Tri-(nitrato)-bis-(hexamethylenetetramine)-nona-(aquo) neodymium (III): Synthesis,crystal structure,IR and Raman spectroscopy

This paper reports the structural and spectroscopic properties of tri-(nitrato)-bis-(hexamethylene-tetramine)-nona-(aquo)neodymium (III). The crystals are monoclinic, space groupP2₁/n,Z=4, witha=17.902(4),b=9.335(2),c=18.489(4)Å, B=112.07(2)°. The crystal structure consists of one [Nd(NO₃)₂(H₂O)₆]⁺ cation, two NO ₃ ^– anions coordinated to the neodymium atom, two hexamethylene tetramine molecules, third free NO ₃ ^– anion and three water molecules. The structure was refined to a finalR index 0.039 and weightedR _w 0.039 for 6221 observed reflections. The IR and Raman spectra are fully consistent with the crystallographic results.     

Catena-μ-(3,5-diamino-1,2,4-triazole N1, N3)-bis(thiocyanato-N) cadmium(II): Synthesis,crystal and molecular structure,and infrared and Raman characterization

The title compound (C₆H₁₀CdN₁₂S₂) was prepared and characterized by means of X-ray, Raman, and IR measurements. The crystals are orthorhombic:Pbcn, (No. 60),a=9.558(2),b=9.491(2),c=15.898(2) Å,Z=4. The structure was solved by the heavy-atom method, and least-squares refinement of structural parameters led toR=0.021 (R _w =0.020) for 863 independent reflections. The compound exhibits two-dimensional Cd(II) networks, with the 1,2,4-triazole molecule acting as a bidentate bridging ligand. The structure consists of centrosymmetric units, in which the cadmium atoms are coordinated in distorted octahedral geometries by six nitrogen atoms. Each cadmium atom is linked by four 1,2,4-triazole molecules, and two thiocyanate ions complete the octahedral coordination around the metal. Each 1,2,4-triazole molecule bridges two cadmium atoms. The NH and NH₂ groups of the guanazole unit are involved in intermolecular hydrogen bonds. Infrared and Raman bands are diagnostic of the coordination environments around the metal atoms.     

Crystal and anion structure, TGA, DTA, and infrared and Raman spectra of managanese(II) nitroprusside dihydrate, Mn [Fe(CN)5NO]·2H2O

The single crystal and anion structure of Mn[Fe(CN)₅NO·2H₂O, obtained by slow interdiffusion of reactant solutions through a TMS gel, was solved by X-ray diffraction methods and refined toR1=0.036. Spatial group: orthorhombic,Pnma,a=14.069(2),b=7.538(1),c=10.543(1)Å,Z=4. The Mn(II) ion and the water molecules are sited on mirror planes, which bisect the nitroprusside ions. One of the water molecules is coordinated to Mn(II) and the other, strongly hydrogen (as acceptor) bonded to the first molecule. The IR spectrum confirms the bonding of the water molecules and TGA results are in accordance with the dihydrate character of the substance and its dehydration in two successive steps. DTA results and the Raman spectrum agree with other results and the comparison between IR and RamanvNO wavenumbers confirms the expected strong vibrational interaction between the closely packed antiparallel (eclipsed) NO groups. There is a topotactic relationship between the dihydrate and the trihydrate, which crystallizes in the space subgroupP2 _1/n.     

1,4-Benzodiazepines as ligands. Synthesis,characterization and crystal and molecular structure ofbis(8-chloro-6-(o-chlorophenyl)-1-methyl-4H-s-triazolo[4,3-a]1,4-benzodiazepine (triazolam)) cadmium (II) dichloride

The compound C₃₄H₂₄CdN₈Cl₆ was prepared and characterized by means of X-ray, IR, and Raman measurements. The crystals are monoclinic, space groupC2/c, (No. 14) witha=22.284(3),b=14.501(2),c=14.595(2) Å=129.77(1)° andZ=4. The structure was solved by the heavy-atom method, and least-squares refinement of structural parameters led to a conventionalR factor of 0.040 for 2379 independent reflections. The structure consists of discrete molecules, in which the Cd atom is coordinated in a distorted tetrahedral geometry by two chlorine atoms and by two nitrogens of two triazolic rings of triazolam molecules. Infrared and Raman bands are assigned on the basis of the known structure. An electronic charge calculation has been performed on the unbonded ligand.     

