Preparation and characterization of indium doped tin oxide (ITO) via a non-aqueous sol-gel

ABSTRACT

Tin-doped indium oxide (ITO) nanoparticles (NPs) were conceived as promising materials using as noncarbon support for Pt NPs on the cathode side of Proton Exchange Membrane Fuel Cells (PEMFC). In this paper, ITO nanoparticles have been synthesized via a nonaqueous sol-gel process using indium acetylacetonate and tin bis(acetylacetonate)dichloride in oleyamine as starting materials. The ITO exhibits solid solution phase, relatively porous, good crystallinity with a uniform size of 15–20 nm, resulting in a high specific surface area and excellent conductivity. The effects of reaction temperature, calcination temperature on the specific surface area as well as the conductivity of ITO nanoparticles were studied in this paper. We found that the ITO nanoparticles synthesized at 235°C and calcination temperature at 500°C for 3 hours shows the excellent conductivity of 1.242 S/cm, was significantly ～8-fold higher than that of commercial ITO produced by Sigma-Aldrich (0.15 S/cm). The results of this research suggested that the ITO synthesized by non-aqueous sol-gel process exhibits relatively good properties as well as can apply this process to prepare the others nanomaterial support based on In₂O₃-materials by doping different oxide into indium oxide.     

Effect of illumination on hydrogenated amorphous silicon thin films doped with chalcogens

Hydrogenated amorphous silicon thin films doped with chalcogens (Se or S) were prepared by the decomposition of silane (SiH₄) and H₂Se/H₂S gas mixtures in an RF plasma glow discharge on 7059 corning glass at a substrate temperature 230 °C. The illumination measurements were performed on these samples as a function of doping concentration, temperature and optical density. The activation energy varied with doping concentration and is higher in Se-doped than S-doped a-Si:H thin films due to a low defect density. From intensity versus photoconductivity data, it is observed that the addition of Se and S changes the recombination mechanism from monomolecular at low doping concentration films to bimolecular at higher doping levels. The photosensitivity (σ_ph/σ_d) of a-Si, Se:H thin films decreases as the gas ratio H₂Se/SiH₄ increased from 10^?4 to 10^?1, while the photosensitivity of a-Si, S:H thin films increases as the gas ratio H₂S/SiH₄ increased from 6.8 × 10^?7 to 1.0×10^?4.     

The X-Ray Structure and Spectroscopic Characterization of [Zn(H2O)6][{Zn(H2O)}2(ttha)]·4H2O (ttha?=?Triethylenetetraamine-N,N,N′,N″,N?,N?-hexaacetate)

Abstract  

[Zn(H₂O)₆][{Zn(H₂O)}₂(ttha)]·4H₂O (ttha = triethylenetetraamine-N,N,N′,N″,N‴,N‴-hexaacetate) has been structurally characterized (triclinic, P-1, a = 7.4014(4) ?, b = 8.5521(4) ?, c = 15.0309(7) ?, α = 73.582(1)°, β = 85.173(1)°, γ = 69.935(1)°; V = 857.15(7) ?³; Z = 1). The two Zn²⁺ ions bound by the [ttha]⁻⁶ ligand are in distorted octahedral environments. While there exists a center of symmetry in the [{Zn(H₂O)}₂(ttha)]²⁻ anion in the crystalline state, ¹³C{¹H} NMR spectroscopy demonstrates the absence of a center of symmetry in aqueous solution. Furthermore, electronic absorption spectroscopy reveals that [Zn(H₂O)₆][{Zn(H₂O)}₂(ttha)]·4H₂O reacts with vanadyl(IV) acetate in aqueous solution at room temperature to yield [(VO)₂(ttha)]²⁻. This reaction implies that Zn²⁺ can dissociate from [{Zn(H₂O)}₂(ttha)]²⁻ in aqueous solution.     

Precipitation of nanometer-sized SnO2 crystals and Sn depth profile in heat-treated float glass

