Preparation,physicochemical and third order nonlinear optical properties of bis(tetrabutylammonium)bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)mercurate(II)

Bis(tetrabutylammonium)bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)mercurate(II) was prepared and characterized by elemental analyses, electronic absorption, infrared and X‐ray powder diffraction spectroscopy. The specific heat of the crystal was measured to be 1878.2 J.mol^–1K^–1 at 300 K. The thermal decomposition process was investigated by means of thermogravimetric analysis and differential thermal analysis measurements in air together with infrared and X‐ray powder diffraction spectra. The third‐order nonlinear optical properties at 800 nm were measured by femtosecond optical Kerr gate technique by using CS₂ as reference. The third‐order optical susceptibility of its acetone solution at the concentration of 9.27 × 10^–4 M was obtained to be 2.53 × 10^–14 esu. The second‐order hyperpolarizability was estimated to be 1.7 × 10^–32 esu and the response time was about 226 fs. The third order nonlinear optical properties at 532 nm were investigated by using the Z‐scan technique with 20 ps. It exhibited self‐focusing effect and saturable absorption. The second molecular hyperpolarizability was estimated to be 8.4 × 10^–32 esu. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal and Molecular Structure of Bis{2,6‐bis(hydroxymethyl)pyridine‐O,O,N}{μ‐bis(2‐hydroxymethylpyridyl)methanolate‐O,N}dicopper(II)di(propionate). First example of non‐coordinate propionate anoins

Bis{2,6‐bis (hydroxymethyl) pyridine‐O,O,N} {μ‐bis(2‐hydroxymethylpyridyl) methanolate‐O,N} dicopper(II) di(propionate) (CCDC 143763) has been prepared and studied by single‐crystal X‐ray diffraction methods at 293(2) K. The crystal structure consists of dimeric complex cation, [Cu₂(μ‐bhmp)₂(bhmpH)₂]⁺² and propionate anions (bhmp ‐ 2,6‐bis(hydroxymethyl) pyridine; bhmpH ‐ 2‐(6‐hydroxymethylpyridyl) methanolate ) and propionate anions. The complex cation contains two neutral and two monodeprotonated bhmp molecules, each coordinate to one Cu(II) atom in a tridentate chelating manner, via two O atoms and N atom. The monodeprotonated bmph molecules are also tridentate coordinate via N atom and only one O atom, which serve as bridge between two CuO₄N₂ moieties. The propionate anions are “ fixed” to the complex by the hydrogen bonds.     

Synthesis,crystal structure and third order nonlinear optical properties of bis(tetra‐n‐propylammonium) bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)cuprate(II)

A novel bis (dmit) complex of copper (II), [(C₃H₇)₄N]₂[Cu(dmit)₂] ( 1 ), where dmit is 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate, was prepared and structurally characterized by X‐ray single crystal diffraction. The copper (II) atom is tetracoordinated by four dmit S atoms, forming a nearly square planar arrangement. The [Cu(dmit)₂]^2‐ anions and the [(C₃H₇)₄N]⁺ counter‐cations form a three‐dimensional solid‐state structure by C–H…S hydrogen bonds. The third‐order nonlinear optical properties of the complex were determined by picosecond Z‐scan technique at a wavelength of 1064 nm. The results indicate the compound exhibits reverse saturation absorption and self‐defocusing performance. The molecular second‐order hyperpolarizability γ is calculated to be as high as (1.8±0.2)×10^‐30 esu. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

pH‐Controlled topologies of two Co(II) complexes based on 5‐Nitro‐1,2,3‐benzenetricarboxylic acid and 1,6‐Bis(1,2,4‐triazole‐1‐yl)hexane

Two new Co(II) coordination polymers, [Co(Hnbta)(bth)]_n ( 1 ) and {[Co₃(nbta)₂(bth)₃(H₂O)]·H₂O}_n ( 2 ), (H₃nbta = 5‐nitro‐1,2,3‐benzenetricarboxylic acid and bth = 1,6‐bis(1,2,4‐triazole‐1‐yl)hexane), have been synthesized under different pH values through hydrothermal reactions. Both complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis (TGA), and single‐crystal X‐ray crystallography. Complex 1 exhibits a 3D polythreaded network based on 4‐connected sql 2D layer. Complex 2 has a (4,4,5)‐connected trinodal 3D pillar‐layered network with a (4²·6⁴)₂(4²·6⁷·8)₂(6⁴·8²) topology. Magnetic susceptibility measurements indicate that complexes 1 and 2 show weak antiferromagnetic interactions between the adjacent Co(II) ions.     

