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)     

Growth and properties of an organometallic nonlinear optical crystal: bis(isothiocyanato)‐bis(4‐methylpyridine)zinc(II) (Zn(SCN)2(C6H7N)2)

Bis(isothiocyanato)‐bis(4‐methylpyridine)zinc(II)(Zn(SCN)₂(C₆H₇N)₂), (abbreviated as ZBNC) single crystals of optical quality have been grown from acetone solution by the slow temperature‐lowering method. Its solubilities at different temperatures in acetone were measured. The X‐ray powder diffraction (XRPD) spectroscopy of ZBNC crystal was performed at room temperature. The second harmonic generation (SHG) efficiency was determined by powder technique of Kurtz and Perry using Nd:YAG laser, which is equivalent to KDP crystal. The thermal decomposition process was characterized by thermal gravity and differential thermal analysis (TG\DTA). The specific heat of the crystal is 1440.67 J/mol·K at 325 K. The IR spectrum was recorded in the 500∼3500 cm^–1 region, using KBr pellets on a Nicolet 170sx FT‐IR spectrometer. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Crystal growth,morphology, spectrographic characterization and thermal properties of 4,5‐bis(benzoylthio)‐1,3‐dithiole‐2‐thione

Single crystals of 4,5‐bis(benzoylthio)‐1,3‐dithiole‐2‐thione (BBDT), were grown from methylene chloride and the growth morphology was deduced by the Bravais–Friedel Donnay–Harker (BFDH) model. The grown crystals were characterized by optical absorption, infrared, Raman and X‐ray powder diffraction spectroscopy. The thermal behavior of BBDT has been investigated by means of thermogravimetric analysis and differential thermal analysis measurements in air. (© 2008 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)     

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.     

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.     

Crystal structure of N‐[(1Z)‐1‐(3‐methyl‐3‐phenylcyclobutyl)‐2‐thiomorpholin‐4‐ylethylidene] thiourea

The crystal structure of N‐[(1Z)‐1‐(3‐methyl‐3‐phenylcyclobutyl)‐2‐thiomorpholin‐4‐ylethylidene] thiourea (C₁₈H₂₆N₄S₂) has been determined by X‐ray crystallographic techniques. The compound crystallizes in the orthorhombic space group Pbca, with unit cell parameters: a = 15.692(3), b = 20.803(8), c = 11.979(6)Å, Z = 8, V = 3911(7)ų. The crystal structure was solved by direct methods and refined by full‐matrix least squares to a final R‐value of 0.084 for 1447 observed reflections [I > 2σ ( I ) ]. In the thiosemicarbazide moiety, the S = C bond length is 1.656(6), N‐C‐N angle is 115.6(5)°. The crystal structure is stabilized by the intermolecular N‐H...S hydrogen bonds. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

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.     

Structural analysis of bis{(N,N′–dimethylformamide) (μ‐formato)[μ‐bis(salicylidene)–1,3‐propanediaminato] nickel(II)} copper(II) and zinc(II) monohydrate hetero‐trinuclear complexes

The two linear hetero‐trinuclear metallic complexes with Cu²⁺, Ni²⁺ and Zn²⁺ ions, [CuNi₂ {(CHO₂)(SALPD)[(CH₃)₂NCHO]}₂],(I) and [ZnNi₂{(CHO₂)(SALPD)[(CH₃)₂NCHO]}₂],(II), form crystals which belong to the monoclinic system, space group P2₁/c, with unit cell dimensions a=10.537(4), b=16.612(5), c=13.837(3) Å, β=111.09(5)°, V=2259.8(12) ų in (I) and a=10.525(4), b=16.658(5), c=13.826(3) Å, β=111.11(5) °, V=2261.4(8) ų in (II), respectively. The coordinations around the M (Ni²⁺, Cu²⁺, Zn²⁺) ions in the title complexes are distorted octahedrals. The stereochemistries of the bridge ligands, linking to the metal ions each other, are changed between Ni…M (Cu²⁺, Zn²⁺) distances. The Ni…M (Cu²⁺, Zn²⁺) distances are 3.0469(13) and 3.0645(14), respectively. (© 2004 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)     

Crystal structure analysis of N,N′‐bis(salicylidene)‐2‐methyl‐1,2‐propanediaminato‐nickel(II)

In the title compound, N,N′‐Bis(salicylidene)‐2‐methyl‐1,2‐propanediaminato‐nickel(II), [NiC₁₈H₁₈N₂O₂], (CCDC 235278), the Ni^II atom is coordinated by two iminic N and two phenolic O atoms of the N,N′‐Bis(salicylidene)‐2‐methyl‐1,2‐propanediaminate (SALPD^2‐) ligand. The geometry of the coordination sphere around the Ni atom is distorted square‐planar. Ni(II) ion, forms crystals which belong to the orthorhombic system, space group P cab, with unit cell dimensions a=11.5531(1), b=15.985(4), c=17.418(1) Å, V=3210.5(9) ų. The cell contains eight molecules. The contact distance Ni...Ni^a between the neighbouring molecules is 4.4704(8) Å. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Synthesis and Structure of Trans‐bis(ethanolamine)bis(saccharinato)mercury(II)

