 4. The structure was solved by direct methods and refined to R = 0.0346 (wR₂ = 0.0863). The analytical result of the crystal structure indicates that a pair of L ligands chelate to a Ni (II) atom in an asymmetric fashion with one Ni‐N bond being longer than the other, the Ni (II) atom is further coordinated by one methanol molecule and one acetate anion to form a distorted octahedral geometry. In the crystal of the complex, the coordination cation [NiL₂(CH₃OH)(CH₃COO)]⁺, the uncoordinated methanol molecule and uncoordinated acetate anion are further assembled into one‐dimensional chain structure via intermolecular hydrogen bonds along the a‐axis. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Three‐Dimensional Structure Constructed via Hydrogen Bonds and π‐π Stacking Interaction. Crystal Structure of [Cu(AFO)2(H2O)2](ClO4)2.2(AFO).2H2O (AFO = 4,5‐Diazafluoren‐9‐one)

The structure of the title complexes [Cu(AFO)₂(H₂O)₂](ClO₄)₂.2(AFO).2H₂O (AFO = 4,5‐Diazafluoren‐9‐one)has been established by single‐crystal X‐ray diffraction. The complex crystallizes in the triclinic space group P‐1 with cell constants a = 7.659(3) Å, b = 11.066(3) Å, c = 14.203(5) Å, alpha = 75.16(3)°, β = 79.87(3)°, gamma = 85.71(3)°, Z = 1. The structure was solved by direct methods and refined to R₁ = 0.0595 (wR₂ = 0.1164). The X‐ray analysis reveals that a pair of AFO ligands chelate to a Cu(II) atom in an asymmetric fashion with one Cu‐N bond being much longer than the other, the Cu(II) atom is further coordinated by a pair of aqua ligands to form an elongated octahedral geometry. In the crystal of the complex, the mononuclear complex cations [Cu(AFO)₂(H₂O)₂]²⁺, uncoordinated AFO molecules, lattice water molecules and perchlorate anions are assembled into 3‐D structure via hydrogen bonds and π‐π stacking interaction.     

Synthesis,crystal structure and photophysical studies on a ruthenium(II) carbonyl hydrido compound based on 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid (H2bpdc)

A novel complex, namely [Ru^II(PPh₃)(CO)(H)(Hbpdc)]·2MeOH ( 1 ) (H₂bpdc = 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid), has been synthesized from the reaction of H₂bpdc with [Ru^II(PPh₃)₃(CO)(H)₂] in methanol under mild condition and characterized by elemental analysis, IR spectrum, ESI mass spectrometry, and single crystal X‐ray diffraction. The structure shows that the complex crystallizes in the monoclinic space group P2₁/c with unit cell parameters a = 11.8984(13) Å, b = 16.5180(18) Å, c = 25.5322(19) Å, β = 115.302(4)°, V = 4536.6(8) ų, Z = 4. This compound features a 1‐D supramolecular chain constructed via hydrogen bonds. Its photophysical properties have been investigated in MeOH solution and in the solid state at room temperature.     

1:1 Crystal Complexes of 2',6'‐Dimethoxyflavone with 3‐Bromo and 3‐Chloro‐2,6‐dimethoxybenzoic Acid

The structures of two solid inclusion compounds with the 2',6'‐dimethoxyflavone host molecule, 1, were investigated by single‐crystal X‐ray analysis. Both compounds, 1�3‐bromo‐2,6‐dimethoxybenzoic acid (1:1) and 1�3‐chloro‐2,6‐dimethoxybenzoic acid (1:1) crystallize in the centrosymmetric group P‐1. The complexation involves an intermolecular hydrogen bond between the carbonyl group of the flavone and the acidic hydrogen of the acid.     

Syntheses and crystal structures of two polymorphs of three‐dimensional silver (I) 5‐(3‐aminophenyl)tetrazolates

Two polymorphs of silver 5‐(3‐aminophenyl)tetrazolates – α‐ and β‐Ag(amphttz) have been obtained by the reaction of amphttzH with AgNO₃ in presence of ammonia either in ambient condition or under the hydrothermal condition, respectively (amphttzH = 5‐(3‐aminophenyl)tetrazole). Both of the two phases of Ag(amphttz) were characterized by elemental analyses, IR spectra and single‐crystal X‐ray diffraction. X‐ray analysis shows α‐, β‐phases crystallize in P ‐1 with a = 8.551 (2) Å, b = 8.720(2) Å, c = 11.173(2) Å, α = 98.15(3)°, β = 90.95(3)°, γ = 95.45(3)° and C 2/c with a = 13.542(3) Å, b = 10.135(2) Å, c = 12.610(3) Å, β = 113.58(3)°, respectively. The two polymorphs exhibit different 3D structures. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure and electrochemical property of one‐dimensional complex: [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]2[Cu(mnt)2]