Crystal and Molecular Structure of mer-Co(4-CH3C5H4N)3(N3)3

The crystal structure of mer-Co(4-CH₃C₅H₄N)₃(N₃)₃has been determined by single crystal X-ray methods at 300 K. The compound crystallizes in the monoclinic space group C 2/c, a = 19.087(6), b = 16.769(4), c = 15.845(4) Å, β = 119.04(2)°, V = 4434(2) ų, M_r = 464.42. Z = 8, D_x = 1.391 Mgm⁻³, F(000) = 1920, λ (MoKα) = 0.71069 Å, μ = 0.802 mm⁻¹. The cobalt(III) ions are octahedrally coordinated to three azide groups and to three 4-methyl-pyridine molecules to form isolated coordination polyhedra.     

Crystal structure investigation of [Mn(3-CH3C5H4N)2(N3)2(H2O)2]

The crystal structure of the title compound has been determined by single crystal X-ray diffraction methods. [Mn(3-CH₃C₅H₄N)₂(N₃)₂(H₂O)₂] crystallizes in the space group P 1 with a = 7.444(2) Å, b = 7.691(2) Å, c = 8.926(3) Å, α = 99.82(3)°, β = 108.80(2)°, γ = 114.99(2)° and Z = 1. Least squares refinement gave a R value of R_w = 0.046 for 1414 observed reflections. The manganese atom in the title complex is octahedrally coordinated by two oxygen atoms of the water molecules and four nitrogen atoms; two N-atoms are the end atoms of azide groups and the other two nitrogen atoms belong to the 3-methylpyridine molecules. The polyhedra are linked via hydrogen bonds between the water molecules and the azide groups.     

2D <Emphasis Type="Italic">s</Emphasis>-<Emphasis Type="Italic">d</Emphasis> Mixed-Metal Coordination Polymer Containing Potassium,Chromium(III) and Dipicolinate Ions: Preparation and Crystal Structure

Abstract  

The reaction of pyridine-2,6-dicarboxylic acid (dipicolinic acid, dipicH₂) with potassium tetraperoxochromate(V) in the mixture of water and ethanol led to the formation of a 2D s-d mixed-metal coordination polymer of {K[Cr(dipic)₂]}_n (1). The compound was characterized by spectroscopic methods (IR, Raman, UV/Vis). Single crystal X-ray diffraction analysis revealed that dipicolinate ligand is coordinated to the chromium(III) ion in an O,N,O′-tridentate fashion, while its uncoordinated and coordinated carboxylate O atoms (with respect to Cr(III) ion) are in turn bound to potassium ions. Therefore, each dipicolinate ligand bridges two potassium ions and a chromium(III) ion between them, giving rise to a 2D coordination network. The coordination of chromium(III) ions is octahedral, while the coordination number of potassium ions is 8. The coordination networks are in turn assembled only by π–π stacking interactions into a 3D structure.     

Syntheses and structures of two new organic–inorganic hybrid lanthanide derivatives based on Keggin-type polyoxometalates

Two new organic–inorganic hybrid Keggin-type polyoxometalates containing lanth-anide(III) cations with 3D supramolecular framework structures, [La(DMSO)₈][PW₁₂O₄₀] (1) and [La(DMSO)₈][PMo₁₂O₄₀] (2) (DMSO = dimethyl sulfoxide), have been synthesized in aqueous solution under moderate conditions and further characterized by elemental analysis, inductively coupled plasma (ICP) analyses, IR spectroscopy, electronic spectra, thermogravimetric analysis, and single-crystal X-ray diffraction analyses. The title complexes exhibit similar 3D supramolecular frameworks directed by the different hydrogen bonding interactions. The TG curve exhibit the weight loss of complex 1, which can be divided into five stages, suggesting that the intensity of coordination bonds are different between La(III) and DMSO molecules.     

