Synthesis and crystal structure of a new bimetallic complex of diethylenetriamine pentaacetic acid: [YbAg2(dtpa)(H2O)]·3H2O

The reaction between Yb(III) nitrate, Ag(I) nitrate, and the diethylenetriamine pentaacetate (dtpa) ligand gives rise to a bimetallic complex. [YbAg₂(dtpa)(H₂O)]·3H₂O is triclinic, space group P-1, with a = 8.768 (3), b = 9.862 (2), c = 13.055 (2) Å, = 75.40 (1), = 83.00 (2) and = 87.46 (2)°. Each dtpa is coordinated to one ytterbium and six silver atoms. The resulting crystal structure can be described as 2D packing. In the layers, the ytterbium atoms are connected through [Ag(COO)]₂ dimers. Strong hydrogen bonds, involving the noncoordinated water molecules, ensure crystal cohesion.     

Synthesis and crystal structure of [Co(phen)(H2O)4](SO4)⋅2(H2O)

The title complex, [Co(phen)(H₂O)₄](SO₄)2(H₂O) (phen = 1,10-phenanthroline) was prepared in aqua tert-butylperoxohydrogen solution. X-ray single crystal structure determination reveals that the complex consists of a phenanthrolinatocobalt(II)tetrahydrate dication, two uncoordinated water molecules and a sulfate anion. It crystallizes in the orthorhombic space group Pbca with a = 8.856(1), b = 18.318(3), c =21.918(5) Å, V = 3555.6(11) ų. The coordination geometry at each cobalt(II) atom is a slightly distorted octahedron.     

Synthesis and crystal structure of Schiff base transition metal complex [Co(PMBP-smdtc)2]⋅2H2O

A cobalt(II) complex, [Co(PMBP-smdtc)₂]2H₂O, in which PMBP-smdtc is the l-phenyl-3-methyl-4-benzoyl-5-pyrazolone Schiff base of S-methyldithiocarbazate, has been synthesized and characterized by IR spectrum and single crystal X-ray diffraction. The crystal is monoclinic: space group C2/c, with a = 12.455(2) Å, b = 16.024(2) Å, c = 20.513(3) Å, = 101.18(1)°, V = 4016.3(10) ų, and Z = 4. The cobalt ion is octahedrally coordinated by two tridentate Schiff base ligands with ONS donor atoms. The molecules are bridged together by two water molecules through H-bond along b axis and one-dimensional indented chain structure is formed.     

Crystal and molecular structure of dipotassium-aquapentachlororhodate (III): (K2)++ [RhCl5(H2O)]2−

The structure of K₂[RhCl₅(H₂O)] has been established by X-ray crystallography. It crystallizes in the orthorhombic space groupPcmn, with cell dimensionsa=7.065(1),b=9.453(1),c=13.567(1) Å,V=906.1(3) ų,Z=4,M _r =376.4,D _x =2.76 g cm^–3,F(000)=712,T=293 K. The final wasR=0.046. The rhodium atom has a distorted octahedral coordination involving five chlorine atoms and an oxygen of the water molecule with Rh, O, and three chlorine atoms on the mirror plane. Rh-Cl distances range from 2.284(7) Å to 2.345(7) Å. The Cl(4)O intermolecular distance, 3.140(12) Å indicates strong hydrogen bonding between oxygen and chlorine atoms of the neighboring octahedra.N. C. L. Communication No. 5353.     