One metalorganic complex [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]₂[Cu(mnt)₂] (mnt = maleonitriledithiolate) has been obtained by the reaction of dicyclohexyl‐18‐crown‐6 with K₂mnt and CuCl₂·2H₂O. The title complex has been characterized by elementary analysis, FT‐IR, UV‐Vis spectroscopy and x‐ray single crystal diffraction. The title complex crystallizes in the triclinic space group P1 with crystallographic data: a = 10.870(6) Å, b = 11.536(6) Å, c = 12.904(7) Å, α = 101.541(10)°, β = 110.573(9)°, γ = 99.441(9)°, V = 1435.2(13) ų, Z = 1, D_calcd = 1.350 g/cm³, F(000) = 615, R₁ = 0.0641, wR₂ = 0.1475. It displays one‐dimensional chain‐like structure formed by [K(cis‐syn‐cis‐ dicyclohexyl‐18‐crown‐6)]⁺ complex cations and [Cu(mnt)₂]^2‐ complex anions through N‐K‐N interactions. Its electrochemical behavior has also been studied by the cyclic voltammetry. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of radial‐like ZnO structure by hydrothermal method with ZnSO4·7H2O and Zn(CH3COO)2·2H2O as zinc sources

Radial‐like ZnO structures were prepared using zinc sulfate (ZnSO₄·7H₂O) and zinc acetate [Zn(CH₃COO)₂·2H₂O] as zinc sources by a facile template‐free hydrothermal method in this paper. Structural and optical properties of radial‐like ZnO structures are characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), UV‐vis spectrophotometer and photoluminescence measurement (PL). It has been found that the distinct surface morphologies of radial‐like ZnO structures grown by different zinc sources. Slim radial‐like ZnO with a hexagonal wurtzite structure is grown by using ZnSO₄·7H₂O as zinc sources, whereas coarse radial‐like ZnO with zincite structure is achieved by zinc acetate. The UV‐vis absorption spectra of them both display an obvious and significant absorption in the ultraviolet region. The room temperature PL spectra of ZnO structures grown by two different zinc sources possess a common feature that consists of a strong ultraviolet (UV) peak and visible emission band.     

Synthesis and X-ray structure studies of complex [Cu(o-phenanthroline)2 (saccharin)] · (saccharin) · 2 H2O

The title compound has been synthesized and its crystal structure determined at room temperature, M_r = 824.34, triclinic, space group P–1(2), a = 13.622(4), b = 13.770(4), c = 11.167(3) Å; α = 104.83(2), β = 110.01(2), γ = 62.04(2) degree; U = 1727.0(9) ų, Z = 2, D_calc = 1.59 g/cm³. The final R is 0.066 for 3299 independent observed reflections with I ≧ 3σ(I). The crystal structure consists of repeated [Cu(o-phen)₂(sac)]⁺ cations, non-coordinated saccharin anion and two lattice water. And the central ion Cu²⁺ forms a trigonal-bipyramidal stereochemistry.     

Synthesis and crystal structure determination of 6,7‐dihydro‐2‐methoxy‐4‐(substituted)‐5H ‐benzo[6,7]cyclohepta[1,2‐b ]pyridine‐3‐carbonitrile

The compounds 6,7‐dihydro‐2‐methoxy‐4‐(4‐methylphenyl)‐5H ‐benzo[6.7]cyclohepta[1,2‐b ]pyridine‐3‐carbonitrile (compound IIIa) and 4‐(4‐chlorophenyl)‐6,7‐dihydro‐2‐methoxy‐5H ‐benzo[6,7]cyclohepta[1,2‐b ]pyridine‐3‐carbonitrile (compound IIIb) were synthesized and their structures have been determined from three dimensional X‐ray data using direct method and refined by full matrix least squares with anisotropic thermal parameters for non‐hydrogen atoms to conventional R(gt) of 0.036 and 0.038 for the two compounds respectively. For compound (IIIa) the crystals are monoclinic, space group C_c, with a=11.2909 (5) Å, b=17.7755(8) Å, c=9.1437(4) Å and β=95.428(3)°, while the crystals of the second compound (IIIb) are triclinic, space group P1, with a=8.7465(3)Å, b=10.3958(3)Å, c=10.9011(4)Å, α= 108.3870(10)°, β=101.3741(12)°, γ=97.9594(12)°. The molecular structure of the two compounds have nearly the same configuration, where the cyclohepta ring takes the boat shape and the methoxy and the carbonitrile groups are attached at the same position C₂ and C₈. The difference occurs only at the position C₄, where the substituent is methylphenyl for compound (IIIa) and chlorophenyl for the other. The bond lengths, valency angles and the hydrogen bonding were calculated and fully discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis, structure and characterization of a new inorganic-organic hybrid complex (C3H5N2)2[Cd(C3H4N2)2Nb2O3F8]·2H2O

