Crystal structures of bis(cyanido)bis(N,N′-diethylthiourea-κS) mercury(II) and bis(cyanido)bis(N,N′-dipropylthiourea-κS) mercury(II)

Two mercury(II) complexes containing cyanide and, N,N′-diethylthiourea (detu) and N,N′-dipropylthiourea (dprtu) ligands, [(detu)₂Hg(CN)₂] (1) and [(dprtu)₂Hg(CN)₂] (2), respectively, have been prepared and characterized by X-ray crystallography. In the both complexes Hg atom lies on a 2-fold rotation axis, and is coordinated to the sulfur atoms of two thiourea ligands and to two cyanide carbon atoms. Both have a distorted tetrahedral environment with bond angles about the Hg atoms in the range of 93.41(4)°–146.75(19)°. In the crystal structures symmetry related molecules are linked via N-H-N hydrogen bonds resulting in the formation of a two-dimensional network in 1, while in 2 a double stranded one-dimensional chain is formed.     

Synthesis and crystal structure of [{V3(μ-Cl)4(μ 3-Cl) (μ 3-OH)(thf)2(teeda)}2]·2(thf) (teeda = N,N,N′N′-tetraethylethane-1,2-diamine)

The title complex was prepared from the reaction of [V₂(-Cl)₃(thf)₃]₂[Zn₂Cl₆] with N,N,NN-tetraethylethane-1,2-diamine (teeda) in refluxing thf and its crystal structure exhibits two triangulo-[V₃(-Cl)₃(-Cl)( ₃-OH)(thf)₂(teeda)]⁺ cations bridged by two chlorides. The molecular structure (monoclinic, space group P2 ₁/n, Z = 2, a = 11.8005(7) Å, b = 18.7492(14) Å, c= 15.6253(9) Å, = 103.600(4) shows each vanadium site in a distorted octahedral geometry. V1 and V2 have two thf molecules bounded in cis configuration, and V3 completes the hexa-coordination with the diamine teeda. Main bond distances are 2.5149(12) Å for V(1)--Cl(1), 2.062(3) Å for V(1)- ₃-O(3), 2.5554(12) Å for V(1)- ₃-Cl(4), 2.140(3) Å for V(1)–O(1)(thf), 2.243(4) Å for V(3)–N(1)(teeda), and 3.0437(9) for V(1)···V(2).     

Structure of N,N′,N″-tris(carboxymethyl)-1,3,5-benzenetricarboxamide trihydrate

The title compound, C₁₅H₁₅N₃O₉·3H₂O, crystallizes in the centrosymmetric space group R with a = 13.642(5), b = 13.642(5), c = 18.692(5) Å, D _calc = 1.440 g cm³, and z = 6. An extensive three-dimensional hydrogen bonded network is observed. The network arises from 15 hydrogen bonds per asymmetric unit. Six identical N—H···O hydrogen bonds are formed between two triacid molecules, which results in the face-to-face dimerization of the two triacid molecules. The dimers form extended sheets through hydrogen bond interaction with water molecules. The sheets are held together by hydrogen bonds via the water molecules. The planes of the benzenoid ring are parallel to each other.     

The structure of N,N′-bis(2-hydroxyphenyl)butanediamide

The structure of N,N-bis(2-hydroxyphenyl)butanediamide has been determined. The molecule consists of two 2-hydroxyphenyl moieties which are attached (at the 2 position) to the two nitrogens of the butanediamide. The compound C₁₆H₁₆N₂O₄ crystallizes in the monoclinic space group P2₁/c witha=5.576(1),b=4.8853(6),c=25.397(6) Å and =90.58(1)°.     