Synthesis and crystal structure of [Ni(H2O)6](C19H17O9S)2·2H2O

A water soluble flavonoid sulfate, [Ni(H₂O)₆](C₁₉H₁₇O₉S)₂·2H₂O was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. The crystal of it belongs to triclinic crystal system, space group P–1. The results show that the title compound consists of [Ni(H₂O)₆]²⁺, C₁₉H₁₇O₆SO₃ ⁻ and H₂O. Ni(II) is located on the symmetry center and octahedrally coordinated by six water molecules. A variety of hydrogen bonds among [Ni(H₂O)₆]²⁺, C₁₉H₁₇O₆SO₃ ⁻ and the lattice water molecules build a hydrophilic region. Aromatic π–π stacking interactions assemble isoflavone skeletons into a column and the columns form a hydrophobic region of the title compound. The sulfo-groups bridge the hydrophilic regions and the hydrophobic regions as well as the inorganic components and organic components. Hydrogen bonds, stacking interactions and the electrostatic interactions between cation [Ni(H₂O)₆]²⁺ and anion sulfonate C₁₉H₁₇O₆SO₃ ⁻ lead the moieties to a three-dimensional structure.     

Synthesis and crystal structure of [Cu(azpy)(H2O)4][Cu2(nta)2(azpy)]····6H2O: A two-dimensional network solid

The copper(II) complex [Cu(azpy)(H₂O)₄][Cu₂(nta)₂(azpy)]····6H₂O (nta = nitrilotriacetate, azpy = 4,4-azobispyridine) has been synthesized and structurally characterized. It crystallizes in the triclinic space group P , a = 8.6985(3) Å, b = 9.4776(3) Å, c = 14.6544(5) Å, = 71.5360(10)°, = 85.7600(10)°, = 88.1420(10)°, V = 1142.74(7) ų, Z = 1. The crystal structure consists of one-dimensional linear chain cations and dimeric anions. The copper centers in the anion possess distorted trigonal bipyramidal geometry, while Cu(2) has a distorted octahedral geometry in the cation. Coordinated water molecules in the one-dimensional chain form interionic hydrogen bonds with the oxygen atoms of the carboxylate of nta of the dimmer anion. These hydrogen bonds result in the formation of a two-dimensional network.     

Crystal structures of acid ethylenediaminetetraacetates [Cd(H2 Edta)(H2O)] · 2H2O and [Mn(H2O)4][Mn(HEdta)(H2O)]2 · 4H2O

The crystal structures of [Cd(H₂ Edta)(H₂O)] · 2H₂O (I) and [Mn(H₂O)₄][Mn(HEdta)(H₂O)]₂ · 4H₂O (II) are studied by X-ray diffraction [R ₁ = 0.0209 (0.0272), wR ₂ = 0.0571 (0.0730) for 2551 (4025) reflections with I > 2σ(I) in I (II), respectively]. Structure I contains mononuclear [Cd(H₂ Edta)(H₂O)] complexes with the C ₂ symmetry, and structure II contains centrosymmetric trinuclear [Mn(H₂O)₄][Mn(HEdta)(H₂O)]₂ complexes. In I and II, the protonated ligands are hexadentate (2N + 4O), and the water molecule increases the coordination number of the metal atom to seven. The acid protons participate in short intermolecular hydrogen bonds, which are symmetric in II and asymmetric in I.     

Preparation and crystal structure of the new ionic bis-[hydrazido]-molybdenum complex [Mo(NNPh2)2(acac)(PPh3)2]+OTf−

The title compound [Mo(NNPh₂)₂ (acac)(PPH₃)₂]⁺OTf^?, Mr=1233.1, crystallizes in the triclinic space group $P\bar 1$ , witha=12.881 (4),b=13.795(3),c=17.160(5)Å, α=90.95(1), β=91.31(1), ψ=103.53(1)°, andZ=2. The structure was solved by Patterson methods, and refined with some difficulties due to extensive disorder in the counterion. The Mo ion is hexacoordinated in an octahedral environment, with two O and two N defining the basal plane, and two P atoms in the apical sites.     