Trans‐bis(ethanolamine)bis(saccharinato)mercury(II), [Hg(ea)₂(sac)₂], where ea and sac denote the ethanolamine molecule and the saccharinate anion, respectively, crystallizes in the triclinic space group P (No. 2) with a = 9.4651 (5), b = 10.4365 (5), c = 11.9314 (6) Å, α = 84.402 (1)° β = 78.313 (1)°, γ = 75.307 (1)°, Z = 2, V = 1115.11 (10) ų. The structure consists of isolated [Hg(ea)₂(sac)₂] units in which the Hg(II) ion is octahedrally coordinated by two nitrogen and two oxygen atoms of two neutral ea ligands, and two nitrogen atoms of two sac ligands. The ea acts as a bidentate N‐ and O‐donor ligand and occupies the trans positions of the equatorial plane of the coordination octahedron forming a fivemembered chelate ring, while sac behaves as a monodentate N‐donor ligand occupying the axial positions. The average Hg‐N_sac and Hg‐N_ea bond distances are 2.739 (3) and 2.114 (7) Å, respectively. The crystal exhibits extensive hydrogen bonds between the hydroxyl and amine hydrogen atoms of the ea ligands and the sulfonyl, carbonyl and amine groups of the sac ligands.     

Crystal and molecular structure of 1‐allyl‐5‐(4‐methylbenzoyl)‐4‐(4‐methylphenyl)pyrimidine‐2(1H)‐thione

The crystal structure of 1‐allyl‐5‐(4‐methylbenzoyl)‐4‐(4‐methylphenyl)pyrimidine‐2(1H)‐thione (C₂₂H₂₀N₂OS) has been determined from three dimensional single crystal X‐ray diffraction data. The title compound crystallizes in the monoclinic space group P 2₁/c, with a = 10.6674(13), b = 10.1077(7), c = 17.9467(19) Å, β = 98.460(9)°, V = 1914.0(3) ų, D_calc = 1.251 g cm^–3, Z = 4. In the title compound, the allyl group shows positional disorder. Molecules are linked by C‐H···O, C‐H···N and C‐H···S intermolecular interactions forming two‐dimensional network. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of 3‐hydroxy methyl 4,6‐dimethoxy‐9‐phenylsulfonyl‐carbazole

The crystal structure of 3‐Hydroxy methyl 4,6‐dimethoxy‐9‐phenylsulfonyl‐carbazole. (C₂₁H₁₉NO₅S) has been determined [CCDC 194425]. The compound crystallizes from methanol in the monoclinic system, space group I2/c, with unit cell parameters: a = 20.498(2), b = 9.258(2), c = 21.866(3)Å, β = 116.450(10)°, Z = 8, V = 3715.2(10)ų. The crystal structure was solved by direct methods and refined by full‐matrix least squares to a final R‐value of 0.050 with 3508 unique reflections. The planar carbazole ring fragment is inclined at an angle of 79.9(1)° to the phenylsulfonyl group. The sum of the angle about N is 351.6(2)°. The atoms linked to the central hexavalent S atom are arranged in a tetrahedral configuration with the larger deviations in the O‐SO angles [O1‐S‐O2 = 119.7(2)°] and the O1‐S‐N and O2‐S‐N angles [106.1(2) and 106.9(1)°, respectively].     

Crystal and molecular structure of 2,6‐bis(4‐chlorophenyl)‐3‐phenylpiperidin‐4‐one

The crystal structure of the title compound is described. The chemical formula of the compound is C₂₃H₁₉Cl₂NO. The compound is found to crystallize in monoclinic system with space group P2₁/c, Z = 4. The unit cell dimensions are a = 15.137(3) Å, b = 8.9171(18) Å, c = 14.779(3) Å, β = 91.461(4)° and V = 1994.2(7) ų, D_calc = 1.320 gcm^‐3. The final R factor is 4.4%. The central piperidone ring of the molecule adopts a slightly distorted chair conformation, the mean torsion angle being 52.3°; the phenyl rings are planar. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

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)     

Crystal Structure of Diethyl 2‐[2,2,2‐ trifluoro‐1‐(indole‐3‐yl)‐ethyl]‐2‐acetamidomalonate

The title compound (C₁₉H₂₁F₃N₂O₅) has been determined from three dimensional X‐ray diffraction data. The crystals are monoclinic, a = 7.626(4)Å, b = 17.515(4)Å, c = 15.066(3)Å, β = 101.02(3)°, V = 1975(1)ų, Z = 4, D_calc = 1.393g cm^‐3, space group P2₁/c. The structure was solved by direct methods and refined by full‐matrix least‐squares method (R = 0.039).