Synthesis and structural characterization of a (N,N′-bis[2(S)-pyrrolidylmethyl]-propane-1,3-diamine) nickel (II) complex

The nickel(II) complex [Ni(C₄H₃NCH=N–(CH₂)₃–N=CHC₄H₃N)], (1) containing the symmetrical N₄ tetradentate Schiff base ligand, which is the 2:1 condensation product of pyrrole-2-carboxaldehyde and 1,3-diaminopropane respectively, was prepared. Structural investigation shows that it is monomeric, having space group P2₁/c, a = 7.989(7), b = 17.406(14), c = 9.193(5) Å, = 90, = 100.39(6), = 90, and Z = 4. The coordination geometry around the nickel atom is slightly distorted square planar and the conformation of the six-membered ring containing the metal,azomethine nitrogens and three carbon atoms of the connecting 1,3-diaminopropane is a symmetric boat.     

A crystallographic study of (2-acetylpyridine-κN 4-phenylthyosemicarbazonate-κ2N1,S) methyl-trans-dichlorotin(IV)

The preparation and characterization of [Sn(C₁₄H₁₃N₄S)(CH₃)Cl₂], an organotin(IV) complex containing 2-acetylpyridine(4)-phenylthiosemicarbazone, is described. The molecular structure was studied by single crystal X-ray diffraction, and IR and Mössbauer spectroscopies. The title compound crystallizes in the centric triclinic space group, P , as discrete neutral complexes, with the Sn(IV) ion in a distorted octahedral coordination geometry, with the thiosemicarbazone derivative in a meridional configuration and the chlorides in trans positions.     

Crystal structure of calcium (Ornithinato-N (α), N (δ), N (δ )-triacetato)cobaltate(III) octahydrate Ca[Co(Orntra)]2 ⋅ 8H2O

The X-ray crystal structure of calcium (ornithinato-N _(α) N _(δ) N _{(δ )}-triacetato)cobaltate(III) octahydrate Ca[Co(Orntra)]₂ ? 8H₂O has been determined. The crystals are orthorhombic, a = 21.163(4) Å, b = 8.391(2) Å, c = 19.101(4) Å, V = 3391.9(9) ų, Z = 4, and space group Pca2₁. In the trinuclear linear molecule [Co(μ-Orntra)]₂Ca(H₂O)₅, two independent anions [Co(Orntra)]^? are joined with the Ca²⁺ cation by the bridging bonds through the terminal O atoms. In each [Co(Orntra)]^? anion, the Co atom occurs in the octahedral environment of two N atoms and four O atoms of the Orntra ligand and closes four five-membered and one seven-membered chelate rings. Two O atoms of two anions occupy axial vertices in a pentagonal bipyramid of the Ca²⁺ ion. Five O(H₂O) atoms are located in the equatorial plane. The asymmetric C atoms in the anions bound to the same Ca²⁺ cation have an identical absolute configuration. The crystal involves the molecules belonging to both configurations. The coordinated and outer-sphere H₂O molecules participate in an extended system of hydrogen bonds.     

(Ti1-xAlx)N硬质涂层的研究进展

TiAlN作为一种三元复合纳米涂层材料,具有非常好的性能.该涂层克服了TiN涂层所存在的一些缺陷,其硬度远远高于TiN涂层,最高可达47GPa, 并且具有很好的热稳定性,在700℃高温下仍很稳定,而TiN涂层在500℃时就已被氧化.TiAlN涂层还具有抗磨损,摩擦系数小,热膨胀系数及热传导系数低等特性,这些特性与涂层中Al含量的多少有关,Al含量的改变会导致涂层微观结构的改变,从而使其性能发生变化.氮分压和基底温度对TiAlN涂层的性质有着极其重要影响.本文结合国内外对TiAlN涂层的最新研究进展,对TiAlN涂层的应用,制备方法,结构,抗氧化性及硬度作了简要论述.     