The crystal and molecular structure of bis(tetramethylammonium) pentachlorooxomolybdate(V)‐acetonitrile(1:1)

The crystal structure of the title compound, C₁₀H₂₇Cl₅MoN₃O was determined by single crystal X‐ray diffraction technique. The crystals are monoclinic, space group C 2/m, with a= 29.075(8) Å, b= 11.843(4) Å, c= 13.252(4) Å, β=117.049(7)°, V = 4064(2) ų, Z=8. The structure was solved by direct methods and refined by least‐squares methods to a final R = 0.0307 for 5095 observed reflections with I>2σ(I). In the pentachlorooxomolybdate anion, the planar chlorines are bent away from the axial oxygen ligand. The Mo‐O bond length is 1.6620(18) Å that indicates significant double bond character. The oxygen trans Mo‐Cl bond is significantly longer than all of the planar Mo‐Cl bonds. These differences can be attributed to a trans influence of the oxygen atom. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation,single crystal growth and characterization of bis(tetrabutylammonium)bis(4,5‐dithiolato‐1,3‐dithiole‐2‐thione)copper

The preparation and single crystal growth of bis(tetrabutylammonium)bis(4,5‐dithiolato‐1,3‐dithiole‐2‐thione)copper, (I), are described. The energy gap Eg of (I) is about 2.38 eV. The nonlinear optical susceptibility χ⁽³⁾ is about 1.3×10^‐3 esu at 1064 nm. The characterization of (I) has been performed by electronic absorption, infrared and X‐ray powder diffraction spectroscopy. The thermal behavior of (I) has been investigated by means of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) measurements in air. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of 4‐Aminopyridinium‐4‐nitro phenolate single crystals

Organic optical material 4‐Aminopyridinium‐4‐nitro phenolate (4AP4NP) has been synthesized, and single crystals of size 20 x 14 x 6 mm³ have been grown from acetone solvent at room temperature by solvent evaporation technique. The grown crystals have been characterized by X‐ray diffraction to determine the cell parameters, and by FT‐IR technique to confirm the formation of the expected compound. The crystal belongs to monoclinic crystal system with space group P2₁/a.The structural perfection of the grown crystals has been analyzed by high‐resolution X‐ray diffraction (HRXRD) rocking curve measurements. The thermal stability of the compound has been determined by TG‐DTA curves. The transmittance of 4AP4NP has been used to determine the refractive index n; the extinction coefficient K and both the real ε_r and imaginary ε_i components of the dielectric constant as functions of photon energy. The optical band gap of 4AP4NP is 2.4 eV. The dielectric and mechanical behavior of the specimen was also studied. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth and characterization of PbI2‐AgI binary system

The crystals of the binary system PbI₂‐AgI (PIAI) were obtained by heating the mixture of individual PbI₂ (PI) and AgI (AI) placed at 30° angle in the horizontal tubular furnace of variable temperature zone. The crystals were characterized by powder XRD, TG/DTA, FT‐IR and SEM. The 3.37% weight loss in the sample after heating at 853 K is due to the presence of water molecules absorbed (3446 cm^–1) by the crystals during sintering and cooling process. The cell parameters of the crystal were determined using the powder X‐ray data. The PbI₂‐AgI crystallizes in monoclinic system a = 10.799 (±0.009), b = 7.492 (±0.004), c = 6.929(±0.004) Å and α = 90°, β = 108.04(±0.073) γ = 90°, V = 533.18 ų. The electrical conductivity measurements of the crystals showed a sudden change in the current value at the temperature range 385–393 K. The activation energy before and after the drift was found to be 0.49 and 0.35 eV respectively. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Crystal and Molecular Structure of (μ‐terephthlato) bis [(N‐Salicylidene ‐N'‐(2‐hydroxyethyl) ethylenediamine) Copper(II)]

The title compound [[Cu(shen)]₂(tp)], {[Cu(C₁₅H₁₇O₄N₂)]2}, where tp = dianion of terephthalic acid and shen = (N‐salicylidene‐N'‐(2‐hydroxyethyl ethylene‐diamine)) has been prepared and its crystal structure determined by single crystal X‐ray diffraction at room temperature. The complex crystallizes in the orthorhombic space group Pbca with four formula units in a unit cell of dimensions a = 12.298(2), b = 14.214(2) and c = 16.436(2)Å. The structure consists of binuclear units with Cu(II) ion bridged by the tp ligand in a bis‐unidentate fashion. The five coordinate Cu(II) complex adopts a distorted square‐based pyramid. A crystallographic inversion center has been located at the center of the benzene ring of the tp bridging ligand. The Cu … Cu distance inside a same binuclear entity is 11.069Å. Intermolecular aromatic ring stacking interactions were observed with the shortest atom to atom contact being 3.423Å.     