The effect of oxygen diffusion from the atmosphere on tin depth profile in the bottom face of a soda-lime-silica float glass at temperatures above T_g was investigated. The heat treatment was performed in ¹⁸O₂/N₂ and argon (Ar) atmospheres. The significant diffusion of tin to the surface was observed for the glass heat-treated in ¹⁸O₂/N₂ atmosphere, resulting in the formation of a tin-enriched layer near the surface region. It was found that the tin was supplied from the region shallower than the ‘hump’ which is commonly observed in the tin profile of a commercial soda-lime-silica float glass. No significant change in the tin depth profile was observed for the glass heat-treated in Ar atmosphere. These results indicate that ¹⁸O diffusion into the glass, which causes the change in chemical state of tin from Sn²⁺ to Sn⁴⁺, induces the significant diffusion of tin. Furthermore, the precipitation of crystalline SnO₂ particles with a diameter of ∼1 nm was clearly recognized in the tin-enriched layer. This fact indicates that a phase separation was induced by the oxygen diffusion into the glass. Consequently, Sn²⁺ may be supplied to the surface in order to compensate for the marked decrease in Sn²⁺ concentration in the glass system. The significant diffusion of tin to the surface was suppressed by increasing the iron content in the glass. This suppression was ascribed to the increase in Sn⁴⁺ concentration as a result of the redox reaction between tin and iron because the diffusion coefficient of Sn⁴⁺ is much smaller than that of Sn²⁺.     

Synthesis and Crystal Structure of New <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-Bis[1-(4-methoxyphenyl)-5-methyl-1<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazole-4-carbonyl]hydrazide

Abstract  The N,N′-bis[1-(4-methoxyphenyl)-5-methyl-1H-1,2,3-triazole-4-carbonyl]hydrazide 6 was synthesized from aryl triazole acids and its structure is established by MS, IR, and ¹H NMR spectral data. Compound 6, C₂₂H₂₂N₈O₄, Mr = 462.48, crystallizes in the monoclinic space group P2(1)/c with unit cell parameters a = 15.3451(8), b = 8.6486(4), c = 16.8502(9) ?, α = 90.00, β = 95.731(2), γ = 90.00o, V = 2225.1(2) ?³, Z = 4, and Dx = 1.381 mg m⁻³. The final R was 0.0450. The four aromatic rings are close to linear because of N···H–N hydrogen bonds. Index Abstract  Synthesis and crystal structures of N,N′-bis[1-(4-methoxyphenyl)-5-methyl-1H-1,2,3-triazole-4-carbonyl]hydrazide Heng-Shan Dong, Yan-Fei, Wang, Hong-Ru Dong, Bin, Wang, Bin Quan N,N′-Bis[1-(4-methoxyphenyl)-5-methyl-1H-1,2,3-triazole-4-carbonyl]hydrazide was synthesized.      

Effect of temperature on the structure of liquid In20Sn80

X-ray diffraction, density and dynamic viscosity measurements on liquid In₂₀Sn₈₀ have been carried out between 300 and 800 °C. An effect of temperature on the atomic structure of molten In₂₀Sn₈₀ is discussed in terms of the model of inhomogeneous structure. It is shown that the structure of liquid In₂₀Sn₈₀ can be presented by atomic clusters with stable composition and atomic packing and a portion of free atoms with higher mobility. The number and the size of clusters decrease and the volume fraction of free atoms increases under heating.     

Two Novel Potential Anticonvulsant Salts of 5-Amino-2-Sulfonamide-1,3,4-Thiadiazole

Abstract  

Two crystal structures of sulfonamide salts were studied by X-Ray diffraction. The compound C₂H₅N₄O₂S₂ ⁺·H₂O·Cl⁻ (I), (Hats·H₂O·Cl, Hats = protonated 5-amino-2-sulfonamide-1,3,4-thiadiazole) crystallizes in orthorhombic space group, P2₁2₁2₁, with unit cell parameters a = 10.047(4), b = 5.186(2), c = 16.766(6) ? and the compound C₂H₅N₄O₂S₂ ⁺·CH₃O₃S⁻ (II), crystallizes in monoclinic space group, Cc, with unit cell parameters a = 5.378(3), b = 19.707(6), c = 10.014(5) ?, beta = 99.97(1)°. The molecules in compound I are arranged in a helix of alternating water and Hats molecules. Helixes are interconnected by hydrogen bonds provided by Cl⁻ ions and one ring with a graph set R₆⁴ (12) is determined. The crystal structure of compound II presents mesylate and Hats molecules bonded by two hydrogen bond determining a ring with a graph set R₂²(8).     