Crystal and molecular structure of the spin-crossover complex bis(pyridine) [N,N′-ethylenebis (3-carboxysalicylaldimine)] cobalt (II)

The average structure of the title compound, Co(H₂fsa₂en)(py)₂, which has been shown previously to exhibit a thermally induced high-spin low-spin crossover, has been investigated by single-crystal X-ray diffraction. This structure has been solved in the monoclinic space groupC2/c (No. 15), with cell dimensionsa=16.641(5),b=9.496(4),c=16.329(6) Å, and=95.47(3)°;V=2569(3) ų,M _r =571.46,Z=4,D _x =1.478 mg m^–3; MoK radiation (graphite crystal monochromator),=0.71073 Å,(MoK)=7.138 cm^–1;T=295 K andR=0.081 for 681 observed [I>3(I)] independent reflections. The cobalt(II) ion resides on a twofold axis in an elongated octahedral environment, the length of the apical bond (formed with pyridine) being 2.262(12) Å and the mean length of the equatorial bonds (formed with the Schiff base) 2.079(12) Å. These values are consistent with the magnetic behavior, which suggested a distorted surrounding for the metal atom. The packing is essentially governed by the parallelism of the salicylaldimine ligands. The two pyridine rings of the molecule are twisted by ~98° on each side of the basal plane; they are probably affected by orientational disorder or, if ordered, they might be described in a superstructure not yet established.     

Crystal structure of [Yb(L(NO3)2(H2O)2](NO3), L = bromo-N,N,N′,N′-tetraethylmalonamide

[Yb(L(NO₃)₂(H₂O)₂](NO₃), L = bromo-N,N,N,N-tetraethylmalonamide crystallizes in the triclinic spacegroup P-1 with cell dimensions a = 9.030(9), b = 12.036(12), c = 12.392(13) Å, = 84.52(1), = 77.58(1), = 67.21(1)° , d_calc = 1.935 g cm^-3 for Z = 2. The ytterbium atom in the complex cation is nine-coordinate being bonded to two oxygen atoms from the malonamide ligand, two nitrate anions, and three water molecules.     

Synthesis and structure of the molecular complex between N-(N′, N′-dimethylaminopropyl)phenothiazine hydrochloride and 7,7,8,8-tetracyano-p-quinodimethane (DAPP-TCNQ)

Synthesis, spectroscopic, and X-ray structural analysis of the molecular complex between the N-(N, N-dimethylaminopropyl)phenothiazine hydrochloride, monohydrate, (DAPP) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), has been carried out. Crystals of C₂₉H₂₇N₆OSCl are monoclinic, P2₁/c,a=12.190(2),b=7.695(2),c=28.928(3)Å, =91.68(1)°. The molecular complex consists of DAPP as donor binding to TCNQ as acceptor by the thiazine central ring and one of the aromatic rings stacking in parallel planes along thec-axis with an interplanar separation of 3.24Å and 3.16Å, respectively. The electronic and epr spectra of the complex are discussed.     

Structure of N,N′-bis[3-(aminocarbonyl)propyl]sulfamide

The title compound, C₈H₁₈N₄O₄S, possesses C₂ symmetry, with the S atom lying on a twofold rotational axis in the unit cell. The sulfamide group of each molecule forms four identical hydrogen bonds with those of its four neighboring molecules, resulting in a rhombic two-dimensional hydrogen bonded network. This network assembles in the third dimension via hydrogen bonds between the primary amide groups of the substituents that extend from the 2D sulfamide sheets. The primary amide groups form a hydrogen-bonded eight-membered cyclic dimer around a two-fold rotational axis. These cyclic dimers are linked into a ribbon-like network via hydrogen bonding interaction between the trans-H and the carbonyl of the amide groups. The compound crystallizes in C2/ca with a = 8.6162(1), b = 57716(1), c = 24.8344(b) Å, = 96.298(1)°, D _calc = 1.441 g cm^–3, and Z = 4.     

Distortions in nitramine substituted cubanes: The structures of N,N′-dinitro-1,4-diaminocubane,N,N′-dinitro-N,N′-(2-pyridyl)-1,4-diaminocubane,and 1,2,4,7-tetrakis(N-methoxycarbonylnitramino)cubane