Phase formation in molten system (Na/K)2O‐TiO2‐P2O5. Crystal structures of NASICON and langbeinite‐related phosphates (K/Na)1+xTi2(PO4)3 (x = 0 and 0.357)

Crystallization of high temperature self‐flux of system Na₂O‐K₂O‐TiO₂‐P₂O₅ was investigated at different molar ratios (Na+K)/P = 0.9; 1.0 or 1.2 and Na/K = 1.0 or 2.0 over the temperature range 1000–650°C. The conditions of formation of complex phosphates K_0.10Na_0.90Ti₂(PO₄)₃ (NASICON‐related) and K_0.877Na_0.48Ti^ІІІ_0.357Ti^ІV_1.643(PO₄)₃ (langbeinite‐related) have been established. The new obtained compounds were investigated using FTIR‐spectroscopy, powder and single crystal X‐ray diffraction and optical microscopy methods. The influence of alkaline metal nature on the structure formation of complex phosphates in the high temperature self‐fluxes is discussed.     

Crystal structure of 3‐(3‐nitrophenylhydrazonocarbonyl)‐(1H)‐1,2,4‐triazole

The title compound, C₁₀H₈N₆O₃, was synthesized by the reaction of 3‐(1H)‐1,2,4‐triazole hydrazine with 3‐nitrobenzaldehyde in ethanol. The single crystal structure has been determined by X‐ray analysis. The crystal belongs to monoclinic system, space group p2₁/c with cell constant, a = 8.0214(17) Å, b = 17.334(4) Å, c = 8.9070(18) Å, V= 1179.4(4) ų. An intramolecular N—H...O and N—H…N hydrogen bond are observed between the ‐NH group with O atom of the carbonyl group and the ‐NH group with N atom. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth,structure and spectroscopic studies of a novel organic single crystal: L‐lysine p‐nitrophenolate monohydrate (LLNP)

A novel organic crystal, L‐lysine p‐nitrophenolate monohydrate (LLNP) has been grown successfully from an aqueous solution by the slow cooling method. Transparent single crystal of dimensions 22 × 12 × 12 mm³ has been obtained. The single crystal X‐ray diffraction has shown that LLNP belongs to the orthorhombic crystallographic system with space group P2₁2₁2₁. The functional groups and vibrational frequencies of the crystal have been identified using IR and Raman spectra. The proton and carbon configurations have been confirmed through ¹H‐NMR and ¹³C‐NMR spectra analyses. The UV‐Vis‐NIR transmittance spectrum for LLNP crystal has been recorded in the range from 200 to 2500 nm. The second harmonic generation (SHG) intensity of LLNP has been measured by powder SHG method and found to be as 4.2 times as that of KDP. The thermal properties have been studied by using thermo gravimetric (TG) and differential thermal analysis (DTA).     

Spin‐Hamiltonian parameters and local lattice structure for Pd(I) center in γ‐irradiated bis(acetylacetonato)palladium(II)

This paper reports on a theoretical analysis of spin‐Hamiltonian parameters and local lattice structure for Pd(I) center in γ‐irradiated Pd(II)(acac)₂. Through the crystal‐ and ligand‐field theory, the microscopic spin‐Hamiltonian parameters and local molecular structure for Pd(I) center in the γ‐irradiated Pd(II)(acac)₂ system have been studied by using the high‐order perturbation formulas and Newman's superposition model. Based on these calculations, it was found that the distance of the metal‐ligand bonds in the square planar complex for Pd(I) center in the γ‐irradiated Pd(II)(acac)₂ system increases by 0.1Å. To understand the detailed physical and chemical properties of the [Pd(I)(acac)₂]^2– complex, the contributions of the spin‐orbit coupling of ligand to spin‐Hamiltonian parameters for Pd(I) ion are considered. The theoretical results are in reasonable agreement with the experimental values. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure,thermal analysis and IR spectrometric investigation of bis (2‐amino‐6‐methyl) pyridinium sulfate

The synthesis method, crystal structure determination, phase transitions studied by thermal analysis and IR spectrometric investigation of 2C₆H₉N₂⁺.SO₄^2– are reported. The compound crystallizes in the monoclinic space group C2/c (no. 15) with a = 10.5068(4) Å, b = 10.2225(5) Å, c = 14.0422(7) Å, and β = 104.489(3)°. The atomic arrangement can be described by layers built by all the components of the structure and centered by planes z = 1/4 and 3/4. The organic molecules form channels parallel to the c direction with dimensions of 4.163(1)Å and 5.148(4)Å. Thermal analysis shows that the anhydrous compound presents an irreversible weak phase transition. The IR study, based on theoretical analyses and on the literature data allows the interpretation of the IR spectrum. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