Different Hydrogen-Bonded Interactions in the Cocrystals of Nicotinamide with Two Aromatic Acids

Abstract  

Nicotinamide crystallizes with 3-hydroxy-2-naphthoic acid and 4-aminobenzoic acid to give rise to cocrystal 1 and 2, respectively. Cocrystal 1, [C₁₁H₈O₃][C₆H₆N₂O], crystallizes in the monoclinic space group C2/c with a = 25.810(4), b = 4.8932(5), c = 23.869(4) ?, β = 107.078(8)o, V = 2881.6(7) ?³, Z = 8, C₁₇H₁₄N₂O₄, M _r  = 310.30, D _c  = 1.431 g/cm³. Cocrystal 2, [C₇H₇NO₂][C₆H₆N₂O]·H₂O, crystallizes in the triclinic space group P-1 with a = 7.214(5), b = 7.326(5), c = 13.484(11) ?, α = 83.23(2), β = 77.189(18), γ = 80.35(2)o, V = 682.7(9) ?³, Z = 2, C₁₃H₁₅N₃O₄, M _r  = 277.28, D _c  = 1.349 g/cm³. Similar carboxylic acid···pyridine synthon R ₂²(7) can be observed in the two cocrystals. In 1, amide of nicotinamide forms a C(4) chain from the anti H to its carbonyl oxygen. In 2, the amide forms a R ₂²(8) homodimer which is linked into 2D layer by water molecule through different hydrogen-bonding interactions. The 3D hydrogen-bonded structure results from a synthon R ₄²(8) from amide, water and amino group of 4-aminobenzoic acid.     

Crystal Structure of Ozagrel Fumarate dihydrate (Ozagrel = (E)-3-[4-(1H-imidiazol-1-ylmethyl)phenyl]-2-propenic acid)

Abstract  

Ozagrel, (E)-3-[4-(1H-imidiazol-1-ylmethyl)phenyl]-2-propenic acid, crystallizes with fumaric acid in absolute ethanol to give the dihydrous fumarate salt, [(C₁₃H₁₃N₂O₂)₂]²⁺ [C₄H₂O₄]²⁻·2H₂O, which crystallizes in the monoclinic space group P2(1)/n with a = 4.7981(19), b = 11.101(6), c = 26.930(11) Å, β = 90.567(16)°, V = 1434.3(11) Å³, Z = 4, C₁₅H₁₆N₂O₅, M _r  = 304.30, D _c  = 1.409 g/cm³. In the crystal structure, fumaric acid transfers two protons to imidazole ring N atoms of ozagrel. And the resulting carboxylate anions are simultaneously hydrogen-boned to carboxylic group and imidazole ring of ozagrel to give rise to a 2D layer structure. Hydrogen-bonding interactions between water and fumarate dianion result in a 3D structure.     

Synthesis, Crystal Structure and Characterization of a New Dabcodiium Hexaaquacobalt(II) Bis(Selenate), (C6H14N2)[Co(H2O)6](SeO4)2

Abstract  

The new hybrid material, cobalt selenate templated by 1,4-diazabicyclo[2.2.2]octane (abbreviated dabco), has been synthesised by the slow evaporation method at room temperature. Its crystal structure was investigated using single crystal X-ray diffraction data. It crystallises in the monoclinic system (space group P2₁/c) with the following unit-cell parameters: a = 12.9169(2) ?, b = 11.9101(2) ?, c = 12.4951(2) ?, β = 108.484(1)°, V = 1823.10(5) ?³ and Z = 4. The supramolecular structure of (C₆H₁₄N₂)[Co(H₂O)₆](SeO₄)₂ consists of isolated [Co(H₂O)]²⁺ and (C₆H₁₄N₂)²⁺ cations and (SeO₄)²⁻ anions linked together by three dimensional hydrogen-bond network. The infrared spectroscopy confirmed the presence of these different entities. The thermal behaviour of the precursor, studied by thermodiffractometry and thermogravimetric analyses, indicates that its decomposition proceeds through three stages giving rise to the cobalt oxide.     