The structures of three nitramine substituted cubane molecules, N,N-dinitro-1,4-diaminocubane (1), N,N-dinitro-N,N-(2-pyridyl)-1,4-diaminocubane (2), and 1,2,4,7-Tetrakis(N-methoxycarbonylnitramino)-cubane (3), have been determined.1 crystallized in the space group P2₁/a with cell dimensionsa=6.545(1),b=9.331(1),c=7.459(1) Å, =105.80(1),2 crystallized in the monoclinic space group P2₁/a with cell dimensionsa=7.545(2),b=8.697(3),c=12.406(4 Å, =96.28(3)°, while3 crystallized in the monoclinic space group P2₁/c with cell dimensionsa=10.866(3),b=6.866(2),c=16.167(6) Å, =108.79(3)°. The metrical parameters of the cubane skeleton showed no significant deviations from those found in other similarly substituted cubane molecules. For2 and3 there were considerable distortions of the nitramine moiety from planarity in contrast to1 where the nitramine moiety was almost exactly planar. The bond distances and angles for the nitramine group in1 indicates a substantial introduction of double bond character into the N–N bond in1, achieved by delocalization of the amine lone pair, compared with2 and3.     

Structures of four- and six-coordinate monomers of [N,N′-bis(5-chlorosalicylidene)-1,3-diaminopropane]nickel(II)

[N,N-Bis(5-chlorosalicylidene)-1,3-diaminopropane]nickel(II) [Ni(C₁₇H₁₄N₂O₂Cl₂)] 1 and [N,N-Bis(5-chlorosalicylidene)-1,3-diaminopropane]nickel(II) dihydrate [Ni(C₁₇H₁₄N₂O₂Cl₂).2(H₂O)] 2 were synthesized, and their crystal structures were determined. Compound 1 is monoclinic, space group C2/c, a = 21.063(4), b = 8.151(1), c = 9.421(2) Å, = 94.16(1)°, V = 1613.2(5) ų, Z = 4 and D_c = 1.680 g cm^–3. Compound 1 contains a crystallographic twofold axis, and the whole molecule is not planar. The two Schiff base moieties, which in themselves are planar, are twisted with respect to one another. The least-squares planes through each half of the molecule are inclined at an angle of 29.1(1)°. The Ni atom is in a square-planar environment. The Ni—N and Ni—O distances are 1.958(2) and 1.910(2) Å, respectively. Compound 2 is orthorhombic, space group Pnma, witha = 7.892(1), b = 23.396(2), c = 9.992(1) Å, V = 1846.3(3) ų, Z = 4 and D_c = 1.597 g cm^–3. Compound 2 has crystallographic mirror symmetry, and again, the whole molecule is not planar. The two planar Schiff base moieties inclined at an angle of 38.7(1)°. The Ni atom is in a distorted octahedral geometry and coordinated by the donor atoms of the ligand in the horizontal plane, and the coordination sphere is completed by O atoms of two water molecules.     

自蔓延高温合成Ti(C,N)材料

采用Ti粉和一种CNx前驱物粉体为原料,通过自蔓延高温合成技术,制备了单相Ti(C,N)材料.并研究了添加过量Ti对反应合成Ti(C,N)材料的影响.研究结果表明,自蔓延反应会产生很高的温度,温度达2782 K.燃烧产物组织均匀,Ti(C,N)颗粒平均大小约为3μm.当原料中Ti含量过量时,容易生成多种C和N配比不同种类的Ti(C,N)材料.最后,通过淬熄实验提出了一种自蔓延反应合成Ti(C,N)的机理.     

Crystal structure of 1,3-(N,N′-benzamide)-2-methyl-1-pentene

Crystals of the title compound are monoclinic (C20H22N2O2): space groupP2₁/n,a=11.800(3),b=13.820(2),c=11.004(3) Å,=92.74(3)°. The structure was solved by direct methods and refined by block-matrix least-squares procedure to giveR=0.078 andRw=0.076 for 1960 reflections above 3(I). The two amide groups are not coplanar with respect to their benzene rings. An intramolecular N-HO hydrogen bond was found in the molecules which are joined in chains by other strong N-HO hydrogen bonds.     