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)     

Growth and characterization of thiourea mixed cadmium – lead chloride – a nonlinear optical crystal

Nonlinear optical (NLO) crystal of thiourea mixed cadmium–lead chloride dihydrate Cd[(PbCl₃)(NH₂CSNH₂)].2H₂O (TCCPC) have been grown in solution by slow evaporation technique at room temperature. The powder X‐ray diffraction pattern has been recorded and indexed. The UV‐Vis‐NIR transmittance and FT‐IR spectrum have been recorded in the range 200‐1090 nm and 400‐4000 cm^‐1, respectively. The lower cut‐off wavelength is 280 nm in the UV region, which is higher than that of pure Cd(PbCl₃) (CCPC) crystal. The presence of functional groups has been confirmed by FT‐IR analysis. The TCCPC crystal was characterized by SEM and EDX spectrum. The second harmonic generation (SHG) of the thiourea mixed cadmium–lead chloride (TCCPC) crystal is demonstrated by the Kurtz Perry method using Nd:YAG laser and the results confirm that the grown crystal is roughly three times more efficient than ADP. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,crystal and molecular structure of trans‐bis(2‐pyridinepropanol)bis(saccharinato)nickel(II)

Trans‐bis(2‐pyridinepropanol)bis(saccharinato)nickel(II), [Ni(sac)₂(pypr)₂], where sac and pypr are the saccharinate anion and the 2‐pyridinepropanol molecule, respectively, crystallizes in the triclinic space group P (No. 2) with a = 8.1981(8), b = 9.9680(10), c = 10.4956(10) Å, α = 90.740(3)° β = 108.142(3)°, γ = 111.025(3)°, Z = 1, V = 1.537 ų. The structure of the nickel(II) complex consists of neutral molecules in which the nickel(II) ion sits on a center of symmetry and is octahedrally coordinated by two sac ligands, and two neutral pypr ligands. The pypr acts as a bidentate N‐ and O‐donor ligand forming a seven‐membered chelate ring, while sac behaves as a monodentate O‐donor ligand via the carbonyl O atom. The Ni‐N bond distance is 2.1016(15) Å, whereas the Ni‐O_pypr and Ni‐O_sac bond distances are 2.1280(12) and 2.0792(11) Å, respectively. The individual molecules are held together with a strong hydrogen bond between the hydroxyl O atom of pypr and N atom of sac and the C‐H…O type weak hydrogen bonds between some ring hydrogen atoms of pypr and sac, and the carbonyl and sulfonyl O atoms of sac in the neighbouring molecules. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal and Molecular Structure of bis[diaaqua(1H‐cyclopenta(2,1‐b:3,4‐b')(dipyridine ‐2,5‐dione))N ickel(II)]dihydrate

The title compound [Ni(CPDD)(H₂O)₂]₂(H ₂O )₂, {]Ni₂(C₄₄H₂₈N₈O₁₂)] (H₂O)₂ }, where CPDD = 1H‐cyclopenta(2,1‐b:3,4‐b')(dipyridine‐2,5‐dione) has been prepared and its crystal structure determined by single crystal X‐ray diffraction at room temperature. The complex crystallizes in the triclinic space group P1 w ith two molecules in the asymmetric unit. The cell dimensions are a=10.452(1),b=14.098(1) & c=16.023 Å; D=110.13(1), E=100.63(1) & J=100.85(1)°. The two independent molecules in the asymmertic unit are related by pseudo two fold symmetry. In both the molecules the coordination environment around the Ni(II) may be best described as a distorted octahedral. Due to some delocalization of charge towards one of the oxygens(O1a) from the O2a atom some degree of bond localization has been observed. The individual diones of both the molecules are almost right angles at the metal atom. A long the y‐axis inversion related molecules are forming pseudo‐dimers through hydrogen bonding.     

Crystal structure of 2‐(3‐amino‐2,4,4‐tricyano‐buta‐1,3‐dienyl)‐ thiophene

The title compound (C₁₁H₆N₄S) crystallizes in the orthorhombic space group Pbca with a = 23.561(4) Å, b = 7.064(1) Å, c = 13.018(3) Å, Z = 8; D_x = 1.387(1) g.cm^‐3 ; R = 0.073 for 1697 observed reflections [F2 ≥ 2σ(F²)]. The interesting feature is disorder in the crystal structure resulting from the existence of two isomeric molecules with interchangable carbon and sulfur positions, occuring at random but with equal probability in the structure.