Molecular Association of Almotriptan with Oxalate and Terephthalate Anions

Abstract  

Crystal structures of anti-migraine drug almotriptan were crystallized with oxalic acid (I) and with terephthalic acid (II) and their crystal structures and molecular associations were determined using X-ray diffraction methods. Crystals of both (I) and (II) are monoclinic, space group P2₁/c, with a = 5.6270(4) ?, b = 27.6419(19) ?, c = 13.6228(9) ?, β = 93.057(1)°, V = 2115.9(3) ?³, Z = 4 (I) and a = 13.3756(15) ?, b = 15.6065(17) ?, c = 10.7238(12) ?, β = 98.017(2)°, V = 2216.7(4) ?³, Z = 4 (II). In almotriptan oxalate {systematic name: N,N-dimethyl-2-[5-(pyrrolidin-1-ylsulfonyl-methyl)-1H-indol-3-yl]-ethanaminium semioxalate}, C₁₇H₂₆N₃O₂S⁺, C₂HO₄ ⁻, (I) and in almotriptan hemi terephthalate hydrate {systematic name: N,N-dimethyl-2-[5-(pyrrolidin-1-ylsulfonyl-methyl)-1H-indol-3-yl]-ethanaminium hemi terephthalate monohydrate}, C₁₇H₂₆N₃O₂S⁺, 0.5(C₈H₄O₄ ²⁻), H₂O, (II), both the almotriptan cations form a trimer with the corresponding anions via N–H···O hydrogen bonds. In (I), the oxalate salt is monoprotonated and in (II), the terephthalic acid is located across the inversion centre and exists as doubly protonated anion. In (I), the cation and anion are interlinked by the N–H···O and O–H···O hydrogen bonds into continuous two-dimensional layers generate an R₆⁶(34) hydrogen-bonded motif tetramers running parallel to the (0 0 1) plane. In (II), the cation and water form a centrosymmetric tetramer of R₄⁴(22) hydrogen-bonded motif via N–H···O and O–H···O hydrogen bonds and further cross-linked by centrosymmetric anions to form an infinite three-dimensional supramolecular hydrogen-bonded networks.     

Square-wave voltammetry and impedance spectroscopy in tin doped melts with the compositions xNa2O · 15Al2O3 · (85 − x)SiO2 (x = 8.5, 11 and 16)

Glasses with the base compositions xNa₂O · 15Al₂O₃ · (85 ? x)SiO₂ (x = 8.5, 11 and 16) doped with 0.5 mol% SnO₂ were investigated by both square-wave voltammetry and impedance spectroscopy in the temperature range from 1300 to 1600 °C. Each recorded square-wave voltammogram exhibits a well pronounced peak attributed to the Sn²⁺/Sn⁴⁺-redox pair. Impedance spectra were measured in a frequency range from 0.1 to 10⁵ s^?1 as a function of the superimposed dc-potential and were simulated using an equivalent circuit taking into account the resistivity of the melt, the electrochemical double layer, a resistor attributed to a kinetically hindered electron transfer and a Warburg parameter which accounts for the diffusion process of Sn⁴⁺ and Sn²⁺ to and from the electrode. Additionally, two impedance elements, a resistor and a capacitance both attributed to adsorption processes were necessary to fit the impedance spectra.     

Hydrogen Bonded Supramolecular Assembly in N6-Benzyladeninium Nitrate and N6-Benzyladeninium 3-Hydroxy Picolinate: A Synthetic Cytokinin

Abstract  

N ⁶-benzyladeninium nitrate, (1), C₁₂H₁₂N₅ ⁺ NO₃ ⁻ crystallizes in P2 ₁/c, with a = 15.0035(13), b = 5.3788(5), c = 16.8954(13) ?, β = 107.331(6)°, Z = 4 and N ⁶-benzyladeninium 3-hydroxy picolinate, (2), C₁₂H₁₂N₅ ⁺ C₆H₄NO₃ ⁻, crystallizes in P1, with a = 8.3017(4), b = 14.6170(7), c = 14.7909 (8) ?, α = 78.801 (4), β = 81.979 (4),γ = 88.849 (4)°, Z = 4. In both the salts, the cation exists as N(7)H tautomer with protonation at the N₃ atom. The dihedral angle of 76.64 (16)° for (1), 67.91(12)° for (cation A) and 68.27 (13)° for (cation B) in (2), between the adenine plane and phenyl ring plane, the distal orientation of the N6 substituent with respect to the imidazole ring and the free N1 position, make these benzyladeninium cations meet all the requirements necessary for cytokinin activity. The crystal structures are stabilized by N–H···N, N–H···O, C–H···O hydrogen bonds and C–H···π stacking interaction between symmetry related benzyladenine molecule.     

Synthesis, Crystal Structures and Fluorescence Property of Bis(benzimidazol-2-yl)methane Dichloride

Abstract  

The title compound, a salt of C₁₅H₁₃N₄ ²⁺2Cl⁻, was synthesized and determined by X-ray crystallography. It crystallizes in the orthorhombic system, space group Pbcn, with lattice parameters a = 9.973(2) ?, b = 9.5012(19) ?, c = 15.574(3) ?, V = 1475.8(5) ?³, Z = 4, C₁₅H₁₃Cl₂N₄, Mr = 320.19, Dc = 1.441 g/cm³. In the crystal structure, the Cl⁻ anion interact with the same benzimidzaole through two kinds of hydrogen bonds forming a 1D hydrogen-bonded chain, two 1D hydrogen-bonded chain cross with each other and form 2D layer structure. The EA, UV, IR and TG-DTG were studied and the possible structures of the title compound were speculated. Moreover, the fluorescence of the title compound was studied. The results reveal that it can emit purple fluorescence in DMF solvent.     