Synthesis and structural characterization of [Co(tren)(Tsal)]ClO4·H2O and [Ni(pn)(py)2(NCS)2]

Complexes [Co(tren)(Tsal)]ClO₄·H₂O 1 and [Ni(pn)(py)₂(NCS)₂] 2, (tren = tris(2-aminoethyl)amine, Tsal = thiosalicylate ion, pn = 1, 2-diamino propane and py = pyridine) have been synthesized and structurally characterized. Both complexes crystallize in the monoclinic space group C2/c with a = 21.3340(6), b = 11.7754(2), c = 14.8076(5) Å, = 100.3831(10)°, Z = 8 (1), and a = 7.2573(8), b = 17.8810(11), c = 15.2681(12) Å, = 101.170(2)°, Z = 4 (2). The metal atoms in both cases have distorted octahedral geometry. In 1, the tren ligand is quadridentate and Tsal is bidentate chelate. In 2, the pn ligand forms a bidentate chelate with the NCS ligands in trans positions. Complex 1 is diamagnetic whereas 2 shows paramagnetism with a magnetic moment of 3.10 B. M.     

Synthesis, crystal structure, and thermal analyses of triaqua-(1,10-phenanthroline-N,N′) succinatomanganese(II) dihydrate, [Mn(H2O)3(phen)(C4H4O4)]·2H2O

[Mn(H₂O)₃(phen)(C₄H₄O₄)]·2H₂O was obtained by reaction of freshly prepared MnCO₃, phen and succinic acid in CH₃OH/H₂O (1:1 v/v), and its crystal structure has been determined by single crystal X-ray diffraction methods. The title mixed ligand complex crystallizes in the triclinic space group with cell dimensions a = 7.590(1) Å, b = 9.324(1) Å, c = 13.917(1) Å, = 85.64(1)°, = 74.56(1)°, = 77.10(1)°, and D _calc = 1.584 g/cm³ for Z = 2. The crystal structure consists of the [Mn(H₂O)₃(phen)(C₄H₄O₄)] complex molecules and lattice H₂O molecules. The Mn atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three H₂O molecules and one succinato ligand with d(Mn—N) = 2.271 and 2.299 Å, and d(Mn—O) = 2.133–2.239 Å. Through intermolecular hydrogen bondings, the complex molecules are interlinked to form 2D layers, which are assembled by – stacking interactions into 3D framework with tunnels occupied by the lattice H₂O molecules. Thermal analyses showed that the title compound decomposes in two steps over the range 25–600°C upon heating in flowing Ar.     

Synthesis,crystal structure and spectral studies of the complex [Ni(C3H4N2)4(H2O)2]·(C6H4COSO2N)2

The title compound has been synthesized and its crystal structure determined at room temperature.M _r =731.39, triclinic, space groupP¯1,a=9.020(3),b=11.280(7),c=7.784(2)Å,=97.05(4),=97.08(2), =105.32(4)°, U=748(1)ų,Z=1,D _calc.=1.624 g/cm³. The finalR is 0.030 for 3095 independent observed reflections withI3(I). The crystal structure consists of repeated [Ni(im)₄(H₂O)₂]²⁺ cations and noncoordinated saccharin anions. In the complex cation [Ni(im)₄(H₂O)₂]²⁺, Ni² is bonded to four N atoms from four imidazole molecules and two O atoms from two water molecules forming an approximately square octahedral stereochemistry. The d-d transition spectrum of the title compound is also reported and is explained perfectly with the scaling radial theory which was proposed by us.     

Crystal and molecular structure of complex compound [Fe3O(CH3COO)6(H2O)3]2[ZnCl4] ⋅ 2H2O

The X-ray crystal structure of trinuclear iron acetate [Fe₃O(CH₃COO)₆(H₂O)₃]₂ [ZnCl₄] ? 2H₂O was determined. The crystal has a ionic structure. It is monoclinic, a = 25.363(7), b = 14.533(4), c = 15.692(4) Å, β = 103.11(2)°, space group _C2/c, and R = 0.0685. The structure of the cationic complex [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ is typical of trinuclear iron(III) compounds containing a μ₃-O bridge: the iron atoms are situated at the vertices of an almost equilateral triangle with the O atom at the center. Each Fe atom is coordinated by four O atoms of bridging carboxy groups, the μ₃-bridging O atom, and the water molecule in the trans position to the latter O atom. Mössbauer spectroscopy evidence indicates the high-spin state (_S = 5/2) of the iron(III) ions.     