Platinum(II) dibromo,bis (3,5-diamino-1(2)-triazolium) dibromide: Synthesis,crystal and molecular structure,and infrared characterization

The title compound C₄H₁₂PtN₁₀Br₄ was prepared and characterized by means of X-ray, and IR measurements. The crystals are monoclinic, space groupP2₁/c, (C _2h ⁵ No. 14) witha=6.875(1),b=15.478(2),c=7.074(1)Å,=90.98(1) andZ=2. The structure was solved by the heavy-atom method, and least-squares refinement of structural parameters led to a conventionalR factor of 0.031 (R _w=0.030) for 733 independent reflections. The compound exhibits discrete monometallic units with the 1,2,4-triazolium ion acting as modentate ligand. The structure consists of centrosymmetric units in which the platinum atom is coordinated in perfectly planar geometry by two nitrogen and two bromine atoms. The NH and NH₂ group of the guanazolium unit are involved in intermolecular hydrogen bonds. Infrared bands are diagnostic of the coordination environments around the metal atoms.     

Structure of the [5S,15S] isomer of the macrocyclic complex, [La(NCS)3(C24H30N6)]

The crystal and molecular structure of the [5S,15S] isomer of the [LaL(NCS)₃] complex (L=C₂₆H₃₀N₆) was determined by single crystal X-ray diffraction analysis. The compound crystallizes in the orthorhombic space group P2₁2₁2₁ witha=13.647(4),b=19.504(4),c=11.606(4)Å. The 9-coordinate La(III) is bound to the N atoms of three monodentate isothiocyanates and to the six N atoms of the macrocycle ligand L, which has an 18-membered, six-nitrogen donor cavity and two peripheral –CH₃ substituents.     

The synthesis and crystal structure of [La(OH2)5(phen)2]Cl3·4H2O·phen

[La(OH₂)₅(phen)₂]Cl₃·4H₂O·phen is centric, Pnna, witha=19.946(7),b=16.458(5),c=12.207(4)Å andD _calc=1.57 g cm^–3 forZ=4. The La(III) ion resides on a crystallographic twofold axis and is coordinated to four nitrogen atoms (from two phen molecules) and five water molecules resulting in a distorted tricapped trigonal prismatic geometry. An uncoordinated phen molecule, two chloride anions, and four uncoordinated water molecules are hydrogen bonded to the coordinated water molecules. The coordinated and uncoordinated phen molecules -stack diagonally through the unit cell.     

Crystal structure of strontium potassium arsenate octahydrate

The crystal structure of strontium potassium arsenate octahydrate, SrKAsO₄·8H₂O, has been determined by single crystal X-ray diffraction. The crystals are tetragonal, a = 7.144(1), c = 23.613(2) Å, space group I4₁md (No. 109), Z = 4, V = 1205.1(1) ų, and d _c = 2.258 g cm^–3. All cations and anions in this compound are completely surrounded by water molecules. Sr²⁺ and K⁺ ions are each coordinated to eight water molecules arranged in an approximately square antiprism. The [Sr(H₂O)₈]²⁺ polyhedron shares one face of four water molecules with a [K(H₂O)₈]⁺ polyhedron forming O₄-Sr-O₄-K-O₄ polyhedra. The O₄-Sr-O₄-K-O₄ units are linked together through a pair of edge-sharing linkages of the outer water molecules, alternating along the a-axis and b-axis. The hydrated cation polyhedra appear to define the host lattice, which accommodates the AsO ₄ ^3- ion in the interstitial space. The environment of the AsO ₄ ^3- ion consists of 16 water molecules; each oxygen atom is the acceptor in hydrogen bonds from four water molecules. The pair distances associated with this environment may be used in investigations of the structure of hydrated ₄ ^n- ions in solutions. Each water molecule is coordinated to one Sr and one K, and hydrogen bonded to two O atoms of two different AsO ₄ ^3- ions. There is no hydrogen bonding between water molecules.     