Synthesis and Crystal Structure of a New Schiff Base 4-[(2-hydroxy-benzylidene)-amino]-<Emphasis Type="Italic">N</Emphasis>-(5-methyl-isoxazol-3-yl)-benzenesulfonamide

Abstract  The structure of the title compound (C₁₇H₁₅N₃O₄S)₂ the schiff base, bis(N-(5-methyl-3-isoxazolyl)-4-[(2-hydroxy benzylidene)-amino]) benzene sulfonamide was elucidated by H¹, C¹³ NMR, UV–VIS and IR spectroscopic techniques. The X-ray structure was determined in order to establish the conformation of the molecule. The compound crystallizes in the triclinic space group P-1, with a = 11.419(1), b = 11.426(0), c = 13.316(1) ?, α = 71.94(2), β = 89.79(1), γ = 89.14(2)° and Z = 4. Two benzene rings and azomethine group are practically coplanar, as a result of intramolecular hydrogen bonds involving the hydroxy O atom and azomethine N atom. The component species further interact via N–H···N and C–H···O hydrogen bonds and π–π stacking interactions. Index Abstract  The title compound (C₁₇H₁₅N₃O₄S)₂, Schiff base, bis(N-(5-methyl-3-isoxazolyl)-4-[(2-hydroxy benzylidene)-amino]) benzene sulfonamide was synthesized by the condensation of 4-amino-N-(5-methyl-3-isoxazolyl) benzene sulfonamide (SMZ) and 2-hydroxy benzaldehyde (SA). Its structure was confirmed by single crystal X-ray diffraction analysis. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Characteristics of ITO films fabricated on glass substrates by high intensity pulsed ion beam method

Transparent conductive oxides such as indium tin oxide (ITO) are interesting materials due to their wide-band gaps, high visible light transmittance, high infrared reflectance, high electrical conductivity, hardness and chemical inertness. ITO films were fabricated on soda lime glass substrates by using high-intensity pulsed ion beam (HIPIB) technique. The as-deposited films comprised of partially crystallized In₂O₃ and after annealing at 500 °C for 1 h the film changed to polycrystalline phase. After annealing carrier concentration and Hall mobility increased while specific resistance and sheet resistance decreased quickly; and this trend was also observed when film thickness increased up to 300 nm for the post-annealed samples. Further increase in thickness of the film changed the electrical properties slightly. Atomic force microscopy (AFM) revealed that roughness decreased after 500 °C annealing for 1 h in air, except for the film of 65 nm thick. The thickness of the film which relates to the carrier concentration and mobility, degree of crystallization, size of the grain, and connections among grains in film are main factors to determine film’s electrical properties.     

Synthesis and Crystal Structure Determination of Methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and Methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate

Abstract  

Dilithiated C(α), N-carbomethoxyhydrazones were condensed with lithiated methyl 2-(aminosulfonyl)benzoate to afford intermediates that were isolated and not characterized but cyclized with acetic anhydride, which also resulted in N-acetylation. The X-ray crystal structure determinations of methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate products were a follow up for absorption spectra, and they confirmed their structures. Mechanistic intermediates to describe the reaction may include C-acylated intermediates that cyclize to spiro(N-benzoisothiazole dioxide-pyrazole) instead of N-carbomethoxypyrazole-ortho-benzenesulfonamides. Crystals of C₁₉H₁₇N₃O₅S 7 are monoclinic, P2₁/c, a = 11.899(2) ?, b = 17.562(4) ?, c = 9.484(2) ?, β = 111.03(3)°, Z = 4, V = 1849.9(6) ?³, R ₁ = 0.0857 and wR ₂ = 0.2216 for reflections with I > 2σ(I); crystals of C₁₇H₁₅N₃O₅S₂ 8 are orthorhombic, Pbca, a = 16.045(3) ?, b = 10.746(2) ?, c = 20.389(4) ?, Z = 8, V = 3516(1) ?³, R ₁ = 0.0841 and wR ₂ = 0.2179 for all reflections with I > 2σ(I).     