Structural and spectroscopic characterization of the macrocyclic complex: [Tb(CrO4)(H2O)(C22H26N6)] ·0.5(Cr2O7)·(H2O)

The title complex was obtained by anion metathesis from [Tb(CH₃COO)₂(C₂₂H₂₆N₆)] (CH₃COO)·4H₂O and K₂CrO₄ in aqueous solution. The compound crystallizes in the triclinic space group witha=8.384(2),b=10.425(2)c=15.752(2)Å, =98.82(2), =93.52(2), =97.22(2)°, andZ=2. The structure is ionic and consists of a (+1) complex cation balanced in a 21 ratio by a disordered dichromate ion. The 9-coordinate Tb(III) is linked to the six nitrogen atoms of the macrocyclic ligand L=C₂₂H₂₆N₆, as well as to a water molecule and a bidentate chelating chromate situated on opposite sides of the macrocycle. The infrared spectrum shows, in addition to the pattern of the macrocyclic ligand, the absorptions arising from the stretching modes of the bidentate chelating CrO₄ ^2– ligand and of the Cr₂O₇ ^2– counterion.     

Synthesis and crystal structure of Nd(III)–Zn(II) complex

A novel heteronuclear complex, [NdZn₂L₆(NO ₃)(phen)₂] (HL = -methylacrylic acid, phen = 1,10-phenanthroline), was synthesized and characterized by elemental analysis, infrared absorption spectra (IR) and its molecular structure was also determined by X-ray structure analysis. The title complex contains a discrete trinuclear ZnNdZn molecule bridged by carboxylate groups between Zn and Nd ions and crystallizes in space group P¯1 with the cell dimensions: a = 13.601(3) Å, b = 16.859(2) Å, c = 12.575(2) Å, = 110.09(1), = 112.21(1), = 81.10(2).     

Synthesis and X-ray crystal structure of an organometallic phosphonate [η6-1,2-C6H4(OCH3)(P(O)(OCH2CH3)2)]Cr(CO)3

The chiral, racemic, arene phosphonate complex, [t⁶-1,2-C₆H₄(OCH₃t)(P(O)(OCH²CH₃t)²)t] Cr(CO)₃ (1), was prepared via the reaction of 1,2-C₆H₄(OCH₃)(P(O)(OCH²CH₃)²) with Cr(CO)₆ in refluxing dioxane/THF. The title complex crystallized in P1 with the cell dimensions: a = 8.4893(4) Å, b = 11.0638(9) Å, c = 11.2135(8) Å, and = 62.151(8), = 105.154(5), = 112.426(6), giving a volume of 856.34(10) ų. The conformation of 1 is described as eclipsed (E) in which the methoxy substituent eclipses a carbonyl ligand of the tripod, and the phosphonate substituent is staggered.     

Crystal and molecular structure of di-μ-chlorobis[N-(2-hydroxyethyl)salicylideneiminato-N,O,O′ copper(II)] methanol solvate

The structure of the title compound, [Cu₂Cl₂(C₉H₁₀NO₂)₂]·CH₃OH, has been determined from single crystal X-ray diffraction data. The dinuclear units crystallize in the orthorhombic space group P2₁2₁2₁ with 4 formula units in a cell of dimensions:a=9.707(1),b=11.785(2),c=19.843(3)Å. The notable feature of the molecular structure is that it is dimeric with distorted square-pyramidal geometry at each, copper center. The two bridges are formed by C11 and C12 atoms where C11 is equatorial to Cu1 and apical to Cu2 and vice versa for atom C12. The apical Cu1–C12 and Cu2–C11 distances are 2.778(2) and 2.700(2)Å, respectively. The Cu1–Cu2 separation is 3.417(1)Å in the dimers. The geometry of the ligands and hydrogen bonds are discussed.     