Crystal structure of (ethylenediammonium-N,N′-di-3-propanoic acid) tetrachloropalladate(II) complex

The title compound was obtained by a synthesis from ethylenediamine-N,N-di-3-propanoic acid dihydrochloride (H₂eddp2HCl) and potassium hexachloropalladate(IV) (molar ratio 1:1, in water). Its structure has been determined by single-crystal X-ray diffraction: monoclinic space group P2₁/n, a = 8.198(1), b = 10.282(1), c = 9.080(1) Å, = 103.62(1)°, V = 743.9(2) ų, and Z = 2. The dianionic complex has a square-planar coordination geometry with four chloro ligands, and ethylenediamine-N,N-di-3-propanoic acid as dication in the second coordination sphere. This is the first reported Pd(II) structure with uncoordinated H₂eddp.     

The crystal structure and IR spectra of μ-(bipyrimidine-N1,N1′,N5,N5′)-bis[(azido-N1)(methanol)(bipyrimidine-N1,N1′)copper(II)] bis(triflate) bis(methanol)

The structure of the title compound [Cu₂(bipym)₃(N₃)₂(CH₃OH)₂](CF₃SO₃)₂(CH₃OH)₂ has been determined by X-ray diffraction. The crystals are triclinic, space group P1, with a = 8.1844(5), b = 11.0253(6), c = 12.9089(7) Å, = 80.249(4), , = 74.933(5), = 74.001(4)°, and Z = 1. The structure consists of a dinuclear Cu(II) unit formed of two didentate bipym ligands, one bis-didentate bipym ligand, two azido anions, and two coordinating methanol molecules. The Cu(II) atom is elongated tetragonally surrounded by two nitrogens of the didentate bipym ligand, one nitrogen of the bis-didentate ligand, and one nitrogen of the azido anion forming the equatorial plane with one nitrogen of the bis-didentate ligand and an oxygen atom of the methanol molecule as the axial atoms. A noncoordinating triflate anion and an additional methanol molecule are also in the crystal lattice and have a hydrogen bond distance of 2.801(3) Å with an angle of 157(4)°. The cations link by O – H ··· N bonds into infinite chains running in the c-direction.     

Synthesis,Spectral, Thermal and Structural Study of Monoaquabis(Acetylsalicylato-κO)bis(Nicotinamide-κN)Copper(II)

Abstract  

The compound has been formed by mononuclear [Cu(C₉H₇O₄)₂(C₆H₆N₂O)₂(H₂O)] units in which the metal ion as well as the water ligand lies on a twofold symmetry axis, so that only one acetylsalicylate ligand and one nicotinamide ligand are independent. The distortion from ideal five-coordinate geometries can be described best by the degree of trigonality τ. For a regular square-pyramidal (SQP) geometry the trigonality parameter is 0 and for a trigonal–bipyramidal (TBP) structure it increases to 1. The copper coordination geometry is that of a square pyramid (τ = 0.23), with the N atoms from nicotinamide ligands and the bonded carboxylate O atoms from acetylsalicylate ligands defining the quasi-planar square base. The apical site is occupied by the aqua ligand, a bond which coincides with the twofold symmetry axis and is thus exactly perpendicular to the basal plane. The thermal decomposition takes place in four steps: removing of moisture, dehydration of aqua ligand, the elimination of the nicotinamide (na) ligand and the decomposition of acetyl-groups and oxidation of salicylate ion ligands. In complex, all ligands are coordinated to the metal ion as monodendate. The IR spectra of the intermediate products showed similar results.     

Hydrogen-bonded dimer of N,N′-(5-n-butyl-5-oxodibenzo[b,d]phosphole-3,7-diyl)bis(benzamide) dimethylformamide solvate

The structure of a large wing-span phosphine, in the oxide form, N,N-(5-n-butyl-5-oxodibenzo[b,d]phosphole-3,7-diyl)bis(benzamide), C₃₀H₂₇N₂O₃P, cocrystallized with dimethylformamide (DMF), C₃H₇NO, is reported. The title compound is crystallized in a triclinic system with cell dimensions of a = 10.295(8) b = 12.743(5) c = 13.239(6) Å, = 108.14(3), = 108.16(5), = 101.20(4)°, and V=1484.4(5) ų, and forms a hydrogen-bonded dimer via two hydrogen bond linkages of the P—O ··· H—N type involving one of the two amide groups.