The crystal structure and supramolecular chain of [La(NO3)3(OH2)2(phen)] ⊙ 15-crown-5

[La(NO₃)₃(OH₂)₂(phen)] · 15-crown-5 is hexagonal,P6₅, witha=10.955(2),c=43.769(9), andD _calc =1.668 g cm^–3 for Z=6. In the complex, two nitrogen atoms (from phen) and eight oxygen atoms (six from three bidentate nitrate anions and two from water molecules) are coordinated to the central La(III) ion, forming a coordination polyhedron which is approximately a bicapped square antiprism. The coordinated water molecules donate hydrogen bonds to the oxygen atoms of the crown ether, forming polymeric hydrogen bonded chains which wrap helically along the unit cell directionc.     

A new phase of the complex trinitratotris (triphenylphosphineoxide)neodymium(III)

The crystal structure of the complex [Nd(NO₃)(OPPh₃)] (1) was obtained by single-crystal X-ray diffraction. The central neodymium(III) ion is nine coordinate arranged in a tricapped trigonal prism geometry. Crystallization of 1 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 14.6496(9), b = 18.4506(11), c = 20.5491(11); = 102.925(3)°; and Z = 4.     

Crystal structure of lanthanum(III) oxalate decahydrate

La₂(C₂O₄)₃·10H₂O crystallizes in space groupP2¹/c (No. 14) witha=11.382(6),b=9.624(5),c=10.502(8) Å,=114.52(4)°, andZ=2. The structure (R=0.029 for 3190 MoK data) is composed of two-dimensional networks of edge-sharing 153 coordination polyhedra matching the (020) set of planes, each La(III) atom being surrounded by three ⁴ chelating oxalate groups and three aqua ligands with La-O distances in the range 2.518(4)–2.622(4) Å. The remaining water molecules are disordered over seven principal sites in the intervening space.     

Crystal structure and spectroscopy of a hydrogen-bridged one-dimensional Cu(II) complex containing both octahedral and square pyramidal geometries in the same unit cell

Single crystals of the helical hydrogen-bridged one-dimensional Cu(II) complex, [Cu(stpy)₂(CH₃COO)₂(H₂O)₂] (1) [Cu(stpy)₂(CH₃COO)₂(H₂O)] (2), are prepared and characterized by elemental and thermal analyses, IR, electronic and X-ray crystal structure determination. The crystals are monoclinic, of space group C2/c, with unit cell parameters a = 31.842(7) Å, b = 5.9829(10) Å, c = 30.970(14) Å, = 111.78(3)°, Z = 4. The asymmetric unit contains two different types of Cu(II) polyhedra, namely, octahedron and square pyramid within the same unit cell. 1 has elongated octahedral geometry with two nitrogen atoms from stpy and two oxygen atoms from synmonodentate acetate ligands, transcoordinated to Cu(II) in the basal plane. The oxygen atoms of the two water molecules occupy the axial positions. 2 has Cu(II) coordination polyhedra similar to 1, except that only one of the apical positions is occupied by a water molecule. The structure consists of two independent linear chains, one involving octahedral (1) and the other involving square-pyramidal (2) polyhedra, held by hydrogen bridges. The Cu–Cu intra- and interchain separations in both 1 and 2 are 5.983 and 8.214 Å. The unit cell packing shows weak -stacking between adjacent coordinated stpy ligands in the chain, resulting in ladder-type structure. Further, the extended packing reveals helical arrangement of Cu(II) polyhedra in the lattice.     