Synthesis and crystal structure of hexaaquamagnesium hydrogen phosphododecatungstate tetrahydrate [Mg(H2O)6][HPW12O40]·4H2O

Crystals suitable for X-ray structure analysis were obtained after the slow evaporation of the reaction mixture containing equimolar quantities of magnesium chloride and dodecatungstophosphoric acid aqueous solution insuring pH of the solution between 1.0 and 1.2. This simple synthetic route yielded stability of Keggin anion and high quality [Mg(H₂O)₆][HPW₁₂O₄₀]·4H₂O single crystals. The obtained compound belongs to the group of heteropoly compounds and its structure is composed of Keggin [PW₁₂O₄₀]^3– anions, [Mg(H₂O)₆]²⁺ cations and lattice water molecules. Zigzag arrangement of Keggin anions along c-axis creates irregular channels occupied by [Mg(H₂O)₆]²⁺ cations and lattice H₂O molecules. The calculation of the total potential solvent volume indicated the presence of 4.1 lattice H₂O lattice molecules per formula unit, which is in agreement with the here presented structural model. The position of one lattice water molecule is well defined, while each of three other molecules is statistically distributed over two locations. Hydrogen bonds involve all coordinated and lattice H₂O molecules, as well as some oxygen atoms from the Keggin anion. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Synthesis and crystal structure of a palladium dimer containing ferrocenyldiphenylphosphine, trans-[Pd(μ-Cl)(CH3)(PPh2Fc)]2

The chloro-bridged dimeric complex, trans-[Pd(-Cl)(CH₃)(PPh₂Fc)]₂, was prepared by reaction of [Pd(Cl)(CH₃)(COD)] (COD = cis,cis-1,5-cyclooctadiene) with 1 equivalent of PPh₂Fc (PPh₂Fc = ferrocenyldiphenylphosphine) in acetone medium. The complex was characterized by ¹H and ³¹P NMR spectroscopy and a single crystal X-ray diffraction study revealed a trans geometry. The compound crystallizes in the triclinic space group P1, a = 11.476(2) Å, b = 14.059(3) Å, c = 14.658(3) Å and = 82.34(3)°, = 75.09(3)°, and = 68.48(3)° with Z = 2. Most important geometrical parameters include bond lengths Pd(1)–P(1) 2.2165(10), Pd(2)–P(2) 2.2290(10), Pd(1)–C(1) 2.157(3), Pd(2)–C(2) 2.079(4), Pd(1)–Cl(1) 2.4329(13), Pd(1)–Cl(2) 2.4106(11), Pd(2)–Cl(1) 2.4169(10), and Pd(2)–Cl(2) 2.4414(13) Å and bond angles P(1)–Pd(1)–C(1) 87.47(8), P(1)–Pd(1)–Cl(2) 176.88(4), C(1)–Pd(1)–Cl(1) 173.93(7), P(2)–Pd(2)–C(2) 89.03(11), P(2)–Pd(2)–Cl(1) 174.18(4), and C(2)–Pd(2)–Cl(2) 173.50(11)°. The effective and Tolman cone angles for P(1) were calculated as 170 and 167° and that for P(2) as 179 and 177°, respectively.     

Synthesis, properties, and crystal structure of barium 1-oxyethylidenediphosphonatohydroxogermanate(IV) polyhydrate Ba3[Ge(μ-OH)(μ-Oedph)]6 · 25H2O

The barium salt of 1-oxyethylidenediphosphonatohydroxogermanium acid Ba₃[Ge(μ-OH)(μ-Oedph)]₆ · 25H₂O (I) (H₄Oedph is 1-oxyethylidenediphosphonic acid) was synthesized and studied by X-ray diffraction. The complex was characterized by elemental analysis, thermogravimetry, and IR spectroscopy. The hexanuclear cyclic complex anions [Ge(μ-OH)(μ-Oedph)] ₆ ^6-t- ] cations, and water molecules of crystallization are the structural units of the crystal of I.