(C₃H₅N₂)₂[Cd(C₃H₄N₂)₂Nb₂O₃F₈]·2H₂O (C₃H₄N₂=imidazole) (1) was prepared from the hydrothermal reaction of Nb₂O₅, 3CdSO₄·8H₂O, C₃H₄N₂, HF and H₂O at 403 K, and characterized by single crystal X-ray diffraction and IR spectra. 1 crystallizes in the orthorhombic system, space group Pba2, with a=11.0192(9), b=16.8012(14), c=6.8717(6) ?, and Z=2. The crystal is made up of [Cd(C₃H₄N₂)₂Nb₂O₃F₈]²⁻ anions, [C₃H₅N₂]⁺ complex cations and H₂O molecules of crystallization. And the backbone of the compound is a one dimension coordination polymeric chain containing the anions. The complex cations and anions are linked through hydrogen bonding interactions. Co-crystallized water molecules fill in the pores and hydrogen bond to the host. Bond valence sums show that O1, O3 and F3 have much more negative charge, which are in agreement with the crystal structure that they act as bridging atoms.Supplementary material CCDC-606794 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at http://www.ccdc.cam.ac.uk/ const/retrieving.html or from the Cambridge Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033 or e-mail: deposit@ccdc.cam.ac.uk.     

Synthesis and crystal structure of [Nd(H2O)2]2(C2O4)3

Some crystals of [Nd(H₂O)₂]₂(C₂O₄)₃ were synthesized hydrothermally by heating at 200°C for 8 days an aqueous suspension of neodymium oxalate decahydrate in presence of terephthallic acid and guanidinium carbonate. They crystallize in the orthorhombic system, space group P2₁2₁2₁, with a = 8.6702(7) Å, b = 9.558(2) Å, and c = 17.009(2) Å. The structure of this complex is built up by two independent neodymium atoms, three bischelating oxalate ligands, and four water molecules forming a rectangle building unit of 6-membered ring, [Ln(H₂O)₂(C₂O₄)]₆. The packing of these units leads to a layer parallel to the plane (001). However, the neodymium atoms of two neighbor layers share an edge of oxalato oxygen atoms thus giving a double-layer. The three dimensionality between these double-layers is insured by hydrogen bonds of water molecules which are bound to the neodymium atoms. There is no zeolitic water molecule. The two neodymium atoms are nine-coordinated. In both cases, the coordination polyhedron can be described as a distorted tricapped trigonal prism.     

Structural features of a new [Fe(nicotinamide)2(H2O)4]·[Fe(H2O)6]·(SO4)2·2H2O complex

A new nicotinamide complex of Fe(II) cation was prepared by reaction between ferrous sulfate and nicotinamide in aqueous solution. The complex was characterized on the basis of elemental analysis, FT IR and UV–VIS spectroscopy, electrochemistry (cyclic voltammetry) and X–ray crystallography. The complex consists of the molecular composition of [Fe(nicotinamide)₂(H₂O)₄]· [Fe(H₂O)₆]·(SO₄)₂·2H₂O. The complex crystallizes in the monoclinic space group P 2₁/c [a = 12.862(3), b = 7.110(3), c = 16.382(3) Å; β = 95.79(2)°]. It has been proven that nicotinamide is coordinated to Fe(II) through the nitrogen atom of its heterocyclic ring. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Nonlinear optical properties of strontium tartrato‐antimonate(III) dihydrate,Sr[Sb2{(+)‐C4H2O6}2]·2H2O

The tensor of nonlinear optical susceptibility for second harmonic generation [d^SHG _ijk ] of hexagonal (point group 6) strontium tartrato‐antimonate(III) dihydrate, Sr[Sb₂{(+)‐C₄H₂O₆}₂]·2H₂O, was determined using the Maker fringes method and a Nd:YAG laser with a wavelength of 1064 nm. The largest component of the tensor d^SHG ₃₃₃ amounts two times d^SHG ₁₁₁ of α‐quartz. Effective nonlinear optical susceptibility d^SHG _eff is given for phase matching type I for several wavelengths (for type II d^SHG _eff is nearly zero). The thermal stability of crystals of Sr[Sb₂{(+)‐C₄H₂O₆}₂]·2H₂O was determined in the temperature range from 153 K to 573 K by means of thermal expansion measurements and thermogravimetry. The temperature dependence of thermal expansion coefficients is given in the range from 153 K to 293 K. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)