Synthesis,Molecular Structure and DFT Study of 2-(<Emphasis Type="Italic">N</Emphasis>-Benzoylbenzamido)pyridine-3-yl benzoate

Abstract  

The biologically important 2-amino-3-hydroxypyridine reacts with benzoyl chloride to give 2-(N-benzoylbenzamido)pyridine-3-yl benzoate. This synthesized compound has been studied by elemental analysis, X-ray crystallography and also theoretically by density functional theory (DFT) framework with B3LYP/6-311++G(d, p) level of theory. The molecules of this compound crystallize in the orthorhombic space group of P2₁2₁2₁ and the crystal packing involves both hydrogen-bonding and C–H⋯π interaction. The vibrational normal modes of the molecular structure are investigated by ab initio method for both infrared intensities (IR) and for Raman activities. Furthermore, the corresponding assignments are discussed. Hydrogen and carbon atoms of the benzene rings are found to be highly active. Also, experimentally obtained IR spectrum is presented and compared with the available theoretical data. Experimentally and theoretically obtained IR spectrum are in good agreement.     

X-ray crystal structure of trans-bis(monoethanolamine) bis(saccharinato)nickel(II)

The crystal structure of trans-bis(monoethanolamine)bis(saccharinato)nickel(II), [Ni(C₇H₄NO₃S)₂(C₂H₇NO)₂], has been determined from X-ray diffraction data. The metal complex is monoclinic, with a = 11.0555(5), b = 8.9103(4), c = 11.3890(5) Å, = 105.0230(10)°, Z = 2, and space group P2_1/c . The structure consists of individual molecules. Two monoethanolamine molecules and two saccharinate anions coordinate the nickel atom forming a distorted octahedron. The monoethanolamine molecules act as a bidentate ligand and form five-membered trans chelate rings, which constitute the plane of the coordination octahedron, while two saccharinate ions behave as a monodentate ligand occupying the axial positions. Intermolecular hydrogen bonds link the molecules to form a three-dimensional infinite structure.     

Synthesis, Fourier-transform Raman and infrared spectroscopic analysis, and crystal structure of (NiL)2, (L = bis(2,4-dimethyldipyrrin-3-yl)methane)

The Ni(II) complex with bis(2,4-dimethyldipyrrin-3-yl)methane, (NiL)₂, has been synthesized and characterized by ¹H-NMR, UV–Vis, FT-IR, FT-Raman, MS, and elemental analysis. X-ray diffraction analysis at room temperature indicates that the complex crystallizes in triclinic system, space group P–1 with a = 11.344(4), b = 12.703(4), c = 14.936(5) Å, = 87.017(6)°, = 75.379(5)°, = 75.318(5)°, M _r = 826.31, V = 2014.5(11) ų, Z = 2. The crystal structure of the title complex reveals that it is a dinuclear double-stranded helical entity. The ligands perform as tetradentate ligands and the ratio of Ni(II) to ligand is 2:2. The central Ni(II) atom is tetracoordinated by four nitrogen donors of two ligands and the coordination geometry of Ni(II) can be considered as a distorted tetrahedron configuration. The IR and Raman spectral analysis, assignment, and discussion are presented.     

Synthesis and crystal structure of a new composite complex between a hepta-coordinate ytterbium(III) and a heteropoly molybdic anion: [Yb(DMSO)<Subscript>7</Subscript>]H[SiMo<Subscript>12</Subscript>O<Subscript>40</Subscript>] (DMSO = dimethyl sulfoxide)

A new composite complex of the general formula [Yb(DMSO)₇]H[SiMo₁₂O₄₀] has been synthesized from H₄SiMo₁₂O₄₀⋅nH₂O, YbCl₃ and DMSO in mixed solvent of acetonitrile and water and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Singe crystal X-ray structure analysis shows that it belongs to monoclinic system, space group P2₁/c, with a = 11.685(2) Å, b = 14.969(3) Å, c = 35.037(7) Å, β = 98.50(3)^∘, and Z = 4. There is one [Yb(DMSO)₇]³⁺ coordinated cation and one [SiMo₁₂O₄₀]⁴⁻ polyanion in one structure unit. The organic ligands (DMSO) do coordinate directly with ytterbium(III) to form a distorted pentagonal bipyramid complex ion by coordination bond, then combines to the SiMo₁₂O₄₀⁴⁻ anion by static electric force. The results of IR and X-ray diffraction show that there is strong interaction between polyoxometalate and organic donors.