Preparation and Characterization of Bis(μ-1,2-diaminoethane)cobalt(II) Hexavanadate: A Layered Polyoxovanadate Pillared by a Cobalt Coordination Complex

Abstract  The first example of polyoxovanadate layered framework with a cobalt coordination complex as a pillaring unit, Co^II(μ-C₂N₂H₈)₂[V₄^IVV₂^VO₁₄], was readily synthesized under hydrothermal conditions. The structure can be solved and refined in monoclinic P2 ₁ /n with a = 9.143(3) ?, b = 6.5034(11) ?, c = 15.874(4) ?, β = 101.90(2), V = 923.6(4) ?³ and Z = 2. The crystal structure comprises two-dimensional {V₄^IVV₂^VO₁₄}²⁻ layers extending parallel to [101], constructed from tetrahedral {V^VO₄} and square pyramidal {V^IVO₅} building units. Adjacent layers are linked through the octahedral {Co^IIO₂(μ-C₂N₂H₈)₂} pillars, within which the Co^II resides on an inversion center. The structure displays N–H···O and C–H···O hydrogen bonding between the ethylenediamine and vanadium oxide layers. Graphical Abstract  A new polyoxovanadate layered framework pillared with a cobalt coordination complex, Co^II(μ-C₂N₂H₈)₂[V₄^IVV₂^VO₁₄], has been prepared hydrothermally and fully characterized.      

Synthesis, Crystal Structures and Molecular Packing of a Series of Pyrazolo-Benzothiazine Hybrid Derivatives

Abstract  

The crystal structures of four derivatives of pyrazolo[4,3-c][1,2]benzothiazine-2,4-dihydro-3,4-dimethyl-,5,5-dioxide containing benzothiazine dioxide and pyrazolo fused rings that have been synthesized were determined. (C₁₁ H₁₁ N₃ O₂ S): Mr = 249.29, monoclinic, P2₁/c, a = 8.3070(3), b = 13.6331(5), c = 10.1661(3) ?, β = 106.924(2)°, V = 1101.45(7) ?^3, Z = 4. (C₁₂ H₁₃ N₃ O₂ S): Mr = 263.31, monoclinic, P2₁/n, a = 9.729(3), b = 11.224(4), c = 11.436(3) ?, β = 98.85(2)°, V = 1233.9(7) ?³, Z = 4. (C₁₄ H₁₅ N₃ O₄ S): Mr = 321.35, monoclinic, P2₁/c, a = 9.2534(3), b = 19.3920(7), c = 7.9489(2) ?, β = 95.323(2)°, V = 1420.21(8) ?^3, Z = 4. (C₁₄ H₁₅ N₃ O₃ S): Mr = 305.35, monoclinic, P2₁ /c, a = 13.816(7), b = 7.464(3), c = 14.674(8) ?, β = 109.05(3)°, V = 1430.3(12) ?³, Z = 4. The heterocyclic thiazine rings adopt half-chair conformations, and the mean-planes of the phenyl and pyrazolo rings lie between 10.43(11) and 15.93(16)° with respect to each other. In each case, the geometry about thiazine N-atom is trigonal pyramidal and only the first compound containing a donor N-atom shows classical hydrogen bonds. However, non-classical H-bonding of the type C–H···O is observed in all structures.     

Solvothermal Syntheses and Crystal Structures of Neodymium Thiostannates [Nd(dien)3]2[(Sn2S6)Cl2] and [Nd(dien)3]2[(Sn2S6)(SH)2]

Abstract  

Two neodymium thiostannates [Nd(dien)₃]₂[(Sn₂S₆)Cl₂] (1) and [Nd(dien)₃]₂[(Sn₂S₆)(SH)₂] (2) (dien = diethylenetriamine) were synthesized by the reaction of tin and sulfur in the presence of NdCl₃ and Nd₂O₃, respectively under solvothermal conditions. Compounds 1 and 2 crystallize in monoclinic space group P2₁/n. Crystallographic data for 1: a = 11.6722(16), b = 15.119(2), c = 14.1566(19) ?, β = 96.213(3)°, V = 2483.6(6) ?³, Z = 4. For 2: a = 11.7190(14), b = 15.2168(19), c = 14.2209(18) ?, β = 95.775(4)°, V = 2523.1(5) ?³, Z = 4. The nine-coordinate [Nd(trien)₃]³⁺ complex cation formed in situ acts as the counter ion to the [Sn₂S₆]⁴⁻ anion. The [Nd(dien)₃]³⁺, [Sn₂S₆]⁴⁻ and Cl^– (or SH^–) ions form a 3-dimensional network structure through the N–H···S and N–H···Cl hydrogen bonds.